Gun Control Essays (2266 words) - Gun Politics In The United States

Firearm Control Firearm Control Gun control and guideline is turning out to be increasingly more famous all through the U.S., in spite of the fact that it might in any case raise opposition among certain individuals. Weapons are kind of an establishment of American culture. This countrys opportunity was prevailed upon ridiculous and brave wars with weapons. Weapons are depicted all through TV, motion pictures, and computer games. Weapons are a mainstream image of intensity, control, authority, predominance, and can be related with security and guard. The job firearms play in our general public is an exceptionally questionable discussion. I will bolster the firearm control and administrative side of this theme as a transient practical objective. There are both ardent supporters of the second change ensuring American residents the option to remain battle ready, and there are individuals who emphatically can't help contradicting the across the board use and accessibility of weapons to youth and hoodlums. Those for ope n weapon use are frequently inspired by the second Amendment, and the privilege many case to chase, ensure the home, or for resistance against expected volunteer armies or government oust. The thought process behind advocates of firearm control then again, is to confine availability to weapons to forestall savagery and passing in our general public. My position at last, with significance to our introductions in class, is neither an endeavor to convince or persuade anybody to utilize firearms nor to control and limit them. From here in any case, let me disclose to you that firearms assume a job of non-significance in my life, and in this manner I have searched out a thinking that has driven me to support a world without any weapons inside and out. This may sound rather hopeful or radical, however it is vital. Our reality needs a significant, aggregate transformation where brutality and weapons are concerned especially in the United States. This is my drawn out objective of possibilit y. Initially, the degree of weapon savagery is gigantic, fundamentally in the U.S. among all other modern countries. Close to vehicle casualty, weapon viciousness is the subsequent driving reason for death by injury in the U.S. It should turn out to be first constantly 2003 except if something is done to forestall it. In the mid nineties for instance, four states Nevada, Virginia, Louisiana, and Texas had patterns of firearm injury as the top reason for death. This sort of savagery it appears is nearly as pestilence as AIDS is in causing passing. That is an alarming interesting point. (gunfree.org) The National Center for Health Statistics reports that guns have ended the lives of 35,957 individuals in the U.S. in 1995. There is a 21.5% gun casualty increment since 1985. What's more, of these fatalities, suicides rank first at 18,503 individuals; murders second at 15,835 individuals; inadvertent shootings next at 1,225 individuals; and 394 were unsure. (gunfree.org) Now I might want to demystify a few contentions utilized against firearm control. The first accept that weapon control wont stop firearm savagery or wrongdoing. Most crooks get firearms through lawful methods in spite of what the weapon campaign says to legitimize having a gigantic accessibility of firearms. This is demonstrated by the Criminal Justice Research Center. They obviously overviewed that lone 27% of grown-up prisoners and 43% of adolescents have purchased handguns unlawfully on the bootleg market. Then again, of these prisoners, 69% of grown-ups and 55% of adolescents acquired firearms through methods like retail, weapon shops, private proprietors, companions or family. This affirms most firearms are gotten legitimately through controlled techniques. (gunfree.org) Also, the FBI has gotten reports of a middle number of around 274,000 weapons taken yearly from 85 to 94. This calls attention to that the firearms sold by proprietors and vendors are a hazard to us and can be directed to brin g down wrongdoing, murder, self destruction, and different fatalities. (gunfree.org) Is claiming a firearm actually a protected right? The second correction of the constitution says: An all around controlled Militia being important to the security of a free State, the privilege of the individuals to keep and remain battle ready, will not be encroached. The Supreme Court clarified in its 1939 case choice of U.S. versus Mill operator, that the second Amendment doesnt ensure ownership of a gun except if there exists some sort of sensible relationship in protecting

The Drinking Age

The base lawful drinking age is 21 years. Every year a huge number of understudies move on from secondary school and in festivity, they hold local gatherings which incorporate liquor utilization. The vast majority of these secondary school leavers are younger than 21. During this period, there are constantly various discussions coming up about whether to bring down the legitimate drinking age or not, be that as it may while this is going on, young people under 21 become gorge consumers (Seaman, 2006).Advertising We will compose a custom paper test on The Drinking Age explicitly for you for just $16.05 $11/page Learn More As the greater part of them are under the liquor purchasing age, they utilize illicit methods like faking distinguishing proof to be permitted to purchase mixed beverages. The legislature is burning through a huge number of dollars in a battle to keep up to keep up the MLDA of 21. The administration considers multi year old adolescents as youthful and that they can't settle on the correct choices. Legitimate age of 18 How can the administration consider multi year olds not develop to settle on choices but then at this age they are viewed as grown-ups? The very meaning of a grown-up is that one has achieved an experienced age, which is 18. The catchphrase here is full grown, along these lines to conflict with this and state multi year olds are not developed to settle on educated decisions on liquor utilization, is conflicting with the law. The legitimate age makes an individual free, the young people who have accomplished this age are permitted to move out of their parents’ houses, land positions and even get hitched and have their own youngsters. Diminishing liquor utilization at this age conflicts with the central privileges of the youthful grown-ups. Military drafting and casting a ballot It is unexpected to such an extent that the administration considers multi year olds grown-ups, when the circumstances chip away at their kindness, b ut contradict a similar youthful grown-ups with regards to liquor. This is a twofold standard utilized by government. In the event that these youthful grown-ups are not permitted to devour liquor by ideals of their age, at that point they ought to likewise not be permitted to be drafted in to the military. In any case, multi year olds are viewed as grown-ups who can cast a ballot, join the military, hold open workplaces, be attempted as grown-ups; they can hold employments and are relied upon to settle charges. In this sense they are much the same as some other grown-ups in the general public. In the event that they are sufficiently developed to settle on the choices to join the military and do battle and even bite the dust for their nation, at that point they ought to likewise be permitted to devour liquor. When government officials need to get to office or look for re-appointment, they don't victimize who votes in favor of, all votes are the equivalent to them.Advertising Looking for exposition on training? How about we check whether we can support you! Get your first paper with 15% OFF Learn More An enormous number of the voters passing by the ongoing democratic pattern appear to be the youthful grown-ups who have recently achieved the lawful age to cast a ballot. They are eager and prepared to practice their privileges. In the event that the lawmakers anticipate that them should settle on the correct decisions with regards to casting a ballot, at that point they are grown-up enough to take liquor (Wechsler, 2002). End There is no avocation in contending that the multi year olds are less open minded than multi year olds. At times, the circumstances are converse. Not each of the multi year olds are juvenile; the greater part of them have created mental and logical character. Denying them from lawfully purchasing and expending liquor will just advance insubordination and violations identified with liquor, such as driving affected by liquor. References Seaman, B. (2006). Gorge: What your understudy won’t let you know. New Jersey: John Wiley Sons ltd. Wechsler, H. (2002). Kicking the bucket to drink: Confronting hard-core boozing in school grounds. New York: St. Martin’s Press. This exposition on The Drinking Age was composed and presented by client Carson H. to help you with your own investigations. You are allowed to utilize it for research and reference purposes so as to compose your own paper; be that as it may, you should refer to it likewise. You can give your paper here.

How GAD Might Influence Your Health Anxiety

How GAD Might Influence Your Health Anxiety GAD Symptoms Print How GAD Might Influence Your Health Anxiety By Arlin Cuncic Arlin Cuncic, MA, is the author of Therapy in Focus: What to Expect from CBT for Social Anxiety Disorder and 7 Weeks to Reduce Anxiety. Learn about our editorial policy Arlin Cuncic Medically reviewed by Medically reviewed by Steven Gans, MD on January 04, 2018 Steven Gans, MD is board-certified in psychiatry and is an active supervisor, teacher, and mentor at Massachusetts General Hospital. Learn about our Medical Review Board Steven Gans, MD Updated on June 21, 2019 Generalized Anxiety Disorder Overview Symptoms & Diagnosis Causes Treatment Living With In Children Tom Merton / Getty Images Health anxiety refers to fear related to developing a dangerous health problem or already having one. In those with generalized anxiety disorder (GAD), this fear can be persistent and hard to let go, even after medical tests show nothing is wrong and the doctor has reassured you that your health is fine. Health anxiety is also known by other names such as hypochondriasis, somatization disorder, or illness anxiety disorder. All these illnesses are related in that there is a fear of something being terribly wrong with your body. Connection to GAD If you have GAD and worry about your health, you might find yourself up at night, researching on the Internet. You might recognize symptoms that you have and think that you have a terrible disease like cancer or other health issues like heart disease. Things like headaches and other symptoms that can occur due to anxiety might be misinterpreted as something else. You might feel like the doctors are missing something, and so you keep asking for more tests and seeking more reassurance. Why Health Anxiety Is a Problem While being on top of your health is important, its also important to do so in a reasonable manner. Health anxiety crosses that boundary because no amount of testing, checking, or reassuring will ever make you feel as though things will be okay. In essence, until you actually contract some terrible disease, your mind will never be at rest. Thats no way to live. You might find yourself focused too much on your body,  such as your rate of breathing or your heartbeat. You might notice changes in your skin and think the worst. Headaches or stomachaches might cause you to seek reassurance that they are not a sign of something lurking. If you hear about a disease on the news, you might worry you will be the next to get it. Symptoms that tend to cause the most fear include changes in vision, heart rate, blood pressure, breathing, and balance. What Your Doctor Doesnt Know About Health Anxiety Additionally, if you continue to visit your doctor with no end in sight and your doctor is not knowledgeable about health anxiety, you may never receive the mental health treatment that you need. Well-meaning doctors may do things that actually make your health anxiety worse, such as telling you to stop reading up on side effects or to stay off the internet. They may also agree to do special tests. These actions make your health anxiety worse for two reasons: When you stop learning about the illnesses that you fear, they grow bigger and more dangerous in your mind. Lack of information can contribute to fear.When your doctor does test after test to assuage your fears, he only proves to you that there is something wrong that needs continued testing to identify. In essence, when you have health anxiety, your mind keeps sounding an alarm about your body that you cant seem to turn off. Your doctor needs to be aware of this issue and treat it carefully. Here are some tips for managing health anxiety with the help of medical professionals: Rule out Physical Problems First, do your best, with the help of your doctor, to rule out physical problems. It might be helpful to gather health information from your relatives as well so that you can assess your risk of different illnesses. With that information, your doctor will be able to recommend what to watch for and what tests might be appropriate. For example, excessive thirst and changes in vision are signs of diabetes. If you have these symptoms and family history, it is reasonable to test for this disease. See a Therapist Once all medical testing is complete, and with a plan for any ongoing check-ups, let it go. Uncertainty is what causes your fear. Be certain that at this moment, it is reasonable to assume that you have no dreaded disease. Now, if your health anxiety persists, ask your doctor about seeing a therapist. While it may be tempting to call your doctor for reassurance each time your anxiety flares, seeing a therapist will have better long-term results. Generalized Anxiety Disorder Discussion Guide Get our printable guide to help you ask the right questions at your next doctors appointment. Download PDF Receive Treatment Ideally, your therapist will provide treatment such as cognitive-behavioral therapy (CBT). Through this therapy, you will learn how thoughts affect how you feel and behave. You will learn that it is not your physical symptoms, but how you interpret them, that creates your anxiety. And you will learn how to correct those irrational thoughts. Get Help From the 7 Best Online Anxiety Support Groups Research In a random telephone survey of 5118 Chinese respondents aged 18 to 64, it was found that people with both GAD and health anxiety tended to be older, less educated, and had lower family income. People with health anxiety were also shown to have more mistrust of doctors. This shows that educating yourself may be important in fighting against health anxiety, but also that lack of trust of doctors may fuel some of your worries. Relationship With Your Doctor While  doctors need to be aware of those with health anxiety, it is also important that your doctor is not dismissive of your concerns. You shouldnt be given labels as a bad patient. As much as it may be frustrating for your doctor to sympathize with your constant worries, a good doctor will be firm but also understanding. A good doctor will also exhibit the following qualities: Encourages you to ask questions and research, but also shares with you when your research is wrong or when your fears are unreasonableTells you to become familiar with how you react to stress and to learn the symptoms of anxiety so that you can distinguish these from symptoms of physical illness. As there is overlap, they can be hard to tell apart sometimes.Might say to you, So if you did have [terrible disease], what would that mean? Its important to talk about your fears and get them out in the open so that they dont grow and fester.Encourages  you to stop checking on your health so often and stop seeking reassurance beyond a reasonable pointShares with you the odds of you actually getting various diseases, so you can see that they are very lowEncourages you to pursue healthy lifestyle habits such as eating well and exercisingTells you that complete certainty and safety are never guaranteed, but that life must go on A Word From Verywell Health anxiety overlapping with generalized anxiety disorder can be a source of great distress. Your best options for managing this type of anxiety are to rule out physical concerns in a reasonable way, seek mental health treatment if appropriate, and find a doctor who is sympathetic to your unique set of issues.

