Saturday, September 7, 2019
Emancipation Proclamation Prliminary Events Essay Example for Free
Emancipation Proclamation Prliminary Events Essay Abraham Lincoln was elected the President of the United States in 1860 with an anti-slavery agenda, and this gave the impression to the Southern States that they no longer belonged in the Union. South Carolina became the first state to secede the Union on December 20, 1860. In the following few months six more states, whose agriculture based economy was dependent on the free labor slavery provided, followed South Carolinaââ¬â¢s lead and followed suit. The seven states, South Carolina, Mississippi, Florida, Alabama, Georgia, Louisiana, and Texas formed the Confederate States of America and chose the Mississippi senator, Jefferson Davis as their interim president (PBS). Lincoln claimed in his inaugural address in March 1861that it was his responsibility to keep the Union intact. He went on to state that he would not end slavery where it existed, or take back the Fugitive Slave Law (a 1850 law requiring all runaway slaves to the Northern states where slavery did not exist, to be returned to their masters in the South). It was understandable why this position of Mr. Lincolnââ¬â¢s did not sit well with the African Americans or the white Americans against slavery, but what was surprising was that it did not do anything to satisfy the Confederacy. Hence, on April 12, 1861 the Confederates attacked Fort Summer and the Civil Started had started. Immediately following the attacks another four states, Virginia, Arkansas, North Carolina, and Tennessee joined the Confederacy. Even though President Lincoln made it abundantly clear that he was fighting to keep the Union intact and not for slavery or for the rights of the blacks, from the very start the free African Americans rushed to enlist in the army. Their services were refused and laws refusing blacks the right to enlist in the army were maintained because Lincoln wanted to prove to the whites in the Northern states that their privileges as the superior race were not in any danger. The Confederacy on the other hand was using the enslaved labor for efforts to win the war. Slave labor was being used as nurses, laundresses, blacksmiths and they were working in factories and armories (PBS). As the Northern army managed to penetrate into the Southern territory, there was a large influx of refugees. The slave fugitives were labeled ââ¬Å"contraband of warâ⬠and if it could be proven that their labor was used to help the Confederacy they were given their freedom. Despite declaring the black fugitives free, Lincoln still firmly held on to the idea that this war was not about setting the slaves free but holding the Union together. By early 1862 Lincoln was beginning to think that some kind of an emancipation order was needed if North was to win. The Proclamation As the war drew on, a number of governments in Europe started to think about recognizing the Confederacy and interceding against the Union. Also at home the Congressional and public opinion grew more towards the fact that slavery was not right and it needed to be abolished as a policy of war. Faced with such mounting pressure from all sides Lincoln felt that if a declaration was made to free the slaves, then European opinion would be with the North, and he would get the support needed for his own administration and the war effort, that he decided to draft the Emancipation Proclamation in 1862 (Emancipation Proclamation). On July 13, 1862, Lincoln read out the prelude proclamation to his Secretaries William H. Seward and Gideon Wells and both were left at a loss for words, and Lincoln did not discuss the matter further. On July 22 Lincoln read the Proclamation at his Cabinet meeting and got a mixed reaction. Secretary of War Edwin M. Stanton, deciphered the measure as a method of taking the slave labor away from the Confederacy while allowing more men into the Union Army and supported its release as soon as possible, the Postmaster General Montgomery Blair predicted doom in the fall elections, while the Attorney General Edward Bates was against equality in the political and civil arena for the Blacks. Since the President was not concerned about his Cabinetââ¬â¢s view of the substance of the Proclamation only its style, the direction on future action was set (www. memory. loc. gov). To show that the proclamation was being issued out of strength and not a sign of weakness, Secretary of State Seward recommended that Lincoln not issue it until there was some significant Union victory. The opportunity presented itself when there was a Union victory at Antietam on September 22, 1862 and five days after that Lincoln issued the Proclamation which became effective on January 1, 1863. The chief function of the proclamation was to bring peace back and restore Union control, and was perceived as a firm commitment to abolish slavery. Proclamation also turned around the strengths of the warring parties by taking away the slave labor from the confederates, whose backbone in war efforts was formed by the slaves and gave this advantage to the Union (Borade). England and France were dependent upon the cotton they got from the South, and the Confederacy was hopeful that these countries would enter the war on their side. By turning the war into a fight against slavery, England and France sided with the Union because their citizens were against slavery (Emancipation Proclamation Prliminary Events, 2009). The purpose of limiting the proclamation to a few states was because Lincoln had the authority to take such an action on his own, a proclamation like this would not have Constitutional