Sunday, January 26, 2020

Kiliani-fischer Synthesis of Monosaccharides

Kiliani-fischer Synthesis of Monosaccharides Teoh Shi Hao Sean Introduction Monosaccharides are the most basic unit of carbohydrates, playing an essential role in the biochemistry of life. The most important and commonly occurring form is glucose, used as an energy source in cells (Solomon et al., 2011). Monosaccharides have the chemical formula (CH2O)n (where n 3) but those with eight or more carbons are uncommon due to their inherent instability (Solomon et al., 2011; McMurry, 2008). In a monosaccharide molecule, each carbon atom has a hydroxyl group bonded to it, except one which has an oxygen atom double bonded to it instead thus forming a carbonyl group (Solomon et al., 2011). The monosaccharide is an aldehyde if the carbonyl group is located at the end of the chain, and a ketone if the carbonyl group is located at any other position. Monosaccharides can exist in acyclic or cyclic forms, and usually switch between the two forms (McMurry, 2008). The Kiliani-Fischer synthesis is a technique for lengthening these important biomolecules. Mechanism Figure 1 below shows the reaction equation of the technique. A starting sugar is first reacted with sodium cyanide to form cyanohydrin, and subsequently hydrolysed through the application of heat to form two diastereomeric aldonic acid lactone intermediates. These intermediates are later separated through separation techniques, such as chromatography, and the desired lactone is reduced using a sodium amalgam to form a resultant sugar that has one carbon atom more than the starting sugar. In this written review, the starting sugar will be a aldopentose and the resultant sugar will be a aldohexose. Figure 1 – Reaction equation of the Kiliani-Fischer synthesis (Kilini-Fischer synthesis, 2014; Fischer, 1890). Nucleophilic addition of aldehyde to form cyanohydrin The first step in Kiliani-Fischer synthesis involves nucleophilic addition of the starting sugar, an aldehyde. NaCN and H2O are used as reagents (McMurry, 2008). Figure 2 below shows the mechanism of the reaction. A lone pair on a CN ion initiates the reaction by attacking the nucleophilic carbon atom at the carbonyl group, forming a tetrahedral intermediate. The O then attacks the H atom of a H2O molecule, forming a cyanohydrin. Figure 2 – Reaction of starting sugar to form cyanohydrin. Hydrolysis of cyanohydrin to form aldonic acid The second step in Kiliani-Fischer synthesis involves the hydrolysis of the cyanohydrin to form aldonic acid (McMurry, 2008). H2O is used as the reagent, with heat applied. Figure 3 below shows the mechanism of the reaction. The lone pair on the O of OH, formed by the auto-ionization of water, attacks the nucleophilic C of the cyanohydrin forming a trigonal planar structure. The lone pair on the N then attacks an H of a H2O molecule, followed by the double bond of C=N attacking the H atom bonded to the OH group. The resultant molecule is an amide. An OH ion then attacks the nucleophilic carbon at the carbonyl group, forming a tetrahedral intermediate that collapses with NH2 leaving as a leaving group. An aldonic acid molecule is formed. Figure 3 – Hydrolysis of cyanohydrin to form aldonic acid. Esterification of aldonic acid to form lactone intermediate and subsequent reduction to form resultant sugar With the same reagent of H2O and conditions of heat, the aldonic acid produced from the hydrolysis of cyanohydrin undergoes esterification to form lactone intermediates (McMurry, 2008). Figure 4 below shows the mechanism of the reaction. A lone pair on the O at the carbonyl group of COOH attacks a proton produced by the auto-ionization of water. The tautomer of the resulting intermediate has a nucleophilic carbon, C1, which is attacked by a lone pair present on the OH group on the other end of the aldonic acid chain. The electrons from the O-H bond of the attacking OH group is withdrawn by the O+, and the resulting proton