The Problem of Racial Discrimination - Free Essay Example

Sample details Pages: 3 Words: 795 Downloads: 2 Date added: 2019/02/05 Category Society Essay Level High school Tags: Racial Discrimination Essay Racism Essay Did you like this example? Racism has been a constant issue today as it was many years ago. Throughout history many groups have been labeled and criticized not only for the race, but for their sex and class as well. People of lower class being criticized for not having economical means to afford common goods. Blacks being put down for their color. The federal government should be the one to initiate a national movement against racism. Although, this cannot be done alone, those in authority and society also play a huge role in this movement. Judgement about other individuals should be considered before expressing yourself outloud. Sometimes with a simple decision your are making you can be committing unconscious bias. According to the article Unconscious Bias, When good intentions aren’t good enough, by Sarah E,. Fiarman, â€Å"a growing body of research shows that we all harbor unconscious bias.† Bringing forward this sort of unconscious bias begins to promote an unpleasant environment for those being targeted. For instance, teachers carry a role with greater responsibilities of not expressing or showing such bias towards anyone based of their skin color, ethnicity, language, and other traits. Still teachers have demonstrated quite the opposite. (indirect quote) â€Å"Educators, he told me, frequently notice misbehavior among black students while ignoring the same behavior among white students.† qtd Unconscious bias article. If students of color are experiencing these prejudiced acts at an early age how can we expect them to develop a positive attitude towards people in authority later in life. When all they have received is racial discrimination. Don’t waste time! Our writers will create an original "The Problem of Racial Discrimination" essay for you Create order The only way we can begin by preventing such issues is starting a national movement that will help bring racism to an end. This national movement can implement a measure to bring awareness of unconscious bias in school and steps to eliminate barriers ensuring groups and individuals being targeted are being more effectively addressed. Now, this can obviously not only be done through the federal government. Solve this unconscious bias by beginning with the staff then spreading the knowledge through schools and into public mindset. Predominantly the lack of implementing this idea can very well be the downfall of this movement. Although, many might think they’re completely unbiased, it is important to recognize and prevent any act of implicit bias. Imagine being told to go back to your country because you speak spanish. Even worse, being pushed aside by your own friends at such a young age because of your skin color. Well this is happening everyday all around the world. As Gayle Kirshenbaum explains, â€Å"This was not the first time she’d seen her child, the only child of color in a playground, excluded in this way an exclusion that was not noticed or challenged by the attendant white parents.† They say we must lead by example, so how can we expect to bring racism to an end when there isn’t anything being done when moments like these are being encountered.quote: , â€Å"Nearly 800,000 students are enrolled in schools where more than 20 percent of teachers have not met certification or license requirements. Black, Latino and American Indian or Alaska Native students are more likely to attend these schools.† A persons skin tone or race shouldn’t define where they will be put, everyone should b e treated equally. How do you get your child to understand it is not okay to be racist when all they have encountered has been discrimination. A national movement can implement measures to ensure that individuals and groups facing racial discrimination have access to any place or service intended for public use, such as schools, educations, and parks. Initiate by defining the current situation and articulating a comprehensive program of activities aimed at bringing improvement. This ensures concerns of individuals facing racial discrimination that measures are being taken. Not only that but eventually it will promote mutual understanding among different groups. As much as the national movement to end racism is promoted it won’t come forward due to the lack of implementing and monitoring activities. Like a business you have to continue forward looking for new ways to progress otherwise it will only go downfall. Racial discrimination should be addressed through the federal government so they see the importance of this issue. Although no federal government can realistically expect to eliminate racism from one day to another, therefore a national movement should be continues with the support of society. A long term process that includes planning, monitoring, setting goals for what has to be overcomed and areas that need to be worked on. These programs and activities will assist in assuring these goals are being accomplished. The knowledge can be passed on for decades so racism doesn’t continue to be the same issue it has been for years.

Questions On Organizational Learning And Change - 2316 Words

Leading Change in One Organization Nichelle Daniels-Wilson Indiana Wesleyan University October 11, 2014 MOL-530: Organizational Learning and Change Professor: Christopher Brumm Indiana Wesleyan University (IWU) Statement of Academic Honesty: I have read and understand the plagiarism policy as outlined in the syllabus and the sections in the Student Bulletin relating to the IWU Honesty/Cheating Policy. By affixing this statement to the title page of my paper, I certify that I have not cheated or plagiarized in the process of completing this assignment. If it is found that cheating and/or plagiarism did take place in the writing of this paper, I understand the possible consequences of the act/s, which could include expulsion†¦show more content†¦An effective leader innately has or acquires a need for desire and willpower to create a learning organization. Good leaders develop through a never ending process of self-study, education, training, and experience (Jago, 1982). Definition of Organizational Change For the purpose of this paper organizational change is defined as a company or organization going through a transformation. Organization change occurs when business strategies or major sections of an organization are altered and or involves reorganization, restructuring and turnaround (Business Dictionary). Organizational change is about reviewing and transforming management structures and business processes. To stay ahead of our competition the Charter School System it is imperative that our organization look for ways to do things more efficiently and economically. There is no reason that we should fear change. We should embrace change as a means of setting the foundation for continuing success (Basu, C., 2014). Organizational change consists of three stages: establishing the need, implementation, and monitoring. To establish a need for change our senior manager (Superintendent) has expressed where she wants our school corporation to be in five to 10 years and what it needs to do to get there which involves changing structures and processes, such as reducing the number of management layers, reassigning personnel, reducing employee headcount, monitoring the resultsShow MoreRelatedAspects Of Organizational Communications : Freddie Macs Has Multiple Communications Systems1067 Words   |  5 PagesAspect II-Organizational Communications Freddie Mac’s has multiple communications systems. There is communicating person to person among staff members. There are regional office centers located in five regional area of the United States. These offices were strategically planned to provide local coverage within the market. This assisted with gaining access in these local and distant markets as to how trend tend to fair in the office location also giving Freddie Mac visibility within different regionsRead MoreOrganizational Behavior1284 Words   |  6 PagesBachelor of Business Administration (Hons) Course Title : Organizational Behavior Course Code : BUS 250 Year of Study : 2 Number of Credits : 3 credits Duration in Weeks : 12 weeks Contact Hours Per Week : 3 hours Pre-requisite Course(s) : BUS 120 Principles and Practice of Management Course Aims The course provides students with a conceptual and a pragmatic approach to understand the employees’ behavior in the organization. This course equips students with the knowledgeRead MoreThe Theory Of Organizational Learning And Performance Management Essay1156 Words   |  5 Pagesclimate and the notion of a global market, corporations all over the world grapple with the idea of management learning as it relates to performance management in an effort to remain competitive. Hall and Rowland’s article explores these ideas in great detail that are rooted in a fifteen-year research project. I will analyze their research problem, purpose of the study, research question, method of research, significance of the study and its global implications, research findings and finally the relevancyRead MoreExecutive Action Learning ( Eal )811 Words   |  4 PagesExecutive Action Learning (EAL) There is a distinction between knowledge and wisdom. Business knowledge comes from memorizing business principles and facts; executive wisdom comes from insights and experiential learning. In action learning, this can be achieved via skillful questioning. Traditional academic and MBA education focuses on the knowledge, while executive action learning focuses on experiential problem-solving (wisdom). In other words Executive Action Learning (EAL) builds wiser managementRead MoreSustainability in Organizations1271 Words   |  6 Pagesliterature review on the topic of change and sustainability in organizations relating to technology, innovation, leadership and human sustainability. The basis of my review is through the use of various journal articles. INTRODUCTION Change is one of the aspects that organizations are faced with almost on a daily basis. Organizations are forced to adapt to it for them to be successful in the industry this is because there are constant changes in the environment. Changes that organizations and companiesRead MoreQuestion case study Essay681 Words   |  3 Pagesï » ¿ List questions Case Studies Bella Healthcare India 2012, HBS #4441 STRAT MAGT – Internationalization; product development; â€Å"local for local† strategy UD: 12/12/2012 Overview and Objectives: The case traces the path taken by an overseas operation from low cost manufacturing to higher value-added activities such as RD. It asks students to consider the factors driving the evolution and this timing and circumstances that would make it successful. It creates the opportunity toRead MoreLeadership Practices Necessary For Organizational Change1567 Words   |  7 PagesEssential Leadership Practices Necessary for Organizational Change I have worked with and known leaders. Leaders who impacted change, leaders who hindered change, and leaders who have simply maintained. Having formed opinions on certain practices that can contribute to enhancing effective leadership, I had never deeply assessed or identified the practices that can promote, guide, and enhance organizational change and improvement. When I read, Implementing Change Patterns, Principles, and Potholes, byRead MoreOrganizational Learning Is Not Built On Firm Foundations1412 Words   |  6 PagesAbstract As organizational learning takes a clear presence in today’s workplaces; I am analyzing various case studies to better understand the intentions and impact of such organizational changes. Who benefits from organizational learning? What impact does it have on the economy? Studies suggest the outcome of organizational learning is not guaranteed to result in a win-win situation for all parties and the outcomes differ from one organization to the next. Furthermore education is still designedRead MoreMba 520 Syllabus1576 Words   |  7 PagesMBA/520 Transformational Leadership Course Syllabus University of Phoenix MBA520 ________________________________________ Please print a copy of this syllabus for handy reference. Whenever there is a question about what assignments are due, please remember this syllabus is considered to be the ruling document. GENERAL COURSE INFORMATION COURSE NUMBER: MBA/520 COURSE TITLE: Transformational Leadership COURSE START DATE: 1 March 2007 COURSE END DATE: 5 April 2007 COURSE LOCATION:Read MoreManagement And Processes Performance Metrics Essay1559 Words   |  7 PagesFreddie Mac to adapt to theirs. Freddie Mac’s federal regulations are provided by the federal registry who also guides their policies, procedures, and best practices which are needed for the successful operation of a GSC (Ellie Mae, 2016). Aspect II-Organizational Communications Freddie Mac functions under multiple communication systems. In addition to person to person communication among local staff members, regional office centers, which have been strategically placed within five United States regions

Is Your Sore Throat Strep Free Essays

Is Your Sore Throat Strep? By Kristin Hayes, About. com Guide Updated October 06, 2009 About. com Health’s Disease and Condition content is reviewed by the Medical Review Board Question: Is Your Sore Throat Strep? It can be difficult to tell if your sore throat is strep or simply a cold virus. We will write a custom essay sample on Is Your Sore Throat Strep? or any similar topic only for you Order Now However, in most cases of strep throat there are some key differences. Answer: The only way to know for sure if your sore throat is strep is to have a rapid strep test or a throat culture. These tests must be performed at a physician’s office, but let’s face it you can’t go running in to the doctor every time your throat gets a little scratchy. Characteristics of strep throat include a severe sore throat that may cause pain or difficulty swallowing. The back of the throat is usually very red and there may be white patches in the back of the throat or on the tonsils. The tonsils and lymph nodes also may be swollen. Some people get a fever. It is not uncommon to be very tired and achy or to lose your appetite. In some cases you may get a rash. The biggest difference between strep throat and a cold virus is that strep throat usually does not cause runny nose, congestion, sneezing or coughing. All cases of strep throat must be treated with an antibiotic to avoid serious complications including heart problems, kidney problems or Scarlett fever — especially in children. For these reasons, it is very important to see the doctor if you or your child have symptoms of strep throat. How to cite Is Your Sore Throat Strep?, Papers