power over Union states since they had certain rights (The Emancipation Proclamation). In reality the proclamation freed very few slaves, because the border states fighting for the Union were not affected by it, nor were the southern areas already under Union control, and the rebellious states ignored the order. The Emancipation Proclamation is made up of two executive orders; the first order stated that if the breakaway did not put an end to the war and return to the Union by 1 January 1863, then all the slaves in the Confederate States would be set free. The second order listed the specific states to which the order applied. The Proclamation also had clauses which focused on rebellion and how to do away with it. It was stated that any individual starting a rebellion would be incarcerated for ten years and would be fined ten thousand dollars. If on the other hand, the individual freed his slaves, the court would not punish them (Borade). The proclamation also said that freed slaves who met with the necessary requirements would be allowed into the armed services of the Union, which was a major shift from the previous policy. The original Emancipation Proclamation is housed in the National Archives in Washington D. C. , and covers five pages of text. It was held together with thin red and blue ribbons which were stuck to the page that has signatures by the seal of the United States. The emancipation document was transferred from the Department of State to the National Archives in 1936 (Emancipation Proclamation). Works Cited Borade, G. (n. d. ). Purpose and Effects of the Emancipation Proclamation. Retrieved August 3, 2010, from www. buzzle. com: http:/www. buzzle. com/articles/purpose-and-effects-of-the-emancipation-proclamation. html Emancipation Proclamation. (n. d. ). Retrieved August 3, 2010, from www. archives. gov: http://www. archives. gov/exhibits/featured_documents/emancipation_proclamation/ Emancipation Proclamation. (n. d. ). Retrieved August 2, 2010, from www. Encyclopaedia Britannica: http://www. britannica. com/EBchecked/topic/185468/Emancipation-Proclamation Emancipation Proclamation Prliminary Events. (2009, January 01). Retrieved August 03, 2010, from www. robinsonlibrary. com: http://robinsonlibrary. com/america/unitedstates/1783/slavery/emancipation. htm PBS. (n. d. ). www. pbs. org. Retrieved August 2, 2010, from http://www. pbs. org/wgbh/aia/part4/4p2967. html The Emancipation Proclamation. (n. d. ). Retrieved August 3, 2010, from www. usconstitution. net: http://www. usconstitution. net/eman. html www. memory. loc. gov. (n. d. ). Retrieved August 2, 2010, from http://memory. loc. gov/ammem/alhtml/almintr. html
Friday, September 6, 2019
Superstitions Essay Example for Free
Superstitions Essay If you want get recover from heartbroken, you must strictly follow the healing broken heart step. It is normal that on one cannot escape from this situation because love exists with everyone and everywhere. People may say on one ever died of broken heart, but when you face with it, it is nearly dead actually. The following suggestions will help you fix the painfully trouble from your relationship that has ended. First, calm down and breathe deeply. An easy step that you can do is surviving from the difficult day. Take one day and give yourself a moral support. Staying with yourself too much in bed room does not help at all. It will worsen. The easy suggestions for this beginning step are sleeping, watching movie, cooking at home, playing game and eating ice cream. All above are easy ways which motivate you to smile again. Second, stay close with friends and family members. Having someone to talk to is very important when you are in trouble especially broken heart. It helps sharing your thoughts with others. Make lists of friends who you can sincerely talk to because your close friends will soothe and give you advices the best. You probably ask them to hang out or find special activities which you interested in to do. These will help refresh your mind and boost up your confident surely. Finally, after following the above steps, next suggestion is continue socializing and exercising regularly. Make sure that those activities are not related to alcohol or drug which will drag you to worse broken heart. Going out to meet other people helps you to get a new aspect of life, for example, in case you are not accept breaking relationship, a surrounding peopleââ¬â¢s life or their experiences that worse than yours may change your thought of being sad. Besides, you should do exercise regularly in order to refresh your mind and appearance. Socializing and exercising are effective if you consider doing it. In conclusion, remember that healing process takes long time. There is no quick way to stop suffering. Mending a broken heart is not easy but it can be done. If possible, consider to date the new one but avoid risky relationship that will hurt you again. I believe that with your attempt, all tasks can be done so believe in yourself and always realize that the man does not right for you. You deserve more. Smile to yourself and never give up. Nevertheless, The Broken Heart is an important contribution to our literature and one of the most penetrating books I have studied in some time. It deals with a subject that needs to be grasped by more Latter-day Saints. An understanding of grace is needed not only as we interact with members of other faiths who hold their own beliefs regarding grace, but particularly as we seek to come unto Christ through a deeper understanding and application of his Atonement. This is a book about hope, a book that extends hope. Sometimes we say, the author writes, that