is attacked by a lone pair on the OH group attached to C1. The lone pair from the O of the other OH group attached to C1 forms a second bond between C and O, and a H2O molecule leaves as a leaving group. The electrons from the O-H bond then forms a second bond between C and O, and a proton leaves. A lactone intermediate is formed. Finally, the lactone intermediate is reduced using a sodium amalgam, Na(Hg), to form the resultant aldohexose monosaccharide (McMurry, 2008). Reagents used are sodium amalgam and sulphuric acid, in cold solution (Fischer, 1890). Figure 5 below shows the reaction equation. The exact mechanism of reduction by sodium amalgam is unknown at this point in time (Keck et al., 1994). Figure 4 – Esterification of aldonic acid to form lactone intermediate. Figure 5 – Reduction of aldonic acid to resultant sugar. History and development The Kiliani-Fischer synthesis is named after German chemists Heinrich Kiliani and Hermann Emil Fischer. Its original purpose was to elucidate all 16 stereoisomers of aldohexoses, as achieved by Fischer. Key discoveries that to the development of this technique included: (1) Louis Pasteur’s insight that the â€Å"molecule of tartaric acid came in two forms that were mirror images†, or isomers, of one another, and that each of these isomers rotated polarized light in different directions (Wagner, 2004, p.240), (2) Jacobus H. van’t Hoff’s and J. A. Le Bel’s insight of the â€Å"concept of an asymmetric carbon atom†, that isomers of compounds exist despite identical chemical formulae because of asymmetric carbon atoms, and the relationship between stereochemistry and optical activity (Wagner, 2004, p.240), and (3) Fischer’s creation of phenylhydrazine, a reagent that reacts with sugar molecules to form osazones. Prior to the discovery of this technique, relatively little was known about the structural properties of monosaccharides. It was difficult to study monosaccharides because of their â€Å"tendency to form syrups rather than solids that could be dissolved and crystallized easily† (Wagner, 2004). However, Fischer discovered phenylhydrazine which when reacted with aldonic acids (formed by oxidation of sugars) forms osazones (Kunz, 2002). These carbohydrate derivatives could be isolated easily through crystallization, and had physical forms that could be distinguished from one another (Kunz, 2002). Their subsequent analysis allowed Fischer to identify and segregate isomers of the monosaccharides (Wagner, 2004). The aldonic acid can be regenerated by addition of baryta water, or aqueous solution of barium hydroxide, to the segregated osazone (Fischer, 1890). The then purified aldonic acid can be evaporated to transform into welling-crystallizing lactone for further study (Fischer, 1 890). Using this technique, Fischer discovered that two distinct monosaccharides, D-glucose and D-mannose, yield the same osazone because osazone formation destroys the asymmetry about C2 without affecting the rest of the molecule (Wagner, 2004). Furthermore, the lactones of D-glucose and D-mannose turned polarized light in different directions. As such, he concluded that D-glucose and D-mannose have identical structures but were mirror images of one another (Wagner, 2004). However, their exact structures were still unknown. In 1886, Kiliani discovered a method to lengthen the carbon chain of an organic molecule, using cyanide as a reagent to form cyanohydrin (McMurry, 2012). Fischer realized the potential of this discovery in advancing the study of carbohydrates, adding on an additional step to convert the cyanohydrin nitrile group into an aldehyde (McMurry, 2012). Thus, the Kiliani-Fischer synthesis was created. This new technique allowed Fischer to research further into the stereoisomerism of monosaccharides and continue off where he last stopped – that D-glucose and D-mannose were stereoisomers but of unknown structures. Applications Elucidation of aldohexose stereoisomers Figure 5 on the