Tell

Tell-Tale Heart (688 words) Essay Tell-Tale HeartTell-Tale Heart?TRUE!nervous ? very, very dreadfully nervous I had been and am; but why will you say that I am mad Edgar Allen Poe shows us the dark part of human kind. Conflict with in ones self, state of madness, and emotional break down all occur within this short story. The narrator of the story is a mad man that is haunted by his idea that the old man has an evil eye. There are two conflicts that occur with the story: internal and external. The internal conflict is the narrators guilt over killing the old man forces him to believe that he hears the dead mans heart beating. ?I talked more quickly?more vehemently; but the noise steadily increased.?. Ones owns conscience can only take so much before the person breaks down. ?Oh God! What could I do? I foamed?I raved?I swore! I swung the chair upon which I had been sitting, and grated it upon the boards, but the noise arose over all and continually increased.? The external conflict is the eye itself; the narrator feels that the old mans eye is always watching him in turn makes him think he can read his mind. ?It was open?wide, wide open?and I grew furious as I gazed upon it. I saw it with perfect distinctness?all a dull blue, with a hideous veil over it that chilled the very marrow in my bones.? A madman can only take so much when he fixated on an eye. We will write a custom essay on Tell-Tale Heart (688 words) specifically for you for only $16.38 $13.9/page Order now State of madness is very implicit in this case. The fact that the narrator was way too overly patient and dedicated to stalking the old man night after night, at midnight, seven days before he decides to commit his evil deed. Was obviously the act of a keen madman. ?Oh, you would have laughed to see how cunningly I thrust in! I moved it slowly?very, very slowly, so that I might not disturb the old mans sleep. It took me an hour to place my whole head within the opening so far that I could see him as he lay upon his bed.? The narrator keeps implying that he is very, very dreadfully nervous. ?I knew that sound well, too. It was the beating of the old mans heart. It increased my fury, as the beating of a drum stimulates the soldier into courage.? This also gives us the reader the hint of him being mad. When ones actions that are thought out with knowing the harsh consequences are a key sign to madness. Basically what I think Edgar Allen Poe is trying to imply to us is that everyone holds a little madness within and subconsciously. We must fight the urge and accept it fully, to be excepted and considered normal. Because everyones got to do it. The emotional feeling of the narrator are those of the depressed. He is neither shy or outgoing. He thinks he is skillful and not mad. ?If you still think me mad, you will think so no longer when I describe the wise precautions I took for the concealment of the body.? He states this because he is trying to persuade the reader into thinking hes smart therefore making the reader come up with the idea how could you be mad if your smart. He does not seem to be caring, yet he does state he loved the old man. ?Object there was none. Passion there was none. I loved the old man.? He is dishonest though for he wasnt going to tell the police about the dead body until his subconscious thoughts made him believe that they too heard the horrifying heart beat of the old man. Which caused his emotional break down. .u4d8b07d483db29b57df1a5ee1a98da70 , .u4d8b07d483db29b57df1a5ee1a98da70 .postImageUrl , .u4d8b07d483db29b57df1a5ee1a98da70 .centered-text-area { min-height: 80px; position: relative; } .u4d8b07d483db29b57df1a5ee1a98da70 , .u4d8b07d483db29b57df1a5ee1a98da70:hover , .u4d8b07d483db29b57df1a5ee1a98da70:visited , .u4d8b07d483db29b57df1a5ee1a98da70:active { border:0!important; } .u4d8b07d483db29b57df1a5ee1a98da70 .clearfix:after { content: ""; display: table; clear: both; } .u4d8b07d483db29b57df1a5ee1a98da70 { display: block; transition: background-color 250ms; webkit-transition: background-color 250ms; width: 100%; opacity: 1; transition: opacity 250ms; webkit-transition: opacity 250ms; background-color: #95A5A6; } .u4d8b07d483db29b57df1a5ee1a98da70:active , .u4d8b07d483db29b57df1a5ee1a98da70:hover { opacity: 1; transition: opacity 250ms; webkit-transition: opacity 250ms; background-color: #2C3E50; } .u4d8b07d483db29b57df1a5ee1a98da70 .centered-text-area { width: 100%; position: relative ; } .u4d8b07d483db29b57df1a5ee1a98da70 .ctaText { border-bottom: 0 solid #fff; color: #2980B9; font-size: 16px; font-weight: bold; margin: 0; padding: 0; text-decoration: underline; } .u4d8b07d483db29b57df1a5ee1a98da70 .postTitle { color: #FFFFFF; font-size: 16px; font-weight: 600; margin: 0; padding: 0; width: 100%; } .u4d8b07d483db29b57df1a5ee1a98da70 .ctaButton { background-color: #7F8C8D!important; color: #2980B9; border: none; border-radius: 3px; box-shadow: none; font-size: 14px; font-weight: bold; line-height: 26px; moz-border-radius: 3px; text-align: center; text-decoration: none; text-shadow: none; width: 80px; min-height: 80px; background: url(https://artscolumbia.org/wp-content/plugins/intelly-related-posts/assets/images/simple-arrow.png)no-repeat; position: absolute; right: 0; top: 0; } .u4d8b07d483db29b57df1a5ee1a98da70:hover .ctaButton { background-color: #34495E!important; } .u4d8b07d483db29b57df1a5ee1a98da70 .centered-text { display: table; height: 80px; padding-left : 18px; top: 0; } .u4d8b07d483db29b57df1a5ee1a98da70 .u4d8b07d483db29b57df1a5ee1a98da70-content { display: table-cell; margin: 0; padding: 0; padding-right: 108px; position: relative; vertical-align: middle; width: 100%; } .u4d8b07d483db29b57df1a5ee1a98da70:after { content: ""; display: block; clear: both; } READ: LIBERAL MEDIA BIAS EssayOnes own subconscious mind could create emotions that can persuade one to do deeds in which he/she never thought of. Either it be good or bad like the narrators feelings towards the old mans eye. Emotions are those not to be put aside or forgotten about. But should be dealt with and conditioned to a norm. Mind over matter. Poetry Essays

Free Essays on Adolescent Depression

Adolescent Depression: The Under Acknowledged Disease Psychology Depression is a disease that afflicts the human psyche in such a way that the afflicted tends to act and react abnormally toward others and themselves. Therefore it comes to no surprise to discover that adolescent depression is strongly linked to teen suicide. Adolescent suicide is now responsible for more deaths in youths aged 15 to 19 than cardiovascular disease or cancer (Blackman, 1995). Despite this increased suicide rate, depression in this age group is greatly underdiagnosed and leads to serious difficulties in school, work and personal adjustment which may often continue into adulthood. How prevalent are mood disorders in children and when should an adolescent with changes in mood be considered clinically depressed? Brown (1996) has said the reason why depression is often over looked in children and adolescents is because "children are not always able to express how they feel." Sometimes the symptoms of mood disorders take on different forms in children than in adults. Adolescence is a time of emotional turmoil, mood swings, gloomy thoughts, and heightened sensitivity. It is a time of rebellion and experimentation. Blackman (1996) observed that the "challenge is to identify depressive symptomatology which may be superimposed on the backdrop of a more transient, but expected, developmental storm." Therefore, diagnosis should not lay only in the physician's hands but be associated with parents, teachers and anyone who interacts with the patient on a daily basis. Unlike adult depression, symptoms of youth depression are often masked. Instead of expressing sadness, teenagers may express boredom and irritability, or may choose to engage in risky behaviors (Oster & Montgomery, 1996). Mood disor ders are often accompanied by other psychological problems such as anxiety (Oster & Montgomery, 1996), eating disorders (Lasko et al., 1996), hyperactivity (Bl... Free Essays on Adolescent Depression Free Essays on Adolescent Depression Adolescent Depression The Under Acknowledged Disease Depression is a disease that afflicts the human psyche in such a way that the afflicted tends to act and react abnormally toward others and themselves. Therefore it comes to no surprise to discover that adolescent depression is strongly linked to teen suicide. Adolescent suicide is now responsible for more deaths in youth’s aged 15 to 19 than cardiovascular disease or cancer. Despite this increased suicide rate, depression in this age group is greatly under diagnosed and leads to serious difficulties in school, work and personal adjustment, which may often continue into adulthood. How prevalent are mood disorders in children and when should an adolescent with changes in mood be considered clinically depressed? Brown (1996) has said the reason why depression is often over looked in children and adolescents is because "children are not always able to express how they feel." Sometimes the symptoms of mood disorders take on different forms in childre n than in adults. Adolescence is a time of emotional turmoil, mood swings, gloomy thoughts, and heightened sensitivity. It is a time of rebellion and experimentation. Blackman (1996) observed that the "challenge is to identify depressive symptomatology which may be superimposed on the backdrop of a more transient, but expected, developmental storm." Therefore, diagnosis should not lie only in the physician's hands but be associated with parents, teachers and anyone who interacts with the patient on a daily basis. Unlike adult depression, symptoms of youth depression are often masked. Instead of expressing sadness, teenagers may express boredom and irritability, or may choose to engage in risky behaviors. Mood disorders are often accompanied by other psychological problems such as anxiety, eating disorders, hyperactivity, substance abuse and suicide, all of which can hide depressive symptoms. The signs of clinical depression include mark... Free Essays on Adolescent Depression Adolescent Depression: The Under Acknowledged Disease Psychology Depression is a disease that afflicts the human psyche in such a way that the afflicted tends to act and react abnormally toward others and themselves. Therefore it comes to no surprise to discover that adolescent depression is strongly linked to teen suicide. Adolescent suicide is now responsible for more deaths in youths aged 15 to 19 than cardiovascular disease or cancer (Blackman, 1995). Despite this increased suicide rate, depression in this age group is greatly underdiagnosed and leads to serious difficulties in school, work and personal adjustment which may often continue into adulthood. How prevalent are mood disorders in children and when should an adolescent with changes in mood be considered clinically depressed? Brown (1996) has said the reason why depression is often over looked in children and adolescents is because "children are not always able to express how they feel." Sometimes the symptoms of mood disorders take on different forms in children than in adults. Adolescence is a time of emotional turmoil, mood swings, gloomy thoughts, and heightened sensitivity. It is a time of rebellion and experimentation. Blackman (1996) observed that the "challenge is to identify depressive symptomatology which may be superimposed on the backdrop of a more transient, but expected, developmental storm." Therefore, diagnosis should not lay only in the physician's hands but be associated with parents, teachers and anyone who interacts with the patient on a daily basis. Unlike adult depression, symptoms of youth depression are often masked. Instead of expressing sadness, teenagers may express boredom and irritability, or may choose to engage in risky behaviors (Oster & Montgomery, 1996). Mood diso rders are often accompanied by other psychological problems such as anxiety (Oster & Montgomery, 1996), eating disorders (Lasko et al., 1996), hyperactivity (Bl...