no other success can compensate for our failures in the home. And while it is true that no other success of ours can fully compensate, there is a success that compensates for all our failures, after all we can do in good faith. That success is the Atonement of Jesus Christ. By its power, we may arise from the ashes of life filled with incomprehensible beauty and joy (22). Certainly no message could be more vital, more central, than that. Did you know that smoking one pack of cigarettes a day for ten years could reduce your bone density by 2 percent! And if this is not shocking enough read on -Tobacco speeds artery damage. It promotes memory loss, Alzheimers disease, causes rapid skin aging, anxiety, impotence, fatigue, headaches hoarseness of voice, smokers cough, peptic ulcers, senility, cramps in the legs stained teeth and nails, hiatal hernia, heart disease cancer, osteoporosis and the list can go on and on and on ( from health magazine) The best way to give up smoking is NOW! Stop smoking is the hardest thing for a smoker, that is why some people make fun of themselves Stop smoking is so easy, see I already did it several times. If you did stop smoking, then congratulation. If you are still smoking, do not worry, there are some tips. First, drink plenty of fluids like fruit juices, vegetable juices, warm water throughout the day to help in cleansing the body and providing antioxidants to lesson the free radical irritation during the detox period. Secondly munch the carrot sticks cucumber strips, radish and plenty of raw vegetables as oral substitutes to deal with the psychological ties to smoking. Thirdly have a positive attitude towards health and life in general, stay busy to prevent boredom and to keep your mind off smoking. Maybe you can get another smoker, to stop smoking with you so that you can discuss common problems and get each others support. Furthermore indulge in health treatments such as a massage, sauna, steam, and teeth cleansing to remove cigarette stains. Lastly if your craving to smoke arises, take a brisk walk, or drink tea or do things with your hands, or exercise, or go for a swim or just practice breathing relaxation techniques, smile (even if you dont feel like) and be thankful that you are not smoking. If you are a smoker, you have undoubtedly tried to quit and have found it difficult. Believe me, it is just a question of mind over body. If you follow the steps above, you will be success.
Thursday, September 5, 2019
Wadsworth-Emmons Cyclopropanation Reaction | Analysis
Wadsworth-Emmons Cyclopropanation Reaction | Analysis Abstract This project aims to look at the development of the Wadsworth-Emmons cyclopropanation reaction and compare it to alternative methods of cyclopropanation in order to understand why it may be used preferentially. Current applications of the WE cyclopropanation reaction are explored to see the efficacy and yield that result. Key of Abbreviations Seen below is a collection of all abbreviations used within this project and their subsequent meaning. à â⬠3: Tertiary Bn: Benzyl group CCR: Corey-Chaykovsky Reagent d.e: DME: Dimethoxyethane e.e: Et: Ethyl group EWG: Electron Withdrawing Group HWE: Horner-Wadsworth-Emmons iPr: isopropyl Me: Methyl NOE: Ph: Phenyl group THF: Tetrahydrofuran WE: Wadsworth-Emmons 1: Introduction Cyclopropaneà [1]à was used as an anaesthetic until it was discovered to be highly reactive and dangerous when combined with oxygen. The reactivity of cyclopropane is mainly due to the high amount of ring strain and the bond strength between the carbons being weaker than normal carbon bonds, allowing the ring to open easily. Cyclopropane structures are often found within compounds in nature (figure 1.)à [2]à that are observed to have medicinal and commercial applications, e.g. degradable insecticides such as the pyrethroid family that are less toxic to other animals in the environmentà [3]à ,à [4]à . Cyclopropanation can also produce a number of hallucinogens and opoid drugs that are most widely used recreationally for there effects on human mental and visual perception, exploiting their psychedelic properties. This type of use has historically been seen within Native American tribes and ancient civilisations. Recently more research shows that they may potentially be useful in therapeutic doses in the treatment of pain, depression, alcoholism and other behavioural problems. An example of this is Codorphone, an analgesic that can be both an agonist and antagonist at ÃŽà ¼-opioid receptors in the body and shows a higher potency than codeine. As a result, efficient synthetic routes that produce high yields have been developed in order to produce synthetic analogues of these natural compounds, with special attention being paid to the cyclopropanation step. Over the years there have been many methods of cyclopropanation, from using zinc carbenoids (Simmons-Smith reactionà [5]à ) to stabilised ylides (Corey-Chaykovsky Reactionà [6]à ), all producing varying ratios of isomers of the product. Often, one enantiomer is the more biologically active molecule, therefore stereoselective reactions are required to obtain high yields of the desired product. The Wadsworth-Emmons cyclopropanation reaction is an example of a reaction that is selective for the generation of the trans-isomer and has advantages over other stereoselective reactions. 