right shows the general structure of a aldohexose. In order to apply the Kiliani-Fischer synthesis in the elucidation of aldohexose stereoisomers, Fischer had to first make a starting assumption that the –OH group of D-glucose at C5 was on the right side (Wagner, 2004). L-arabinose is an aldopentose having five carbon atoms. Its exact structure had been deciphered by Fischer, and is asymmetric at C2, C3 and C ­4 as shown in Figure 6 on the right. Fischer discovered that the Kiliani-Fischer synthesis converted L-arabinose into both D-glucose and D-mannose (Wagner, 2004). This therefore implied that D-glucose and D-mannose shared the same configuration about C3, C4 and C5 as the analogous carbons in L-arabinose (C2, C3 and C4 respectively) (Wagner, 2004). This insight led Fischer to use L-arabinose in conjunction with D-glucose and D-mannose as materials for further research. Fischer discovered that oxidizing L-arabinose created a product that was optically active (Wagner, 2004). If the starting assumption made by Fischer was true, then this implied that the –OH group at C2 in L-arabinose (and thus C3 in D-glucose and D-mannose) must be on the left side or the product would be optically inactive (Wagner, 2004). Next, Fischer determined that oxidizing D-glucose and D-mannose resulted in dicarboxylic acids that were optically active (Wagner, 2004). This implied that the –OH group at C4 in D-glucose and D-mannose (and thus C3 in L-arabinose) must be on the right side or the product would be optically inactive (Wagner, 2004). Finally, Fischer found that oxidizing D-gulose resulted in the same dicarboxylic acid as that of D-glucose (Wagner, 2004). Through logic, Fischer realized this implied that the –OH group at C2 in D-glucose must be on the right side. Piecing together all the information, Fischer finally determined the exact structure of D-glucose and D-mannose, as shown in Figure 7 below. Problems and improvements The Kiliani-Fischer synthesis is a commonly used technique in preparing aldoses. However, the last step in the reaction process, reduction, produces â€Å"mixtures containing product aldoses, unreacted lactone, aldonic acid salts, and alditols† (Serianni et al., 1979; p.71). Reduction by sodium amalgam allows the production of acylated aldoses in high yields but the subsequent removal of the acyl groups often degrades the product aldose (Serianni et al., 1979). An improvement to this method would be to reduce the nitrile over a palladium catalyst (Serianni et al., 1979; McMurry, 2012). This would yield an imine intermediate instead, that can be hydrolysed to an aldehyde. References Fischer, E. (1890). Synthesis in the sugar group. Journal of the American Chemical Society, 12(8), 400-409. Fischer, E. (1902). Syntheses in the purine and sugar group. Nobel Lectures, Chemistry 1901, 1921, 21-35. Keck, G. E., Savin, K. A. Weglarz, M. A. (1995). Use of samarium diiodide as an alternative to sodium/mercury amalgam in the Julia-Lythgoe Olefination. Journal of Organic Chemistry, 60(10), 3194–3204. Kiliani-Fischer synthesis (2014). Wikipedia. Retrieved April 2, 2014 from http://en.wikipedia.org/wiki/Kiliani%E2%80%93Fischer_synthesis. Kunz, H. (2002). Emil Fischer – unequalled classicist, master of organic chemistry, and inspired trailblazer of biological chemistry. Angewandte Chemie International Edition, 41(23), 4439-4451. Magner, J. A. (2004). Emil Fischer (1852-1919): The stereochemical nature of sugars. The Endocrinologist, 14(5), 239-244. McMurry, J. (2008). Organic Chemistry (7th edition). Belmont, CA: Thomson Brooks/Cole. McMurry, J. (2012). Organic Chemistry (8th edition). Belmont, CA: Thomson Brooks/Cole Serianni, A. S., Nunez, H. A. Barker, R. (1979). Carbon-13 enriched carbohydrates: Preparation of aldonitrile and their reduction with a palladium catalyst. Carbohydrate Research, 72, 71-78. Solomon, E. P., Berg, L. R., Martin, D. W. (2011). Biology (9th edition). Singapore, CA: Cengage Learning Asia Pte Ltd.