Understanding Javas Cannot Find Symbol Error Message

Understanding Java's Cannot Find Symbol Error Message When a Java program is being compiled, the compiler creates a list of all the identifiers in use. If it cant find what an identifier refers to (e.g., there is no declaration statement for a variable) it cannot complete the compilation. This is what the cannot find symbol error message is saying- the compiler  doesnt have enough information to piece together what the Java code is intended to execute. Possible Causes For the  Cannot Find Symbol Error Although the Java source code contains other things like keywords, comments, and operators, the Cannot Find Symbol error references the name of a specific package, interface, class, method or variable. The compiler needs to know what every identifier references. If it doesnt, the code is basically looking for something that the compiler doesnt yet comprehend. Some possible causes for the Cannot Find Symbol Java error include: Trying to use a variable without declaring it.Misspelling a class or method name.  Remember that  Java is case sensitive  and spelling errors are not  corrected for you. Also, underscores may or may not be necessary, so watch out for code that use them when they shouldnt be used or vice versa.The parameters used do not match a methods signature.The packaged class has not been referenced correctly using an import declaration.Identifiers  look  the same but are actually different. This problem can be hard to spot, but in this case, if the source files use UTF-8 encoding, you may be using some identifiers as if theyre identical but really theyre not because they simply appear to be spelled the same.Youre looking at the wrong source code. It may seem hard to believe that youre reading a different source code than the one producing the error, but its definitely possible, and especially for new Java programmers. Check file names and version histories carefully.You forgot a new, like this:  String s String();, which should be  String s new String(); Sometimes, the error arises from a combination of problems. Therefore, if you fix one thing, and the error persists, check for different problems still affecting your code. For example, its possible that you are trying to use an undeclared variable and when you fix it, the code still contains spelling errors. Example of a Cannot Find Symbol Java Error Lets use this code as an example: This code will cause a cannot find symbol error because the System.out class does not have a method called â€Å"prontln†: The two lines below the message will explain exactly what part of the code is confusing the compiler. Mistakes like capitalization mismatches are often flagged in a dedicated integrated development environment. Although you can write your Java code in any text editor, using IDEs and their associated linting tools reduces typos and mismatches. Common Java IDEs include Eclipse and NetBeans.

Gender and the Media Essay Example | Topics and Well Written Essays - 1500 words

Gender and the Media - Essay Example This paper stresses that a good number of women lived in fear of their sexuality since this was one matter not examined for subtext and submerged meanings. For instance, majority of Inuit people of Canada live in isolated arctic communities that make it impossible for them to access consumer goods and medical services. Femininity made the women especially in the eighteenth century fall victims of housing crisis. In fact, the problematic housing condition leaves the then urban woman with quite insecure situations of living. To some readers more familiar with femininity politics and with issues of recognition, the politics may appear unusual or even odd. The author says that some independent films have empowered featured women as cultural product interpreters. Hook pioneered a research field in black women readers of culture that put together the cultural studies and the African American studies. This was possible through the techniques of interviewing and textual interpretation based on criticism. The research’s intentions were to join the two studies and eradicate criticism. This report makes a conclusion that nobody hates looking at women’s funny character in movies. Something that Caroline well put across. The conditions of watching Mr.mom a movie in the cinema gives authority to a voyeuristic spectatorship. All spectators are chirping characters taking pleasure and watching others while they remain unseen. In other fields, feminists have identified voyeurism as conflict that is because of gender. The chirping character is most often a man-watching female without her knowledge. As a result, for Stuart Hall insights, Hooks and other critics bring up many questions about the response of women regarding the visual arts in the modern world, which includes photography and film. The black looks say a lot about race and representation. Basing this on Hook’s argument, critical spectatorship of the black female only comes up when an individual woman resist becoming the subject of looking and knowing or in other words image and story. Their resista nce to identifying themselves with settings of gender and race tender for their consumption. Men critic their positive decisions and creates opposite texts and interpretations. This makes the black woman lack freedom to make decisions on her own since her wish means end of career. Hook says that any black woman featured on Hollywood’s films creates either a good image or a bad image to her race (McWilliams, 183). Some independent films have empowered featured women as cultural product interpreters. Hook pioneered a research field in black women readers of culture that put together the cultural studies and the African American studies. This was possible through the techniques of interviewing and textual interpretation based on criticism. The research’s intentions were to join the two studies and eradicate criticism. After a series of lengthy interviews, she came up with conclusive answers that the black women were not happy with the image instilled on them especially on the interpretations of the press, which contrasted theirs. Her work was difficult and a historical moment is the only thing that helps. Women interpretive images from the positions they held dominated the constructions of gender and race. Hook paid extra attention to images of gender and race gotten from the gallery and the museum. At the same time, many scholars paid attention to the images intersection depicting gender and race. One of the scholars did examinations on two images totally unrelated. The images were that of the Hottentots women and that of a prostitute. There is no way the two could ever be in the same relationship. Prostitution is a very bad image in the society and no body likes the association. Names used to refer to the black race were very off putting and mean. Some of these names included lesbians and gays. Nothing good according to Hook comes from a black woman. When you combine power, gender and race, a black woman has nothing more to shelter under. They are helpless and the only thing they do is to try to survive. The mechanisms for survival are minimal as the only place their voice has priority is through the media. Although there are no reasons to justify this, the important part is Jack argument of the threat content cinematically. The woman’s figure according to Jack provides means of compensation because she becomes the reason for the men’s gaze and to whom they direct probe, look at, control and

Summary and critical analysis of journal article Essay

Summary and critical analysis of journal article - Essay Example The tourists have direct contact with the tourist Guide .The tourist Guides assures those who hesitate to walk on the grave could always avoid it. In Savannah the dead were buried beyond the city limits, there the tour begins, the tourists have got chance to know about the dead people; Halloween company is good for ghost walk tour. In Savannah they have created different type of tourism where people come know the economy, geography and sociological importance." As different tourist attractions and cities increasingly compete with each other to attract tourists, the need to present the tourists with more spectacular, exotic, and titillating attractions increases."(Gotham 2002, 1737) Savannah has invested heavily into ghost tourism development and the use of murder, tragedy, and mystery as marketing tools. Ghost walk tours are an increasingly popular alternative to traditional tourism activities. These tourists companies appoint guides who take them by walk through sections of a city, telling stories of supernatural and macabre events believed to have occurred at sites along the way. According to internet information there are hundreds of tour are available both in urban and rural settings of the United States and in a variety of countries. "The Dark Tourism" with the new title doing very good business tourism where they are able to attract many people taking them to cemeteries, prisons, roman catacombs, castle dungeons, battlefields, sites of assassination, and museums that focus as the Holocaust(miles 2002; Ingles and Holmes 2003; strange and Kemp 2003).The tourists able to find out tragic aspect of history. Ghost walk tours offers firstly, it is different from the normal tourism; here the tourists have entertainment, fun and education. The tragedies are presented in a light hearted manner. Secondly it is geographically dynamic where wide number of people participates in performances without any differences culturally socially.According to Tuan Walking through the place involves sensory interaction with a location, helping to develop a more complete sense of place. It gives better experience than going by bus or car travel alone. One can explore the ever- changing nature of the urban landscape, street scene and liste ning to another's narrative. There are two type of tourism one is Enclave and heterogeneous. The former gives less space and time, it influence tourist performances through signs, imagery, rules, and actions of destination employees, locals and other tourists. In this tourists might want to explore the dark side of the tour (unseen) which is not