1.1: Chemistry of the Cyclopropane Ring Cyclopropane is the smallest of the cycloalkanes that can be formed and consists of three sp3 hybridised carbon atoms bonded to each other to form a triangular ring. Although it is the smallest cycloalkane it is also the most reactive due to the bond angle within the ring. The ideal bond angle for sp3 hybridised carbons is 109.5à ° as it at this angle that orbitals can overlap correctly and form the highest strength carbon-carbon bonds possible. As the propane ring is planar and made up of only three carbon atoms, a bond angle of 109.5à ° is not possible and is reduced to a bond angle of ~60à °. In order to achieve bond angles of 60à ° the sp3 orbitals need to form bent bondsà [8]à where their p-characteristics are increased, causing the carbon-hydrogen bond length to shorten (figure.2). It is this significant difference between the ideal bond angle and the actual bond angle exhibited that causes a high amount of ring strain. Also, the bond angle and the modified overlap of orbitals results in carbon-carbon bonds which are weaker than normal. In figure.3, as the ring size increases from cyclopropane to cyclohexane, the ring strain decreases because the ideal bond angle is reached (when in a planar conformation) and larger rings can assume a non-planar conformation. In comparison to cyclopropane, the most strained and planar ring, cyclohexane has ideal bond angles and can form both chair and boat folded conformations in order to be the least strained ring possible. Further strain in the cyclopropane ring is due to the planar conformation of the molecule, where the two hydrogens present on each carbon atom are in an eclipsed position (figure.4)2. The carbon-hydrogen bonds are locked into this high energy conformation, as the carbon-carbon bonds of the ring are unable to rotate to form a more staggered conformation and reduce torsion strain. The total strain felt by the molecule leads to the ring structure being highly unstable and is ultimately responsible for the high reactivity of cyclopropane. Due to instability, the cyclopropane ring is able to break open very easily and releases a lot of energy in the process. This ring strain causes cyclopropane to release more energy on combustion than a standard strain-free propane chain. 2: Precursors of the Wadsworth Emmons Cyclopropanation Reaction As with most reactions the Wadsworth-Emmons cyclopropanation reaction is simply a different application of an older reaction, the Horner-Wadsworth-Emmons reaction, which has the purpose of forming E- alkenes selectively. This in turn is a derivation of the original Wittig reaction first discovered in 1954 by Georg Wittig in which phosphonium ylides are used in order to form alkenes products from aldehyde or ketone reactants. 2.1: Wittig Reaction The Wittig reaction is very useful in that it will form a carbon-carbon double bond in one site specifically on the desired molecule but the stereoselectivity of the reaction is controlled by the type of phosphonium ylide used. An ylide is a species that carries a positive and a negative charge on adjacent atoms of the molecule, and in this instance it is a phosphorus atom that carries the positive charge. As seen in scheme 12, the negatively charged carbon atom of the ylide acts as a nucleophile towards the carbonyl of the ketone (electrophile) and forms a betaine species. The betaine cyclises into an oxaphosphetane ring which quickly collapses to form a very strong phosphorus-oxygen double bond and results in the production of an alkene and a triphenyl phosphine oxide. When an unstablised ylide is present in the reaction, the kinetic isomer (Z-alkene) is produced preferentially (figure. 5)2 as the intermediate oxaphosphetane ring forms irreversibly. As the stereochemistry of the substituents are locked into a syn-conformation (figure. 7), when elimination of the triphenyl phosphine oxide occurs the alkene formed has its substituents on the same side of the plane. When the negatively charged carbon is adjacent to an electron withdrawing group (EWG), in figure 6 this is represented by the ester substituent, the ylide group becomes more stable as the charge can be dispersed. This leads to the formation of the enolate resonance form and is referred to as a stabilised ylide. Unlike the unstabilised ylide, the oxaphosphetane ring that is formed is now a reversible reaction allowing interconversion between Z-orientation to E-orientation of groups in the ring before an elimination step occurs. Under the right conditions, the interconversion step can become faster than the elimination of phosphine oxide step (collapse of the ring) allowing the reaction to proceed via the thermodynamic product route. The E- isomer is the thermodynamic product as the anti- conformation (Figure.7) of the oxaphosphetane ring has the substituents on opposite sides of the molecule, reducing steric effects and producing a conformation lower in energy. The elimination of the Z-isomer is slower than that of the E-isomer, allowing the oxaphosphetane ring to open and rotation about the carbon-carbon bond to occur to form more of the E-isomer. Although the Wittig reaction works efficiently with simple carbonyl reactants, the more sterically hindered a ketone reactant is, the slower the reaction can become. This does not necessarily have a negative effect on the yield of product but will affect the suitability of the reaction in time sensitive application, e.g. the commercial industry wants a high yield of product with a moderately fast synthetic route in order to keep costs low. 2.2: Horner-Wadsworth-Emmons reaction The Horner-Wadsworth-Emmons reactionà [9]à (scheme 2.) is the preferred method to select for the E-alkenes product and instead of using phosphonium ylides (figure 6.) uses much more nucleophilic phosphonate-stabilized carbanions with an EWG attached, usually in the form of phosphonate esters. Firstly, the phosphonate ester is deprotonated using sodium hydride leading to the generation of an enolate species. This enolate/stabilised carbanion is then reacted with the chosen aldehyde or ketone to give product. As a result of its more nucleophilic nature, similar or better yields are produced and faster rates of reactions for aldehydes and ketones that are more sterically hindered are observed. The stereoselectivity of the reaction for E-alkene can be further increased by modifying the reaction conditions and the substituent groups of the phosphonate ester (figure 8.)