Saturday, January 18, 2020

Internet: Sociology and People Essay

Internet Internet has become a big part of our life these days because of the many things that we can get from it from the latest news and research findings to self- expression. We also get to learn about the latest trends in our profession and instantly become fashion chic. It also updates us of our favorite basketball tea, and thespians. Truly, it becomes a great help in the workplace, education, entertainment, health care, and communication. However, the Internet has also served as a venue for the infringement of copyright. Everyone has the access to information which makes it almost impossible to protect copyright. This for of piracy is really widespread on the web. Aside from this, the proliferation of pornographic materials is undeniably one of the alarming things that has brought about by the Internet. It does not only corrupt the minds of the young people that are exposed to them but also it paves the way for the degradation of human dignity. It also strains the moral make up of society. The Internet also alienates the person from his social self. While most think that talking to loved ones through the computer screens allows or offers the same satisfaction of social needs just like engaging in conversations personally, there really is a big difference between the virtual self and the social self. This could further lead to addiction which could hamper a person’s way of living and those who are directly in contact with him. The Internet was intended to be used for military purposes. However, due to its versatility and applicability, we have it as how it is used today. It exists as our friend when used properly and our foe when misused. THE INFLUENCE OF THE INTERNET ON PEOPLE’S SOCIAL AND PSYCHOL Uploaded by nikolovska1 (149) on Jul 8, 2007 THE INFLUENCE OF THE INTERNET ON PEOPLE’S SOCIAL AND PSYCHOLOGICAL REALITIES The influence of the Internet has caused a change in the way we communicate, learn and shop. The Internet is probably most famous for the ability to spread information, fact or fiction. We were once limited to news editors of a local paper, then to national cable news. Now anyone can search the globe, visit local papers in foreign countries, and see the views of all sides. This ease of information has also brought with it a large amount of hoaxes, money schemes, and fallacies. There is no question that easy access to the Internet, like the introduction of mail service and the invention of the telephone, has changed the nature of people’s connection to others in their social world. Mail made possible connections among people without physical proximity, and the telephone facilitated communication among distant people, making rapid connections possible across long distancies. But has this communication revolution changed the pure nature of interpersonal and group processes? On the one hand, since the primary use of the Internet is communication, some people might speculate that the Internet will have positive social consequences in people’s everyday lives because it increases the frequency and quality of interpersonal communications among people. People with easy access to others would feel better connected and more strongly supported by others, leading to happiness and engagement in families, organizations, communities, and society more generally. But, on the other hand, the ease of electronic communication may lead to weaker social ties, because people have less reason to leave their homes and actually interact face to face with other people. The Internet allows people to more easily work from their home, to form and sustain friendships and even romantic attacments from their home, to bank from their home, to vote and engage in political and soci al issue based discussions with others (from home). In this variety of ways, Internet communications can potentially displace face-to-face communications. I think this point is important because psychologists in many researches have described and proved such face to face and telephone connections as being of higher quality, when viewed in terms of their contribution to satisfaction and well-being. Reading a seriees of longitudinal and experimental studies (e.x. McKenna, Green, and Gleason), who test a theory of relationship formation on the Internet, these researchers directly adress the argument that the psychological quality of Internet social interaction is lower than is the psychological quality of traditional face-to-face interaction. Consider my own use. I’ve received several e-mail messages in the past hour. My boyfriend confirms the dinner for tonight. Even though it is weekend, my coleagues send me questions about the pending exam expects a quick answer. So does some graduate student from Europe, that I recently met on â€Å"MySpace† with an urgent request for a letter of recommendation. My friend Ksenija sends me an IM to tell me the latest news about her new love. And so on and so on†¦ I assume that I am also living a virtual life, and what’s the most interesting of all, all of my friends online, are also my friends in real life. And if they weren’t that