Carbon Mesoporous Material Hybrid Catalyst

Carbon Mesoporous Material Hybrid Catalyst Facile and clean transformation for synthesizing secondary arylamines through one-pot reductive amination of aniline, using aldehyde catalyzed by the supported nickel and poly(vinyl sulfonic acid) on mesoporous carbon CMK-3 (Ni/PVSA/CMK-3) as a novel acid-metal bi-functional heterogeneous catalyst. Sodium borohydride was used as the source of hydrogen for the reduction of imine. The reaction was performed at room temperature, in a short reaction time, without any by-products. Various characterization techniques including FT-IR, XRD, TG, BET, SEM, TEM, DRS-UV and AAS were employed to reveal the relationship between catalyst nature and catalytic performance. Reaction results demonstrate that the optimized Ni/PVSA/CMK-3 catalyst shows comparable catalytic performance thanks to the nickel metals and the acidic nature of polymer in mesopore channels of CMK-3. This method has several advantages such as, eco-friendly (used water as solvent), moderate to high yields, simple work-up procedure and catalyst filtered easily and reused without obvious loss of activity. 1. Introduction Nowadays, amines are privileged in industry that have found prevalent applications as intermediates for pharmaceuticals, biologically active compounds, rubber, solvents, fine chemicals, dyes, herbicides, and in the manufacture of detergents and plastics. Reductive amination demonstrate one of the most versatile and convenient methods of amine synthesis. This reaction has two steps including formation of an imine during reaction between primary amine and a carbonyl substrate, and reduction of the imine with adequate hydride source. There are two detached approaches for the reductive amination: the direct approach, which uses the in situ-generated imine, and the indirect approach, which uses the prior isolated imine. The former approach has several advantages such as one-pot procedure, increasing yields, having simple setup, easily separated from the product, being stable and compatible reagents, and the mild reaction conditions. To this end, over the past decades, researchers have been reported several studies on reductive amination reaction with several different catalysts, which among them, heterogeneous catalysis are prominent than homogenous catalysis owing to separate and recover capabilities. Moreover, it has been proven that accomplish this reaction needs two character including metallic and acidic; consequently, bi-functional heterogeneous catalysts are useful in this reaction. Recently, several metal nanoparticles acted as a hydride transfer such as Pt, Ni, Cu, and Pd. Despite of the fact that an effective control of particle size and a uniform distribution of nanoparticles in catalytic applications are generally predicted, nanoparticles typically accumulate together in bulk-like materials that hardly reduce selectivity and the activity of catalysts. To overcome with this problem, mesoporous silica, zeolites, polymers or macromolecular organic ligands have been used in order to immobilize metal nanoparticles in their pores. Mesoporous silica materials and zeolites have excellent order and surface area than other materials like polymer and etc.; subsequently, they are sufficient for catalysis approaches. Lately, mesoporous silica used for producing mesoporous carbon (CMK-n) as hard template. These materials contain several benefits compared to mesoporous silica and zeolites for instance, high mechanical stability, high thermal stability in nitrogen atmosphere, superb stability in strong acids and bases, and other engrossing properties such as narrow pore size distributions, high surface areas, and ordered frameworks. In addition, mesoporous carbon materials have hydrophobic nature on their surfaces and it helps to embed nanopolymers in their pores. In our previous studies, it asserts that when polymer embedded into mesoporous materials, they have perfect function. Owing to the fact that they have small particles and subsequently having high surface areas. Moreover, polymer nanoparticles fix in porous and they could not leach from their supporters. Accordingly, in this work, we will introduce a novel heterogeneous organic hybrid catalyst based on a carbon mesoporous material. In this circumstance, mesoporous carbon CMK-3 replicating from mesoporous silica SBA-15 was prepared and used as suitable support for Nickel nanoparticle/poly vinyl sulfonic acid/CMK-3 (Ni/PVSA/CMK-3). Furthermore, the catalyst was used effectively for the one-pot reductive amination of amine compounds using aldehyde in the presence of a small amount of NaBH4 as a mild reducing agent and two sort of solvent containing water and acetonitrile at room temperature without any by-products. 2. Experimental method 2.1. Catalyst characterization The samples have been analyzed by FT-IR spectroscopy (using a PerkinElmer 65 in KBr matrix in the range of 4000-400 cm-1). The thermal gravimetric analysis (TGA) data were obtained by a Setaram Labsys TG (STA) in a temperature range of 30-650 -C and heating rate 10 -C min-1 in nitrogen atmosphere. The X-ray powder diffraction (XRD) of the catalyst was carried out on a Bruker D8Advance X-ray diffractometer using nickel filtered Cu KÃŽ ± radiation at 40 kV and 20 mA. The BET specific surface areas and BJH pore size distribution of the samples were determined by adsorption-desorption of nitrogen at liquid nitrogen temperature, using a Series BEL SORP 18. For the measurement of nickel, a Perkin Elmer AAnalyst 300 atomic absorption spectrophotometer was used. The slit width, linear range and wave length for Ni were 0.2 nm, 2 and ppm232 nm, respectively. Scanning electron microscope (SEM) studies were performed on Philips, XL30, SE detector. Transmission electron microscope (TEM) observati ons were performed on a JEOL JEM.2011 electron microscope at an accelerating voltage of 200.00 kV using EX24093JGT detector in order to obtain information on the size of nickel nanoparticles and the DRS UV-vis spectra were recorded with JASCO spectrometer, V-670 from 190 to 2700 nm. Moreover, X-ray photoelectron spectra (XPS) was recorded on ESCA SSX-100 (Shimadzu) using a non-monochromatized Mg KÃŽ ± X-ray as the excitation source. The products were characterized by 1H NMR and 13C NMR spectra (Bruker DRX-500 Avance spectrometer at 500.13 and 125.47 MHz, respectively). Melting points were measured on an Electrothermal 9100 apparatus and they were uncorrected. All the products were known compounds and they were characterized by FT-IR, 1H NMR and 13C NMR. All melting points are compared satisfactorily with those reported in the literature. 2.2. Catalyst preparation The employed mesoporous carbon (CMK-3) was synthesized following the method reported by Ryoo using SBA-15 as template. 2.2.1. Preparation of SBA-15 Mesoporous silica SBA-15 was prepared using block copolymer Pluronic P123 (EO20PO70EO20) template as a structure directing agent and tetraethylorthosilicate (TEOS) as the silica precursor through the addition of H3PO4 by novel method as described in the literature. In a general synthesis, Pluronic P123 (2 g) was dissolved at room temperature in deionized water (75.4 mL) and H3PO4 (4.2 mL, 85%), after that TEOS (4.6 mL) was added to the solution and synthesis was fulfilled by stirring at 35 -C for 24 h in sealed Teflon breakers, and it was consequently placed at 100 -C for 24 h. Afterwards, the solution was filtered, washed with deionized water, and lastly dried at 95 -C for 12 h in air. Template removal was accomplished by calcination in air using two successive steps; first heating at 250 -C for 3 h and then at 550 -C for 4 h. 2.2.2. Preparation of CMK-3 Mesoporous carbon CMK-3 was prepared using mesoporous silica SBA-15 as template and sucrose as the carbon precursor. 1.0 g SBA-15 was added to 5 mL aqueous solution containing 1.25 g (3.65 mmol) sucrose and 0.14 g (1.42 mmol) of H2SO4 (98%). The resulting mixture was heated in an oven at 100 -C for 6 h and next 160 -C for another 6 h. In order to obtain entirely polymerized sucrose inside the pores of the SBA-15 template, 5 mL aqueous solution containing 0.8 g (2.33 mmol) sucrose and 0.09 g (0.917 mmol) of H2SO4 were added again, and the mixture was subjected to the thermal treatment described above one more time. Then, it was carbonized under nitrogen gas flow at 900 -C for 6 h with a heating rate of 5 -C min-1. Finally, the resulting solid was washed with 1 M NaOH solution (50 vol. % ethanol-50 vol. % H2O) twice to remove the silica template, filtered, washed with ethanol until pH = 7, and dried at 100 -C for 4 h. 2.2.3. Preparation of Poly(vinyl sulfonic acid)/CMK-3 2.2.4. Preparation of Ni nanoparticle-poly(vinyl sulfonic acid)/CMK-3 At first, Vinylsulfonic acid sodium was converted into its acidic form using the ion exchange resin (Amberjet 1200 H, 2 equiv. L-1, Aldrich). Ni/PVSA/CMK-3 was synthesized as follows: in the first place, 1 mL aqueous solution of NiCl2.6H2O (0.5 M) was added to the obtained PVSA/CMK-3 (0.1 g) together with 3 mL of H2O. The mixture was heated for 5 h at 353 K. Next, the solution of NaBH4 [0.057 g (1.5 mmol)] dissolved in 5 mL methanol was added to the mixture drop by drop in 20-30 min. Then, the solution was stirred for 3 h. After that, adding the same amount of NaBH4 was repeated and again the mixture was stirred for 3 h. Consequently, the solution was filtered and washed sequentially with deionized water and methanol to remove excess NaBH4 and NiCl2, and was dried in room temperature to yield Ni/PVSA/CMK-3. The Ni content of the catalyst was estimated by decomposing. Known amount of the catalyst by perchloric acid, nitric acid, fluoric acid, hydrochloric acid, and the Ni content was estimated by atomic absorption spectrometer. The Ni content of Ni/PVSA/CMK-3 estimated by atomic absorption spectrometer was 2.1 mmol g−1. 2.3. General procedure for one-pot reductive amination of aldehydes. A mixture of Aniline (2 mmol) and benzaldehyde (2 mmol) in water or acetonitrile (3 mL) was placed in a round bottom flask and stirred for 1 min at room temperature. Afterward, to the resulting mixture, Ni/PVSA/CMK-3 (0.04 g) and NaBH4 (6 mmol) were added and the mixture was stirred at room temperature until TLC showed the complete disappearance of the benzaldehyde. Then, the reaction mixture was quenched with water (10 mL) and the product was extracted with diethylether (2 10 mL). After they finished, the organic phase was dried over anhydrous Na2SO4, filtered and concentrated. In the end, the products were obtained very pure just by extract with diethylether in the majority of the reactions. The product was identified with a melting point, FT-IR spectroscopy techniques, 1HNMR and 13CNMR. 3. Results and discussion 3.1. Catalyst characterization Figure 1 shows the FTIR spectra of CMK-3 (a), PVSA/CMK-3 (b) and Ni/PVSA/CMK-3 (c). A broad band at around 3380-3470 cm−1 was observed in all samples. The O-H stretching vibration of the adsorbed water molecules mainly caused it. Moreover, in the CMK-3 spectrum, there are not any signals belong to organic bonds, resulting from the complete carbonization of sucrose (Fig. 1a). The presence of a new absorption bands at 1041 and 1186 cm-1 attributed to the S=O group of PVS, affirming the existence of the grafted PVSA chains on the CMk-3. In addition, the band at about 1650 cm-1 is attributed to adsorbed water, which is similar to related reports[]. The presence of peaks at around 2940 cm−1 and 1450 cm−1 correspond to the aliphatic C-H stretching and bending in PVSA/CMK-3, respectively (Fig. 2b). The appearance of the above bands shows that PVSA has been attached into mesoporous of CMK-3 and the synthesis of PVSA/CMK-3 has been successful. The profiles of thermogravimetric analysis of PVSA/CMK-3 and Ni/PVSA/CMK-3 under nitrogen atmosphere are shown in Fig. 2. The degradation of Poly(vinyl-sulfonic acid) commences at 150C and this stage continues to a little less than 300C. The next stage involves only a little degradation and occurs over the temperature range of 300 to 500C. These evidence are shown Poly(vinyl-sulfonic acid) cannot tolerant the temperature due to polymers are not protect by any supporter. The TGA curves of PVSA/CMK-3 shows a small mass loss (around 5%, w/w) in the temperature range of 100-330 -C, which is apparently associated with degradation of SO2 and ethylene from PVSA (Fig. 2). At temperatures above 330 -C, PVSA shows one main stage of degradation. The mass loss for PVSA in the second step is equal to 11.5% (w/w) which correspond to the degradation of the methane. In light of the difference between the PVSA and PVSA/CMK-3 curves, it is clear that PVSA/CMK-3 has higher thermal stability and slower degradation rate than PVSAP. Hence, after hybridization, the thermal stability is enhanced significantly that is beneficial for the catalyst application. In addition, Ni/PVSA/CMK-3 shows two separate weight loss steps that are almost similar to the PVSA/CMK-3. The only difference is temperature between 330 and 445 C, which Ni/PVSA/CMK-3 shows slower degradation rate than PVSA/CMK-3 in these range. It asserts that the hybrid Ni/PVSA/CMK-3 had higher thermal stability than PVSA/CMK-3. It may be related to the presence of Nickel nanoparticles in the composite structure. Consequently, it is proper thermal stability is boosted after hybridization because of intense the catalyst application. Figure 1 shows the powder XRD patterns of SBA-15, CMK-3, PVSA/CMK-3 and Ni/PVSA/CMK-3. The low angle diffraction pattern of SBA-15 shows three reflections at 2à Ã‚ ´ values from 0.5 to 2 ° including one strong peak at (100) and two weak peaks at (110) and (200), which corresponds to the well-known ordered arrangement of SBA-15 in the space group p6mm of 2-D hexagonal symmetry. The silica SBA-15 used as template to synthesis CMK-3. As can be seen, the XRD pattern of CMK-3 show three diffraction