à [10]à . The larger the alkyl groups attached to the phosphate and ester functional groups the greater the propor tion of E-isomer obtained. Using the same idea, the larger the substituent group attached to the aldehyde/ketone reagent a more improved E-selectivity is seen, for example a phenyl ring. Increasing the temperature of the reaction to room temperature (23à °C) and changing the solvent from THF to DME will also encourage E-selectivity. Figure 9 shows that the pka of the HWE reagent is lower than that of the Wittig reagent and this is due to the ester EWG on the adjacent carbon to the acidic hydrogen. The EWG helps to stabilise the carbanion that will be formed by the loss of hydrogen making the phosphonate ester a stronger acid than the phosphonium salt, whose conjugate base will be less stabilised. As seen in Scheme 2, along side the E-alkene, there is a water soluble phosphate molecule present in solution. Due to its solubility, the recovery of the pure product from the solution can be done via a simple work up and this is one of the advantages of the HWE reaction over the use of stabilised ylides where a à â⬠3 phosphine oxide is formed. Through Wadsworth and Emmons investigations into the formation of alkenes such as stilbene in 19619, it was reported that the use of phosphonate carbanions was a more cost effective process that led to faster rates of reactions. It also produced very good yields in more mild conditions in comparison to stabilised phosphonium ylides. Phosphonate carbanions have a greater scope in number of different ketone and aldehyde reagents that they can successfully react with. Comparing both methods, when using stabilised ylides the resulting solution will contain a mixture of the isomers and therefore a suitable method is needed in order to separate them. Scheme 2. 2.3: Wadsworth-Emmons Cyclopropanation Similarly to the HWE reaction and keeping in mind the steric effects of large substituents, the reaction uses phosphonate-stabilised carbanions like the phosphonoacetate anion with epoxide and lactone reagents in order to form trans-cyclopropane rings within molecules. As seen in scheme 3à [12]à , the phosphonate carbanion acts as a nucleophile towards the electrophilic carbon of the epoxide resulting in the opening of the strained ring. Due to the negative charge present on the oxygen atom the phosphoryl group undergoes 1, 4 migration on to the oxygen, forming another carbanion. The carbanion can then cyclise leading to the ÃŽà ³-elimination of the phosphono- ÃŽà ³-oxyalkanoate and the closure of the cyclopropane ring. These stabilised phosphonates give a similar yield of trans-cyclopropane to reactions using phosphonium ylides but with faster reaction times and improved diastereoselectivityà [13]à . 3: Other Methods of Cyclopropanation In order to understand how effective the WE cyclopropanation reaction is and its advantages, other methods with slightly different approaches to the same problem can be looked at. 3.1: Simmons-Smith Reaction First developed in 1958, the Simmons-Smith reaction uses the chemistry of carbenes groups, producing cyclopropyl rings from the interaction between alkenes and a carbene derivative, zinc carbenoid. A standard carbene is a neutral species containing a carbon atom with only six valence electrons2 and can be inserted into à Ãâ-bonds and/or à â⠬-bonds of other reagents. Examples of these carbenes are :CH2 and :CCl2, where the whole carbene reagent is incorporated into the final product structure. In cases using reagents like :CCl2, further steps are required to remove the halide atoms if a standard cycloproyl ring is desired. In comparison, the zinc carbenoid is a species capable of forming carbenes but does not react in exactly the same way as them. The zinc carbenoid is formed by the insertion of a zinc atom into a molecule diiodomethane using a copper catalyst, as seen below, and its mechanism of action is compared to that of a singlet carbene where the reaction is concert ed. The carbon structure (-CH2) within the zinc carbenoid is incorporated into the cyclopropyl ring whilst the resulting metal halide is released into solution. This is done via an intermediate complex formed between the alkene, carbene and metal halide so that the carbene is not released on its own. One of the advantages of this method of cyclopropanation is the ease with which the stereochemistry of the product can be controlled. As the reaction is stereospecific, in order to obtain a product with a trans-cyclopropane ring, an alkene with E- stereochemistry can be used as the original stereochemistry will be retained. The rate of reaction of this can be dramatically increased by the presence of allylic alcohols with the same stereochemistry as the alkene, as the zinc atom can coordinate with the oxygen in a transition state to add the carbene to the same face of the molecule. The example below (figure. 