in the past, I somehow managed to bring my cyber friends into my real life, so I could here in my real life enable real communication, real face-to-face â€Å"talks†, real exchange of emotions, feeligs of happiness, satisfaction and well-being. I’d say for me, the Internet is a great new way for doing old things. So, what else conclusion can I bring except the one that Internet life cannot stand on itself without real-life communication. It is simple: If we understand the qualities of face-to-face communication that influence the impact of su ch communication on people and their social interaction, we would be able to predict the probable influence of any new communication technology. However, researchers show that people sooner or later convert their cyber contacts into more traditional face-to-face, the same as I do. People use the Internet, in other words to help them achieve their real-life goals. And rather than technology’s changing people’s social and psychological reality, in other words, people change their use of technology to facilitate their creation of a desired social reality. Internet users should closely examine their behavior, to ensure that excessive time online will not negatively impact their personal well-being. We shouldn’t throw our computers out the window, but neither should we charge on blindly into complete dependence on the Internet. As with many things in life, it seems that moderation and balance are key to maximizing the Internet’s positive effect.| The Internet has provided a new medium with which children and teens can bully their peers. While no direct physical harm can actually be done, the rise of Cyber Bullying can be much more dangerous than the bullying that takes place on school grounds. The Internet provides a false sense of safety and anonymity, which means that more and more children are likely to engage in ridiculing their peers and spreading vicious rumors. Children that would never dream of belittling one of their classmates face to face won’t think twice about doing so in a chat room, on their MySpace page or in a blog. How does the expression go? â€Å"Sticks and stones may break my bones, but words will never hurt me†? As we all know, this simply isn’t true. Hurtful words and false accusations can do a world of hurt and can sometimes even lead to physical harm, especially among people who are young and impressionable. The Internet allows users of all ages, not just young people, the opportu nity to reinvent themselves and their image. If they don’t feel accepted at school they may go looking for acceptance on the net, and as we all know, for young people acceptance often comes at the expense of others. What makes Cyber Bullying all the more problematic is the fact that it can be difficult to regulate. Teachers and other staff are present at school to observe students’ behavior and hopefully put an end to bullying when they witness it. However, more and more young people are being given unlimited and unsupervised access to the Internet, which is more vast a place that we can imagine. Parents who aren’t watching what their children are doing on the Internet, whether its because they are technologically challenged, incredibly naive, or just negligent, have no idea what sorts of behavior their children are engaging in. When most parents finally wise up, they are shocked and appalled at what sites little Ryan has been visiting or who precious little Jamie has been conversing with. Possibly the most dangerous aspect of the Internet is the way that it encourages dangerous and hurtful behavior. Young girls are praised for posting inappropriate and revealing photographs of themselves and ridicule and rumors among classmates are answered and supported with even more hurtful behavior. It is up to society as a whole to help bring this problem of children and the Internet under control. The Internet is a wonderful tool, don’t get me wrong, but it is very hard to regulate and it is very easy for children too obtain a myriad of images and information that should not be seen by their impressionable eyes. Unfortunately, many parents are naive to this problem and refuse to believe that their children would get involved in anything dangerous or inappropriate on the Internet. Programs and other tools are available to help parents monitor their children’s Internet usage, but these alone are not enough. Young people today are more likely to know more about these devices than their parents, and often can find ways to bypass them. Therefore, you also need to be limiting the total amount of time that your children spend on the Internet each day and know what sort of access and supervision is taking place when they are visiting friends. Never, ever, allow children to have a computer in their room or their own laptop. The computer that your children use should always be in a main and heavily trafficked room of the house, where you can keep a watchful eye on their activity. It is up to you to help make this world a safer place for your children and you cannot underestimate the danger that is lurking in your very own home every time they sit down in front of the computer.