peaks at 2à Ã‚ ´ = 1.04 °, 1.79 ° and 2.05 ° (Fig. 3b). It could be marked to (100), (110) and (200) diffractions of the 2D hexagonal space group p6mm, which is compatible with previous articles. After polymerization by poly (vinyl sulfonic acid), the X-ray diffraction of PVSA/CMK-3 shows the same pattern with CMK-3. This evidence indicates that the structure of the CMK-3 was retained after the polymerization (Fig. 3c). Albeit, the intensity of the characteristic reflection peaks of the PVSA/CMK-3 is found to be diminished (Fig. 1b). Composite contains less CMK-3 due to the dilution of the carbon material by PVSA; subsequently, this dilution can be responsible for a decrease in the peak intensity. By the way, the XRD patterns of CMK-3 and PVSA/CMK-3 are almost similar to SBA-15, which it shows CMK-3 is a accurate replica of the mesoporous silica SBA-15 and the polymerization process does not damage the structure of CMK-3. After immobilize nickel in the PVSA/CMK-3, Ni peak cannot be seen in XRD since the homogeneity of Ni particles in the Ni/PVSA/CMK-3, and it lonely shows an amorphous pattern at 2ÃŽ ¸ values of about 44ËÅ ¡ (Fig. 3, inside). In order to demonstrate the e xistence of Ni nanoparticles in the Ni/PVSA/CMK-3 catalyst was exposed to temperature (400ËÅ ¡C). Meanwhile, amorphous Ni changed to crystalline and appear a peak with low intensity at 2ÃŽ ¸ = 44.29ËÅ ¡, which can be attributed to the small size of nickel nanoparticles and the plane (111) of fcc nickel. Eventually, after immobilize the nickel nanoparticles on composite, structure has not changed and it is represented a successful synthesis of the catalyst. The specific surface area, pore volume and the pore size of the CMK-3, PVSA/CMK-3 and Ni/PVSA/CMK-3 samples are summarized in Table 1. All samples exhibit a type IV adsorption isotherm with an H1 hysteresis loop by capillary condensation at relative pressure around 0.3-0.7 (Fig. 4). It is clear in table 1 that the PVSA/CMK-3 and Ni/PVSA/CMK-3 exhibits a smaller specific surface area, and pore volume in comparison to those of pure CMK-3. Thanks to the successful incorporation of the poly(vinyl sulfonic acid) into the mesoporous carbon. As can be seen, pore diameter increases in the PVSA/CMK-3 and Ni/PVSA/CMK-3 in comparison to CMK-3. This evidence shows the incorporation and growth of hyperbranched polymers and consequently produces the pressure (physical pressure on the wall of the channels) inside the CMK-3 mesoporous. By adding Ni nanoparticles into the PVSA/CMK-3, the specific surface area and pore volume decrease, asserting that nickel nanoparticles are located inside the pores o f the CMK-3. In spite of the fact that there are significant decreases in the pore volume and surface area, the pores of Ni/PVSA/CMK-3 were not blocked by deposition of the hyperbranched homopolymer and nickel nanoparticles. Moreover, the BJH pore size distribution curves of the PVSA/CMK-3 and Ni/PVSA/CMK-3 are exhibited a narrow pore size distribution (Fig. 5). It clarifies that the homopolymer and nickel nanoparticles are satisfactory distributed on the channels of the Ni/PVSA/CMK-3. This result is agreement with TEM analysis and shows the effective role of the hyperbranched polymer to entrap and uniformly disperse nickel nanoparticles. , , Fig. 6 gave the scanning electron microscopy (SEM) photographs of CMK-3 and PVSA/CMK-3 and Ni/PVSA/CMK-3. All the SEM images are shown rod-like morphology, which is attributed to carbon mesoporous. Although, virtually no significant differences observe in surface morphology between CMK-3 and PVSA/CMK-3, it is obvious that after hybridization the surface of CMK-3 is become coarser; indicating the most of polymerization of PVSA occurred in the pores of CMK-3, which was also supported by the decrease in surface area and pore volume as shown in Table 1. In addition, by immobilizing Ni nanoparticles, several spherical beads are seen on the mesoporous carbon. However, most of them are incorporated inside the carbon mesoporous structure, which is not observable in the SEM images. It is necessary to mention that after loading nickel nanoparticles on the surface of CMK-3, the structure of the mesoporous carbon is remained. Moreover, XRD analysis and TEM images confirmed this claim. The PVSA/CMK-3 and Ni/PVSA/CMK-3 were inspected by means of TEM micrographs technique (Fig. 7). The ordered hexagonal p6mm mesostructure of PVSA/CMK-3 and Ni/PVSA/CMK- 3 can be seen, indicating after polymerization and incorporation of PVSA and Ni nanoparticles, the ordered structure of mesoporous carbon is retained. Additionally, the places with darker contrast could be assigned to the presence of Pd particles with different distribution (Fig. 7c-d). As can be seen, the small dark spots could be ascribed to nickel nanoparticles with ∠¼X nm average diameter, presumably located into the mesoporous channels. On the other hand, larger dark spots are shown in fig. 7 c-d, which are corresponded to Ni nanoparticles agglomerate on the external surface with average diameter of ∠¼5-10 nm. Fig. 8 shows the DRS-UV of PVSA/CMK-3 and Ni/PVSA/CMK-3. previous reports were proven that DRS-UV of the cationic nickel have only d-d transitions peaks including 3T1g(P)↠3A2g (F) (368 nm) and 3T1g (F)↠3A2g (F) (576 nm), which these two peak do not show in Ni/PVSA/CMK-3. Moreover, the DRS-UV of Ni/PVSA/CMK-3 shows feature bands around 205 nm and 330 nm, which are attributed to the presence of Ni nanoparticles in these samples. By comparing these data, it can be found that cationic nickels are converted to the nickel nanoparticles by reduction of NaBH4. 3.2. Catalytic activity Synthesized nanocomposite was characterized by different methods in the former section. This section is introduced the application of this bi-functional catalyst to the reductive amination reaction. During two decade, enormous investigation devoted to develop environmental friendly synthesis. Since, using water as a reaction medium in transition metal-catalyzed processes is one of the most essential goal of sustainable chemistry. Water is nontoxic solvent, readily available, an inexpensive, nontoxic solvent and non-inflammable. It provides privilege over organic solvents from an environmental and an economic aspect. Accordingly, the effect of several parameters on the one-pot tandem reductive amination of aldehydes with aniline over Ni/PVSA/CMK-3 as acid-metal bifunctional catalyst was perused in water at room temperature and the outcome are as follows: At the first monitoring of experiments, diverse amounts of NiCl2.6H2O were tested to identify the effect of nickel nanoparticles concentration on the reductive amination reaction. Hence, the amount of NiCl2.6H2O to prepare Ni/PVSA/CMK-3 was changed from 1 mmol/g to 15 mmol/g and then measured by the Atomic Absorption spectroscopy technique (AAS) which are shown in Table 2. It is clear that the activity of catalytic steadily improved by increasing NiCl2.6H2O form 1 mmol/g to 5 mmol/g. According to the catalytic reaction mechanism, nickel nanoparticle mediated electron transfer from BH4- ion to the imine intermediates (Scheme 1). Subsequently, the amounts of H- sites on the catalyst surface are grown by increasing nickel nanoparticles. Thus, larger amount of hydrides can be transferred to the imine groups through the catalyst. On the other hand, by further increasing the amount of NiCl2.6H2O (more than 5 mmol/g), the catalytic activity was diminished, which can be attributed to after a certain amount of nickel chloride increases, a larger amount of nanoparticles is loaded on the surface of the CMK-3 that may have caused the mesopore channels to narrow. In Fact, the nanoparticle size will increase by increasing the amount of NiCl2.6H2O. Therefore, in some places, the pore size will narrow and it is able to lessen the rate of reactants diffusion into the porous. In one word, lower performance of the catalyst produced with higher NiCl2.6H2O concentration will be anticipated. Despite of this fact, it does not mean the pores are throughout clogged. According to these results, the catalyst provided by 5 mmol/g NiCl2.6H2O presented the best catalytic activity. To identify the effect of NaBH4 amount (as a hydride donor) on the reductive amination the reaction was carried out using various amounts of NaBH4 in the presence of Ni/PVSA/CMK-3 as catalyst. As shown in Table 3, the yield was increased by increasing the amount of NaBH4 (until 6 mmol). The excess values did not have any effect on the reaction. Therefore, 6 mmol NaBH4 was the best value to perform reductive amination reaction. The influence of the solvent on catalytic activity was investigated in the reductive amination reaction using Ni-PVSA/CMK-3 catalyst and NaBH4 as hydride donor, at room temperature. The results are gathered in Table 4. Four vital factor acts to fulfil reductive amination reaction including dielectric constant, dipole moment, solubility in NaBH4, hydrophobic effect, protic and aprotic solvent effect. The results revealed that the reaction time in ethanol solvent is slow due to NaBH4 hardly solving in ethanol and the reaction rate is tardy. In addition, the reaction rate in water solvent is slow because although dielectric constant and solubility of water in NaBH4 is high, carbon mesoporous CMK-3 have hydrophobic nature. It causes substances and catalyst cannot have perfect interaction together. The hydrophobic nature of acetonitrile and oxolane are higher than other solvent that presented above; thus, these two solvent have more similarity to hydrophobic nature of CMK-3. Moreover, dipole moment of acetonitrile is higher than other solvent. Thanks to this feature, the reaction rate increase. Whereas the methanol solvent has mediate circumstance of dielectric constant, solubility in NaBH4, and hydrophobic effect aspect, the reaction time diminish. It is noteworthy to mention that the combination of all these factors together cause this process. Regarding these situation, water and acetonitrile were finally selected as the solvent for the reaction because of their environmental friendly and highly efficient, respectively; and all other optimization and reaction separately accomplished by these two solvent. The effect of the amount of catalyst was defined for reductive amination reaction (Table 5). Due to the fact, the catalyst synthesized is worthy, it is decided that the amount of catalyst optimize by decreasing down to the 0.04 g, nevertheless the reaction time were increased. However, reducing the amount of catalysts until 0.02 g was not sufficient. Since, the quantity of 0.04 g for both solvent was found to be the best weight of catalyst. The reusability of the catalyst was studied by using Ni/PVSA/CMK-3 in water and acetonitrile solvent (Chart 1). After each cycle, the catalyst was filtered off, washed with water (10 mL) and ethanol (3 mL 5 mL). After that, catalyst dried at 60 ËÅ ¡C and reused in the reductive amination reaction with a fresh reaction substances. It might be noted that after each run, a slight amount of the catalysts were lost in the filtration process. Herein, to overcome this problem, after each experiment the amount of remaining catalyst was specified and the molar ratio of the reactants was adjusted according to the remaining amount of the catalyst. The catalyst was reused up to 5 times. The catalyst that react in acetonitrile solvent have serious loss activity. In further investigation, it recognized that the catalyst used in acetonitrile solvent was somewhat destroyed. It can be attributed to the interaction between acetonitrile as a solvent and PVSA/CMK-3 composite. In other cases, not o nly the reusability of the catalyst that performed in water was adequate, but also the catalyst exhibit high stability in this status. This result obtained by SEM and XRD characterization, which can be seen in Figure 9 and 10. As shown in SEM images of reused catalyst in water as reaction solvent is well retained, which is very essential for the catalyst applications. Similarly, the XRD pattern shows a diffraction peak at low angle (1.04 °). It display that the catalyst structure remain. Because of this fact that the reusability in the heterogeneous catalysts is fundamental, water in reductive amination reaction chosen as a compatible solvent. The catalytic activity of the Ni/PVSA/CMK-3 in the reductive amination was compared with CMK-3, PVSA/CMK-3, and without a catalyst. The results are available in Table 6. The consequences affirm the significance role of the acid-metal heterogeneous catalyst in sort of reaction. As shown, the reaction dose not fulfil up to 5% without catalyst. There is the important issue that NaBH4 function as a mild hydride donor agent, which is incapable reagent for reducing imine groups solely. In a similar manner, this result obtained by using CMK-3 due to the fact that mesoporous carbon CMK-3 does not have any active sites to carry out the reaction. By using the PVSA/CMK-3, with improve acidic feature of the mesoporous carbon the carbonyl group activated and thus the yield moderately increased to 40% and 35% in acetonitrile and water solvent, respectively. In addition, using Ni/PVSA/CMK-3, the reaction efficiency was increased to 97% in 35 and 63 min in acetonitrile and water solvent, respectivel y; Because of the role of nickel nanoparticles as species to transfer hydride ions from NaBH4 to imine groups. The interesting point in catalyst investigation is heterogeneous nature. In this regard, the catalyst was separated from the reaction mixture at approximately 50% conversion of the starting substances by filtration and then centrifugation. The reaction progress in the filtrate circumstance was monitored (data not shown). No further reductive amination reaction occurred even at addition times, representing that the nature of reaction process is heterogeneous and there is not any progress for the reaction in homogeneous phase.