10)à [14]à shows that this reaction is extremely effective at producing hig h yields of trans-cyclopropane product. Scheme 4. This reaction exhibits easy control over stereoselectivity and undergoes a relatively simple mechanism, making it easy to understand why this is one of the most popular methods of cyclopropanation. A disadvantage that the WE cyclopropanation reaction does not share is that there will have to be further steps taken in order to remove the product from the solution containing the zinc halide (insoluble) whilst preventing impurities being obtained. Although in some instances the Simmons-Smith reaction has greater stereoselectivity than the WE cyclopropanation reaction with comparable yields. 3.2: Corey-Chaykovsky Reactionà [15]à This reaction uses sulphonium ylides, as opposed to the phosphonium ylides of the Wittig reaction, reacting with enones in order to form cyclopropyl structures in the molecule. Firstly there is the generation in situ of the dimethyloxosulfonium methylide, often called the Corey-Chaykovsky Reagent (CCR), from dimethyl sulfoxide and methyl iodide reacting to give a trimethyl sulfoxonium iodide salt. This salt is then deprotonated using a strong base like sodium hydride resulting in the CCR. In the mechanism of cyclopropanation, the CCR acts as a methylene transfer agent, with the carbanion acting as a nucleophile towards the alkene carbon-carbon double bond of the enone. This 1, 4 addition is followed by cyclisation within the molecule using the new carbon double bond reacting as a nucleophile toward the now electrophilic ylide carbon to form the cyclopropyl structure and a sulfonium cation (Scheme 5). In an attempt to make the reaction stereoselective more substituted sulfonium ylides with specific chirality can be used to encourage the formation of a specific enantiomer as they transfer other substituents to the enone as well as methylene (figure.)à [16]à . Scheme 5. 4: Uses of the Wadsworth-Emmons Cyclopropanation Reaction Though there are only a few specific examples of WE cyclcopropanation in action, a good idea of its efficacy can be obtained. 4.1: Synthesis of Belactosin Aà [17]à (+)-Belactosin A is a naturally occurring antitumor antibacterial compound that acts as an alkylating agent in chemotherapy treatment. As an alkylating agentà [18]à it adds alkyl groups to electronegative groups such as phosphates or the amines found on guanine nucleotide bases, which are present in all cells of the body, although it is used to target mutating cancer cells. Belactosin A specifically stops the cell cycle of cancer cells at the G2/M phase, where normal DNA will have been replicated and the cell undergoes mitosis. In mutated DNA, the areas on the nucleotide bases affected by alkylation form cross bridges with other atoms on the complementary base of the opposite strand of DNA. These bridges prevent the DNA strands from separating at these specific points, stopping steps such as transcription. As a result this prevents the mutated DNA from being copied, cells from dividing into more cancer cells and halts proliferation of these cells through out the body. It affects mutated DNA cells more readily as they undergo cell cycle at a faster and uncontrolled rate and their repair mechanisms are less effective. Armstrong and Scutt reported a good yield of 63% of the cyclopropane intermediate with greater than 95%e.e. By using H1 NMR and NOE they determined that the product obtained was the trans-isomer. 4.2: Synthesis of (R,R)- 2-Methylcyclopropanecarboxylic Acidà [19]à In agriculture and veterinary practices, insecticides like Cyromazine and Pyrethrum Extract4 are formed using the WE cyclopropanation reaction in the synthesis of (+) and (-)-chrysanthemum dicarboxylic acids from anhydro sugarsà [20]à . The pyrethroids are active molecules that prevent normal transmission and excitation along the nerve cells in insects by acting on sodium/potassium channels. This results in immediate death to agricultural pests such as locusts and parasitic insects such as ticks and fleas on household pets. Due to the number of nerve cells and the speed of transmission these insecticides are up to 100 times more effective on insects than humans. Consequently, Pyrethrum extract can be used pharmaceutically without detrimental effects in the treatment of worms and scabies. Using the WE cyclopropanation method to obtain the biologically active enantiomer, Brione and company obtained excellent product yields of ~85-90% with exceptional trans-selectivity (>98%). These results were obtained under the conditions of 150à °C with HexLi/MeTHF solvent. 5: Conclusion Whilst the WE cyclopropanation reaction proves itself to be a useful step in the mechanism of formation of a few interesting biologically active compounds, the fact remains that it is an underused method. This is shown in the small volume of literature that can be obtained specifically for this reaction. As with most reactions the right balance of factors and reaction conditions are needed to get the most efficiency, and excellent yields have proved that the WE cyclopropanation reaction is capable of this in the cases of (R, R)- 2-Methylcyclopropanecarboxylic Acid and Belactosin A. Perhaps one of the reasons it is overlooked as a synthetic route is the presence of better known reactions like the Simmons-Smith reaction, as there are still some small areas that are not fully known e.g the degree of specificity of the reaction. The field of chemistry is one based on the evolution of ideas and continued search for improved yields and rates of reaction, especially in a growing area such a s the synthesis of synthetic analogues of natural compounds. In the same way that the WE cyclopropanation reaction was derived from the Wittig reaction, it could provide as a good basis for future improved methods of cyclopropanation that arise from the modification of its reagents.