Friday, January 10, 2020

New Questions About College Services Answered and Why You Must Read Every Word of This Report

New Questions About College Services Answered and Why You Must Read Every Word of This Report The 30-Second Trick for College Services An indicator of succeeding is that the majority of the university doesn't realize that a service is being provided by means of a partner. All you will need is at Bentley. AWS provides us with a means to do that. Tutors are an immensely valuable resource that may indicate the difference between passing and failing. This is going to be the ideal investment you could ever make in helping your child realize her or his dream of playing golf in college. The True Meaning of College Services You might not be asked this at all with a number of the resources. Excelsior partners are making a workforce not just with an ability to grow academically, but with an ability to boost productivity and innovation. The student is going to be taught to do hazard and risk assessment techniques required to mitigate a hazardous materials incident. The parcel tax equation is likewise an accurate method to find out how much the Colleges should pay. Income plays a massive part in deciding the affordability of higher education. Every one of these services can assist you in a multitude of means. A counselor at the career services office will be able to help you pick a career, whether you don't have any idea what you would like to do or are leaning toward a specific occupation. Besides getting a hard-working, passionate new employee, the business has an opportunity to mentor and train a number of the upcoming small business leaders in our region. Whether your existing employees will need to brush up on a soft skill or a new hire demands a specific technical skill, we've got the trainers and expertise to assist you. Oakton and the CCJobNet partnership doesn't promote opportunities where job seekers are required to supply a monetary commitment or that don't supply a guaranteed wage or compensation. She's also involved in several other diversity-focused community groups. There's no project too large or too tiny. Our aim is to work with each other to attain the very best possible outcome... PROGRESS! We are here in order to help you accomplish your academic objectives, while assisting you to take advantage of what Hunter's diverse community offers! Why Almost Everything You've Learned About College Services Is Wrong It helps he has become the interim CEO since February 5. We're Corporate College. Career Services is here to aid you with all things career-related. College Services has the ability to supply a high degree of service by attracting and retaining amazing leaders. If you've been wanting to enter the medical field but thought it may be too costly, now's your opportunity. As our service offerings keep growing, we're always searching for new methods to support our care recipients. If you wish to attain a mature transformation with internal high quality assurance and fidelity, look at using a consultant over a prolonged period. On the flip side, should you ever will need to earn some money, becoming a tutor is an excellent way to receive paid while also helping struggling students. Some scholarships could have restrictions, including students with numerous tribal lineages may just receive assistance from 1 tribe. Some offices and organizations provide non-work-study positions also. Furthermore, students will be required to remain in New York for exactly the same quantity of time they are covered by the scholarship. International Education There are several students who'd love an opportunity to study abroad for a semester. The Argument About College Services You have to present your ID card when you enter the Brockport Downtown. Call 314-539-5316 to find out more. Call 314-539-5041 to learn more. Call 314-539-5305 to learn more. If you try to activate your account early, it is going to fail. Once you have filled in the details, you are going to be able to opt for a password and begin using your account. You are then going to be requested to login. Complete and submit the on-line registration. Ok, I Think I Understand College Services, Now Tell Me About College Services! Participating employees won't be billed for their present semester charges until final grades are posted. All students are eligible to be viewed at Health Services, no matter their insurance policy coverage. You'll have a number of program alternatives, you will spend less, and you're going to have faculty and staff committed to helping you succeed! SHS has launched an on-line patient portal. Rumors, Deception and College Services There are lots of services which are available to you at college which can help with a range of things. It's strongly advisable that students purchase needed books and course materials ahead of their very first class. If you're shopping about for a college, you might want to make certain yours provides these services. The college isn't accredited, as it does not provide credit-bearing courses.

Thursday, January 2, 2020

How Does The Linked Learning Approach Increase The College...

How does the Linked Learning Approach increase the college and career readiness of Latino and African American males at the high school level? 11. DESCRIPTION OF THE PROJECT: There are many factors that could affect the college and career readiness of African American and Latino males, however programs that marry career and technical skills with academics like the Linked Learning Approach may help to improve that readiness drastically Growing up, my family has always been close, especially my brother and I. Although we are six years apart, we have a very strong relationship. My brother is far more intelligent than I, knows more about things that I ever thought to know. Yet, he struggled with finishing high school, going to college, and completing his degree while I graduated from high school and went straight to a four-year university. I saw the same scenario happen again with my four younger cousins who all went to school in the same district as my brother and I. Three were boys, all very intelligent, and one girl. All three boys finished high school at a continuation school, while the girl went on to a 4-year university, just like I did. I began to wond er what pushed me and my younger female cousin to success, but left my brother and male cousins floundering in the educational system? As I began my teaching career, I observed the same phenomena. My male African-American and Latino students were performing at a lower rate than other subgroups. At a newer high school inShow MoreRelatedIdentifying Strategies to Improve African American College Student Retention and Graduation Rates1690 Words   |  7 Pageseducation. Obtaining an advanced degree remains a likely predictor of future career success. The problem facing the minority student is that barriers persist which continue to hinder enrollment, retention, and graduation rates in institutions of higher education. 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