Carbon Mesoporous Material Hybrid Catalyst

Carbon Mesoporous Material Hybrid Catalyst Facile and clean transformation for synthesizing secondary arylamines through one-pot reductive amination of aniline, using aldehyde catalyzed by the supported nickel and poly(vinyl sulfonic acid) on mesoporous carbon CMK-3 (Ni/PVSA/CMK-3) as a novel acid-metal bi-functional heterogeneous catalyst. Sodium borohydride was used as the source of hydrogen for the reduction of imine. The reaction was performed at room temperature, in a short reaction time, without any by-products. Various characterization techniques including FT-IR, XRD, TG, BET, SEM, TEM, DRS-UV and AAS were employed to reveal the relationship between catalyst nature and catalytic performance. Reaction results demonstrate that the optimized Ni/PVSA/CMK-3 catalyst shows comparable catalytic performance thanks to the nickel metals and the acidic nature of polymer in mesopore channels of CMK-3. This method has several advantages such as, eco-friendly (used water as solvent), moderate to high yields, simple work-up procedure and catalyst filtered easily and reused without obvious loss of activity. 1. Introduction Nowadays, amines are privileged in industry that have found prevalent applications as intermediates for pharmaceuticals, biologically active compounds, rubber, solvents, fine chemicals, dyes, herbicides, and in the manufacture of detergents and plastics. Reductive amination demonstrate one of the most versatile and convenient methods of amine synthesis. This reaction has two steps including formation of an imine during reaction between primary amine and a carbonyl substrate, and reduction of the imine with adequate hydride source. There are two detached approaches for the reductive amination: the direct approach, which uses the in situ-generated imine, and the indirect approach, which uses the prior isolated imine. The former approach has several advantages such as one-pot procedure, increasing yields, having simple setup, easily separated from the product, being stable and compatible reagents, and the mild reaction conditions. To this end, over the past decades, researchers have been reported several studies on reductive amination reaction with several different catalysts, which among them, heterogeneous catalysis are prominent than homogenous catalysis owing to separate and recover capabilities. Moreover, it has been proven that accomplish this reaction needs two character including metallic and acidic; consequently, bi-functional heterogeneous catalysts are useful in this reaction. Recently, several metal nanoparticles acted as a hydride transfer such as Pt, Ni, Cu, and Pd. Despite of the fact that an effective control of particle size and a uniform distribution of nanoparticles in catalytic applications are generally predicted, nanoparticles typically accumulate together in bulk-like materials that hardly reduce selectivity and the activity of catalysts. To overcome with this problem, mesoporous silica, zeolites, polymers or macromolecular organic ligands have been used in order to immobilize metal nanoparticles in their pores. Mesoporous silica materials and zeolites have excellent order and surface area than other materials like polymer and etc.; subsequently, they are sufficient for catalysis approaches. Lately, mesoporous silica used for producing mesoporous carbon (CMK-n) as hard template. These materials contain several benefits compared to mesoporous silica and zeolites for instance, high mechanical stability, high thermal stability in nitrogen atmosphere, superb stability in strong acids and bases, and other engrossing properties such as narrow pore size distributions, high surface areas, and ordered frameworks. In addition, mesoporous carbon materials have hydrophobic nature on their surfaces and it helps to embed nanopolymers in their pores. In our previous studies, it asserts that when polymer embedded into mesoporous materials, they have perfect function. Owing to the fact that they have small particles and subsequently having high surface areas. Moreover, polymer nanoparticles fix in porous and they could not leach from their supporters. Accordingly, in this work, we will introduce a novel heterogeneous organic hybrid catalyst based on a carbon mesoporous material. In this circumstance, mesoporous carbon CMK-3 replicating from mesoporous silica SBA-15 was prepared and used as suitable support for Nickel nanoparticle/poly vinyl sulfonic acid/CMK-3 (Ni/PVSA/CMK-3). Furthermore, the catalyst was used effectively for the one-pot reductive amination of amine compounds using aldehyde in the presence of a small amount of NaBH4 as a mild reducing agent and two sort of solvent containing water and acetonitrile at room temperature without any by-products. 2. Experimental method 2.1. Catalyst characterization The samples have been analyzed by FT-IR spectroscopy (using a PerkinElmer 65 in KBr matrix in the range of 4000-400 cm-1). The thermal gravimetric analysis (TGA) data were obtained by a Setaram Labsys TG (STA) in a temperature range of 30-650 -C and heating rate 10 -C min-1 in nitrogen atmosphere. The X-ray powder diffraction (XRD) of the catalyst was carried out on a Bruker D8Advance X-ray diffractometer using nickel filtered Cu KÃŽ ± radiation at 40 kV and 20 mA. The BET specific surface areas and BJH pore size distribution of the samples were determined by adsorption-desorption of nitrogen at liquid nitrogen temperature, using a Series BEL SORP 18. For the measurement of nickel, a Perkin Elmer AAnalyst 300 atomic absorption spectrophotometer was used. The slit width, linear range and wave length for Ni were 0.2 nm, 2 and ppm232 nm, respectively. Scanning electron microscope (SEM) studies were performed on Philips, XL30, SE detector. Transmission electron microscope (TEM) observati ons were performed on a JEOL JEM.2011 electron microscope at an accelerating voltage of 200.00 kV using EX24093JGT detector in order to obtain information on the size of nickel nanoparticles and the DRS UV-vis spectra were recorded with JASCO spectrometer, V-670 from 190 to 2700 nm. Moreover, X-ray photoelectron spectra (XPS) was recorded on ESCA SSX-100 (Shimadzu) using a non-monochromatized Mg KÃŽ ± X-ray as the excitation source. The products were characterized by 1H NMR and 13C NMR spectra (Bruker DRX-500 Avance spectrometer at 500.13 and 125.47 MHz, respectively). Melting points were measured on an Electrothermal 9100 apparatus and they were uncorrected. All the products were known compounds and they were characterized by FT-IR, 1H NMR and 13C NMR. All melting points are compared satisfactorily with those reported in the literature. 2.2. Catalyst preparation The employed mesoporous carbon (CMK-3) was synthesized following the method reported by Ryoo using SBA-15 as template. 2.2.1. Preparation of SBA-15 Mesoporous silica SBA-15 was prepared using block copolymer Pluronic P123 (EO20PO70EO20) template as a structure directing agent and tetraethylorthosilicate (TEOS) as the silica precursor through the addition of H3PO4 by novel method as described in the literature. In a general synthesis, Pluronic P123 (2 g) was dissolved at room temperature in deionized water (75.4 mL) and H3PO4 (4.2 mL, 85%), after that TEOS (4.6 mL) was added to the solution and synthesis was fulfilled by stirring at 35 -C for 24 h in sealed Teflon breakers, and it was consequently placed at 100 -C for 24 h. Afterwards, the solution was filtered, washed with deionized water, and lastly dried at 95 -C for 12 h in air. Template removal was accomplished by calcination in air using two successive steps; first heating at 250 -C for 3 h and then at 550 -C for 4 h. 2.2.2. Preparation of CMK-3 Mesoporous carbon CMK-3 was prepared using mesoporous silica SBA-15 as template and sucrose as the carbon precursor. 1.0 g SBA-15 was added to 5 mL aqueous solution containing 1.25 g (3.65 mmol) sucrose and 0.14 g (1.42 mmol) of H2SO4 (98%). The resulting mixture was heated in an oven at 100 -C for 6 h and next 160 -C for another 6 h. In order to obtain entirely polymerized sucrose inside the pores of the SBA-15 template, 5 mL aqueous solution containing 0.8 g (2.33 mmol) sucrose and 0.09 g (0.917 mmol) of H2SO4 were added again, and the mixture was subjected to the thermal treatment described above one more time. Then, it was carbonized under nitrogen gas flow at 900 -C for 6 h with a heating rate of 5 -C min-1. Finally, the resulting solid was washed with 1 M NaOH solution (50 vol. % ethanol-50 vol. % H2O) twice to remove the silica template, filtered, washed with ethanol until pH = 7, and dried at 100 -C for 4 h. 2.2.3. Preparation of Poly(vinyl sulfonic acid)/CMK-3 2.2.4. Preparation of Ni nanoparticle-poly(vinyl sulfonic acid)/CMK-3 At first, Vinylsulfonic acid sodium was converted into its acidic form using the ion exchange resin (Amberjet 1200 H, 2 equiv. L-1, Aldrich). Ni/PVSA/CMK-3 was synthesized as follows: in the first place, 1 mL aqueous solution of NiCl2.6H2O (0.5 M) was added to the obtained PVSA/CMK-3 (0.1 g) together with 3 mL of H2O. The mixture was heated for 5 h at 353 K. Next, the solution of NaBH4 [0.057 g (1.5 mmol)] dissolved in 5 mL methanol was added to the mixture drop by drop in 20-30 min. Then, the solution was stirred for 3 h. After that, adding the same amount of NaBH4 was repeated and again the mixture was stirred for 3 h. Consequently, the solution was filtered and washed sequentially with deionized water and methanol to remove excess NaBH4 and NiCl2, and was dried in room temperature to yield Ni/PVSA/CMK-3. The Ni content of the catalyst was estimated by decomposing. Known amount of the catalyst by perchloric acid, nitric acid, fluoric acid, hydrochloric acid, and the Ni content was estimated by atomic absorption spectrometer. The Ni content of Ni/PVSA/CMK-3 estimated by atomic absorption spectrometer was 2.1 mmol g−1. 2.3. General procedure for one-pot reductive amination of aldehydes. A mixture of Aniline (2 mmol) and benzaldehyde (2 mmol) in water or acetonitrile (3 mL) was placed in a round bottom flask and stirred for 1 min at room temperature. Afterward, to the resulting mixture, Ni/PVSA/CMK-3 (0.04 g) and NaBH4 (6 mmol) were added and the mixture was stirred at room temperature until TLC showed the complete disappearance of the benzaldehyde. Then, the reaction mixture was quenched with water (10 mL) and the product was extracted with diethylether (2 10 mL). After they finished, the organic phase was dried over anhydrous Na2SO4, filtered and concentrated. In the end, the products were obtained very pure just by extract with diethylether in the majority of the reactions. The product was identified with a melting point, FT-IR spectroscopy techniques, 1HNMR and 13CNMR. 3. Results and discussion 3.1. Catalyst characterization Figure 1 shows the FTIR spectra of CMK-3 (a), PVSA/CMK-3 (b) and Ni/PVSA/CMK-3 (c). A broad band at around 3380-3470 cm−1 was observed in all samples. The O-H stretching vibration of the adsorbed water molecules mainly caused it. Moreover, in the CMK-3 spectrum, there are not any signals belong to organic bonds, resulting from the complete carbonization of sucrose (Fig. 1a). The presence of a new absorption bands at 1041 and 1186 cm-1 attributed to the S=O group of PVS, affirming the existence of the grafted PVSA chains on the CMk-3. In addition, the band at about 1650 cm-1 is attributed to adsorbed water, which is similar to related reports[]. The presence of peaks at around 2940 cm−1 and 1450 cm−1 correspond to the aliphatic C-H stretching and bending in PVSA/CMK-3, respectively (Fig. 2b). The appearance of the above bands shows that PVSA has been attached into mesoporous of CMK-3 and the synthesis of PVSA/CMK-3 has been successful. The profiles of thermogravimetric analysis of PVSA/CMK-3 and Ni/PVSA/CMK-3 under nitrogen atmosphere are shown in Fig. 2. The degradation of Poly(vinyl-sulfonic acid) commences at 150C and this stage continues to a little less than 300C. The next stage involves only a little degradation and occurs over the temperature range of 300 to 500C. These evidence are shown Poly(vinyl-sulfonic acid) cannot tolerant the temperature due to polymers are not protect by any supporter. The TGA curves of PVSA/CMK-3 shows a small mass loss (around 5%, w/w) in the temperature range of 100-330 -C, which is apparently associated with degradation of SO2 and ethylene from PVSA (Fig. 2). At temperatures above 330 -C, PVSA shows one main stage of degradation. The mass loss for PVSA in the second step is equal to 11.5% (w/w) which correspond to the degradation of the methane. In light of the difference between the PVSA and PVSA/CMK-3 curves, it is clear that PVSA/CMK-3 has higher thermal stability and slower degradation rate than PVSAP. Hence, after hybridization, the thermal stability is enhanced significantly that is beneficial for the catalyst application. In addition, Ni/PVSA/CMK-3 shows two separate weight loss steps that are almost similar to the PVSA/CMK-3. The only difference is temperature between 330 and 445 C, which Ni/PVSA/CMK-3 shows slower degradation rate than PVSA/CMK-3 in these range. It asserts that the hybrid Ni/PVSA/CMK-3 had higher thermal stability than PVSA/CMK-3. It may be related to the presence of Nickel nanoparticles in the composite structure. Consequently, it is proper thermal stability is boosted after hybridization because of intense the catalyst application. Figure 1 shows the powder XRD patterns of SBA-15, CMK-3, PVSA/CMK-3 and Ni/PVSA/CMK-3. The low angle diffraction pattern of SBA-15 shows three reflections at 2à Ã‚ ´ values from 0.5 to 2 ° including one strong peak at (100) and two weak peaks at (110) and (200), which corresponds to the well-known ordered arrangement of SBA-15 in the space group p6mm of 2-D hexagonal symmetry. The silica SBA-15 used as template to synthesis CMK-3. As can be seen, the XRD pattern of CMK-3 show three diffraction