Wednesday, September 4, 2019
Cuisine Essay -- Health, Food
A cuisine cannot simply be defined as a particular group of food associated with a geographic location. To understand a cuisine equal understanding of the culture to which it belongs must exist. A culture, such as the population of Italy, manipulates the presentation and substances of a cuisine to something representative of that culture. This makes a cuisine much more than food on a plate; a cuisine includes history, both of those making the dish and the ingredients and cooking styles that form the final product. A cuisine includes pride of nationality and personality. Similarly culture is more than a geographic location; it is a way of living and a respect for a group of beliefs and traditions. To understand this relationship between culture and cuisine certain information must be addressed; information such as the demographic figures surrounding a culture, the specific effect Italian culture has on Italian food, as well as the ingredients and cooking skills applied in the Italian cuisine. Consequences of the Italian cuisine will also be identified, both nutritional value and health detriments and how these effects may continue into the future. Cuisine can be split into two stages: pre-swallow and post-swallow (Crotty 1995). Pre-swallow is based around social aspects of cuisine (Gallegos 2011) such as who does the cooking and why people eat the food that they eat. Post-swallow is concerned with the effects food has once eaten; post-swallow also deals with the nutritional and health impacts that food has on consumers. When deconstructing a cuisine it becomes clear that demographic information plays an important role in the pre-swallow stage. Gender, age, location, religion and government influence all have a contribution to s... ... continue to rise. A symptom of obesity, cardiovascular disease, remains the highest cause of death in Italy at 16% (World Health Organisation 2006) followed by cerebrovascular disease, better known as a stroke, at 14%. Both of these diseases are caused by diet, particularly a high cholesterol diet and with western food chains such as McDonalds becoming more entrenched in Italian culture it is reasonable to believe these causes of death will remain the same into the future unless a regression into healthy local Italian cuisine is taken. To conclude, Italy is a diverse location both in terms of geographic regions and cultural traditions, it is only fitting that it has a diverse cuisine, full of history, religion and most important of all the soul of the Italian people. Its mark on world cuisine through innovation and passion last a long time.
Tuesday, September 3, 2019
Sumerian Culture :: essays research papers
While researching Sumerian culture I learned many interesting things that I was not aware of before. Many little known facts about Sumer will change the way that people feel about other ancient societies. Many advances that are not attributed to Sumeria, often were pioneered by this advanced culture long before others. Most people don't even know much about the origan of the Sumerian culture. The people who originally lived in Sumer in 4000 BC were not really Sumerians. Sumers original inhabitants were in fact Ubaidians. The Ubaidian culture was already quite advanced for that time, and had a large variety of unique farming techniques. Between 4000 and 3000 BC Sumer was infiltrated by many nomadic tribes. This constant movement of peoples caused a cross-fertilization of culture. Technology from many different regions were becoming centralized in Sumer. So were different theological viewpoints. During this millennium the people that we think of as Sumerians moved into Sumer. These people originated near the Caspian sea and did not even arrive in Sumer until 3300 BC. When these people ended up in Sumer it created the worlds first "high civilization". All who lived in Sumer were now recognized as Sumerian, because Sumerian was the common language. Sumer, like most early middle-eastern nations, was in the fertile crescent. These small waterways provided excellant irrigation, and transportation. Sumer was one of the first large civilizations that had a very developed textile industry. Wool sheared from goats and sheep was made into garments. The usage of linen was reserved for only high priests and other dignitaries. Flax and wool was used for everyone else. Farming was also a very predominant industry in this nation. All of the mixed culture taught the Sumerians about many different farming methods. Sickles and other tools aided in the farming. The harvested grain was preserved in granaries and pots. This allowed grain to be shipped without spoiling or molding. All of the waterways in Sumeria allowed products to be shipped up and down rivers to other destinations. One popular shipping method was called the "Turnip". The turnip was a buoy shaped boat that was attached to a long rope. The turnip would float along in the water, while the merchant rode on horseback on a near by road. Transportation methods increased in efficiency and new types of them arrived during the Sumerian rule, for instance, more types of boats were invented, and the Sumerians introduced the sail to the world of travel. The wheel was also first implemented in the Sumerian nation. When these advanced forms of transportation were not available, people still used donkeys with baskets strapped to their sides. Iron working was used to create tools that aided