peaks at 2à Ã‚ ´ = 1.04 °, 1.79 ° and 2.05 ° (Fig. 3b). It could be marked to (100), (110) and (200) diffractions of the 2D hexagonal space group p6mm, which is compatible with previous articles. After polymerization by poly (vinyl sulfonic acid), the X-ray diffraction of PVSA/CMK-3 shows the same pattern with CMK-3. This evidence indicates that the structure of the CMK-3 was retained after the polymerization (Fig. 3c). Albeit, the intensity of the characteristic reflection peaks of the PVSA/CMK-3 is found to be diminished (Fig. 1b). Composite contains less CMK-3 due to the dilution of the carbon material by PVSA; subsequently, this dilution can be responsible for a decrease in the peak intensity. By the way, the XRD patterns of CMK-3 and PVSA/CMK-3 are almost similar to SBA-15, which it shows CMK-3 is a accurate replica of the mesoporous silica SBA-15 and the polymerization process does not damage the structure of CMK-3. After immobilize nickel in the PVSA/CMK-3, Ni peak cannot be seen in XRD since the homogeneity of Ni particles in the Ni/PVSA/CMK-3, and it lonely shows an amorphous pattern at 2ÃŽ ¸ values of about 44ËÅ ¡ (Fig. 3, inside). In order to demonstrate the e xistence of Ni nanoparticles in the Ni/PVSA/CMK-3 catalyst was exposed to temperature (400ËÅ ¡C). Meanwhile, amorphous Ni changed to crystalline and appear a peak with low intensity at 2ÃŽ ¸ = 44.29ËÅ ¡, which can be attributed to the small size of nickel nanoparticles and the plane (111) of fcc nickel. Eventually, after immobilize the nickel nanoparticles on composite, structure has not changed and it is represented a successful synthesis of the catalyst. The specific surface area, pore volume and the pore size of the CMK-3, PVSA/CMK-3 and Ni/PVSA/CMK-3 samples are summarized in Table 1. All samples exhibit a type IV adsorption isotherm with an H1 hysteresis loop by capillary condensation at relative pressure around 0.3-0.7 (Fig. 4). It is clear in table 1 that the PVSA/CMK-3 and Ni/PVSA/CMK-3 exhibits a smaller specific surface area, and pore volume in comparison to those of pure CMK-3. Thanks to the successful incorporation of the poly(vinyl sulfonic acid) into the mesoporous carbon. As can be seen, pore diameter increases in the PVSA/CMK-3 and Ni/PVSA/CMK-3 in comparison to CMK-3. This evidence shows the incorporation and growth of hyperbranched polymers and consequently produces the pressure (physical pressure on the wall of the channels) inside the CMK-3 mesoporous. By adding Ni nanoparticles into the PVSA/CMK-3, the specific surface area and pore volume decrease, asserting that nickel nanoparticles are located inside the pores o f the CMK-3. In spite of the fact that there are significant decreases in the pore volume and surface area, the pores of Ni/PVSA/CMK-3 were not blocked by deposition of the hyperbranched homopolymer and nickel nanoparticles. Moreover, the BJH pore size distribution curves of the PVSA/CMK-3 and Ni/PVSA/CMK-3 are exhibited a narrow pore size distribution (Fig. 5). It clarifies that the homopolymer and nickel nanoparticles are satisfactory distributed on the channels of the Ni/PVSA/CMK-3. This result is agreement with TEM analysis and shows the effective role of the hyperbranched polymer to entrap and uniformly disperse nickel nanoparticles. , , Fig. 6 gave the scanning electron microscopy (SEM) photographs of CMK-3 and PVSA/CMK-3 and Ni/PVSA/CMK-3. All the SEM images are shown rod-like morphology, which is attributed to carbon mesoporous. Although, virtually no significant differences observe in surface morphology between CMK-3 and PVSA/CMK-3, it is obvious that after hybridization the surface of CMK-3 is become coarser; indicating the most of polymerization of PVSA occurred in the pores of CMK-3, which was also supported by the decrease in surface area and pore volume as shown in Table 1. In addition, by immobilizing Ni nanoparticles, several spherical beads are seen on the mesoporous carbon. However, most of them are incorporated inside the carbon mesoporous structure, which is not observable in the SEM images. It is necessary to mention that after loading nickel nanoparticles on the surface of CMK-3, the structure of the mesoporous carbon is remained. Moreover, XRD analysis and TEM images confirmed this claim. The PVSA/CMK-3 and Ni/PVSA/CMK-3 were inspected by means of TEM micrographs technique (Fig. 7). The ordered hexagonal p6mm mesostructure of PVSA/CMK-3 and Ni/PVSA/CMK- 3 can be seen, indicating after polymerization and incorporation of PVSA and Ni nanoparticles, the ordered structure of mesoporous carbon is retained. Additionally, the places with darker contrast could be assigned to the presence of Pd particles with different distribution (Fig. 7c-d). As can be seen, the small dark spots could be ascribed to nickel nanoparticles with ∠¼X nm average diameter, presumably located into the mesoporous channels. On the other hand, larger dark spots are shown in fig. 7 c-d, which are corresponded to Ni nanoparticles agglomerate on the external surface with average diameter of ∠¼5-10 nm. Fig. 8 shows the DRS-UV of PVSA/CMK-3 and Ni/PVSA/CMK-3. previous reports were proven that DRS-UV of the cationic nickel have only d-d transitions peaks including 3T1g(P)↠3A2g (F) (368 nm) and 3T1g (F)↠3A2g (F) (576 nm), which these two peak do not show in Ni/PVSA/CMK-3. Moreover, the DRS-UV of Ni/PVSA/CMK-3 shows feature bands around 205 nm and 330 nm, which are attributed to the presence of Ni nanoparticles in these samples. By comparing these data, it can be found that cationic nickels are converted to the nickel nanoparticles by reduction of NaBH4. 3.2. Catalytic activity Synthesized nanocomposite was characterized by different methods in the former section. This section is introduced the application of this bi-functional catalyst to the reductive amination reaction. During two decade, enormous investigation devoted to develop environmental friendly synthesis. Since, using water as a reaction medium in transition metal-catalyzed processes is one of the most essential goal of sustainable chemistry. Water is nontoxic solvent, readily available, an inexpensive, nontoxic solvent and non-inflammable. It provides privilege over organic solvents from an environmental and an economic aspect. Accordingly, the effect of several parameters on the one-pot tandem reductive amination of aldehydes with aniline over Ni/PVSA/CMK-3 as acid-metal bifunctional catalyst was perused in water at room temperature and the outcome are as follows: At the first monitoring of experiments, diverse amounts of NiCl2.6H2O were tested to identify the effect of nickel nanoparticles concentration on the reductive amination reaction. Hence, the amount of NiCl2.6H2O to prepare Ni/PVSA/CMK-3 was changed from 1 mmol/g to 15 mmol/g and then measured by the Atomic Absorption spectroscopy technique (AAS) which are shown in Table 2. It is clear that the activity of catalytic steadily improved by increasing NiCl2.6H2O form 1 mmol/g to 5 mmol/g. According to the catalytic reaction mechanism, nickel nanoparticle mediated electron transfer from BH4- ion to the imine intermediates (Scheme 1). Subsequently, the amounts of H- sites on the catalyst surface are grown by increasing nickel nanoparticles. Thus, larger amount of hydrides can be transferred to the imine groups through the catalyst. On the other hand, by further increasing the amount of NiCl2.6H2O (more than 5 mmol/g), the catalytic activity was diminished, which can be attributed to after a certain amount of nickel chloride increases, a larger amount of nanoparticles is loaded on the surface of the CMK-3 that may have caused the mesopore channels to narrow. In Fact, the nanoparticle size will increase by increasing the amount of NiCl2.6H2O. Therefore, in some places, the pore size will narrow and it is able to lessen the rate of reactants diffusion into the porous. In one word, lower performance of the catalyst produced with higher NiCl2.6H2O concentration will be anticipated. Despite of this fact, it does not mean the pores are throughout clogged. According to these results, the catalyst provided by 5 mmol/g NiCl2.6H2O presented the best catalytic activity. To identify the effect of NaBH4 amount (as a hydride donor) on the reductive amination the reaction was carried out using various amounts of NaBH4 in the presence of Ni/PVSA/CMK-3 as catalyst. As shown in Table 3, the yield was increased by increasing the amount of NaBH4 (until 6 mmol). The excess values did not have any effect on the reaction. Therefore, 6 mmol NaBH4 was the best value to perform reductive amination reaction. The influence of the solvent on catalytic activity was investigated in the reductive amination reaction using Ni-PVSA/CMK-3 catalyst and NaBH4 as hydride donor, at room temperature. The results are gathered in Table 4. Four vital factor acts to fulfil reductive amination reaction including dielectric constant, dipole moment, solubility in NaBH4, hydrophobic effect, protic and aprotic solvent effect. The results revealed that the reaction time in ethanol solvent is slow due to NaBH4 hardly solving in ethanol and the reaction rate is tardy. In addition, the reaction rate in water solvent is slow because although dielectric constant and solubility of water in NaBH4 is high, carbon mesoporous CMK-3 have hydrophobic nature. It causes substances and catalyst cannot have perfect interaction together. The hydrophobic nature of acetonitrile and oxolane are higher than other solvent that presented above; thus, these two solvent have more similarity to hydrophobic nature of CMK-3. Moreover, dipole moment of acetonitrile is higher than other solvent. Thanks to this feature, the reaction rate increase. Whereas the methanol solvent has mediate circumstance of dielectric constant, solubility in NaBH4, and hydrophobic effect aspect, the reaction time diminish. It is noteworthy to mention that the combination of all these factors together cause this process. Regarding these situation, water and acetonitrile were finally selected as the solvent for the reaction because of their environmental friendly and highly efficient, respectively; and all other optimization and reaction separately accomplished by these two solvent. The effect of the amount of catalyst was defined for reductive amination reaction (Table 5). Due to the fact, the catalyst synthesized is worthy, it is decided that the amount of catalyst optimize by decreasing down to the 0.04 g, nevertheless the reaction time were increased. However, reducing the amount of catalysts until 0.02 g was not sufficient. Since, the quantity of 0.04 g for both solvent was found to be the best weight of catalyst. The reusability of the catalyst was studied by using Ni/PVSA/CMK-3 in water and acetonitrile solvent (Chart 1). After each cycle, the catalyst was filtered off, washed with water (10 mL) and ethanol (3 mL 5 mL). After that, catalyst dried at 60 ËÅ ¡C and reused in the reductive amination reaction with a fresh reaction substances. It might be noted that after each run, a slight amount of the catalysts were lost in the filtration process. Herein, to overcome this problem, after each experiment the amount of remaining catalyst was specified and the molar ratio of the reactants was adjusted according to the remaining amount of the catalyst. The catalyst was reused up to 5 times. The catalyst that react in acetonitrile solvent have serious loss activity. In further investigation, it recognized that the catalyst used in acetonitrile solvent was somewhat destroyed. It can be attributed to the interaction between acetonitrile as a solvent and PVSA/CMK-3 composite. In other cases, not o nly the reusability of the catalyst that performed in water was adequate, but also the catalyst exhibit high stability in this status. This result obtained by SEM and XRD characterization, which can be seen in Figure 9 and 10. As shown in SEM images of reused catalyst in water as reaction solvent is well retained, which is very essential for the catalyst applications. Similarly, the XRD pattern shows a diffraction peak at low angle (1.04 °). It display that the catalyst structure remain. Because of this fact that the reusability in the heterogeneous catalysts is fundamental, water in reductive amination reaction chosen as a compatible solvent. The catalytic activity of the Ni/PVSA/CMK-3 in the reductive amination was compared with CMK-3, PVSA/CMK-3, and without a catalyst. The results are available in Table 6. The consequences affirm the significance role of the acid-metal heterogeneous catalyst in sort of reaction. As shown, the reaction dose not fulfil up to 5% without catalyst. There is the important issue that NaBH4 function as a mild hydride donor agent, which is incapable reagent for reducing imine groups solely. In a similar manner, this result obtained by using CMK-3 due to the fact that mesoporous carbon CMK-3 does not have any active sites to carry out the reaction. By using the PVSA/CMK-3, with improve acidic feature of the mesoporous carbon the carbonyl group activated and thus the yield moderately increased to 40% and 35% in acetonitrile and water solvent, respectively. In addition, using Ni/PVSA/CMK-3, the reaction efficiency was increased to 97% in 35 and 63 min in acetonitrile and water solvent, respectivel y; Because of the role of nickel nanoparticles as species to transfer hydride ions from NaBH4 to imine groups. The interesting point in catalyst investigation is heterogeneous nature. In this regard, the catalyst was separated from the reaction mixture at approximately 50% conversion of the starting substances by filtration and then centrifugation. The reaction progress in the filtrate circumstance was monitored (data not shown). No further reductive amination reaction occurred even at addition times, representing that the nature of reaction process is heterogeneous and there is not any progress for the reaction in homogeneous phase.