Monday, September 2, 2019
Essay on Mr. and Mrs. Bennets Parenting in Pride and Prejudice
Analysis of Mr. and Mrs. Bennet's Parenting in Pride and Prejudiceà à The roles of Mr. and Mrs. Bennet in Jane Austenââ¬â¢s novel Pride and Prejudice are contrasted between a father who cares about whatââ¬â¢s inside of people and a mother who only worries about vanity and appearance. Mr. and Mrs. Bennetââ¬â¢s parental guidance is unique to their personalities. Because of their two opposing personas, Mr. and Mrs. Bennetââ¬â¢s ideas of marriage are contradictory for their daughters; Mr. Bennet believes in a loving respectful marriage whereas Mrs. Bennet values a marriage which concerns wealth and social status. Their aspirations for Lydia, Jane, Mary, Kitty and Elizabeth mirror their conflicting ideologies. Mr. Bennet seems to have a quiet deep love for his daughters while, on the contrary, Mrs. Bennetââ¬â¢s love is over-acted and conditional. Both parents help to shape their daughtersââ¬â¢ characteristics and beliefs: Lydia reflecting Mrs. Bennetââ¬â¢s flighty and excessive behavior while Elizabeth inherits Mr. Bennetââ¬â¢s pensi ve and reflective temperament. Looking past their dissimilar personality traits and contradicting convictions, both parents hold the family together and play an integral role in the household structure. à à à The constant topic among the majority of the women in the Bennet household was marriage and future suitors. Mrs. Bennet prides in the hope that someday all her daughters will be married off to wealthy individuals who can even help support the Bennet family and increase their social status: ââ¬Å"The business of her life was to get her daughters married...â⬠(9). Mr. Bennet, on the other hand, only cares to see his daughters happy and content with themselves. Although Mr. and Mrs. Bennetââ¬â¢s estate is endowed to Mr. Collins, Mr. Benn... ...igued with the raptures of his wifeâ⬠(9). Their children provide them with companions as well as people to take their sides. Mr. and Mrs. Bennetââ¬â¢s relationship revolves around their children because without them, they would have an impossible time living alone together. à à à When evaluating Mr. and Mrs. Bennetââ¬â¢s role in the family structure, they both provide insight into the origins of their daughtersââ¬â¢ personalities. Mr. and Mrs. Bennet both play integral parts in their childrenââ¬â¢s lives; they give or attempt to give them guidance in marriage, in happiness, and in love. Whether itââ¬â¢s Mrs. Bennet expressing her over-bearing love or Mr. Bennet giving Elizabeth some well-needed advice, they both aim to help their daughters using their inborn parental love. Works Cited: Austen, Jane. Pride and Prejudice. Ed. Donald Gray. New York: WW Norton &. Company, 1996.
Sunday, September 1, 2019
Macduff vs. Macbeth: a True Case of Good vs. Evil?
Macduff vs. Macbeth: A True Instance of Good vs. Evil? At the end of the play Macbeth, Macduff kills Macbeth in a scene easily read as the victory of good over evil, but is this accurate? Is Macbeth completely evil? Is Macduff completely good? Or is there an in between? I believe that Macduff is good, but there is definitely an in-between with Macbeth. I see Macduff as being a good person. He does everything he can to improve the state that Scotland is in. When he flees to England and leaves his family behind, some people may interpret it as him doing bad since his family is slaughtered in his absence.I do not see it this way. I believe Macduff is doing what he thinks is best for Scotland when he flees to England. That is to get Malcolm to come back and take his rightful place as king of Scotland. This is evident when Macduff is in England talking to Malcolm. Malcolm says ââ¬Å"let us seek out some desolate shade, and there/weep our sad bosoms emptyâ⬠(4. 3:1-2, Page 70). Basic ally, he is feels sorry for the state into which Scotland has fallen since Macbeth has become king. To this Macduff replies ââ¬Å"Let us rather hold fast the mortal sword, and like good men bestride our down-fallââ¬â¢n birthdomâ⬠(4. :3-4, Page 71). This translates to ââ¬Å"let us rather hold fast the deadly sword, and like good men protectively stand over our native land. â⬠Basically what Macduff is trying to say is that instead of crying for Scotland, they should fight for their land to bring her back to the state they knew and loved. Further on into this same conversation, there is further proof that Macduff was seen as good. He tells Malcolm ââ¬Å"I am not treacherousâ⬠to which Malcolm replies ââ¬Å"but Macbeth isâ⬠4. 3:18-19, Page 71).This also goes toward the argument of Macbeth being evil. He is seen as treacherous and a tyrant. He brings sadness to Scotland. Macduff says that ââ¬Å"each new morn/New widows howl, new orphans cry, new sorrow/Stri ke heaven on the faceâ⬠(4. 3: 4-6, Page 71). This is just a hint of how bad the state of Scotland has gotten. Macbeth is also evil in that he murdered and framed people to become king of Scotland. He murdered the current king, Duncan, and made it appear that the guards in his chambers of the crime.He was told by the Weird Sisters that he would be king. He was just too impatient to wait his turn and turned to murder instead. Although he did do a lot of things that could be considered evil, I do not believe that Macbeth was wholly evil. He was brave and seen as a hero in the war against Norway. This heroism even got him the title of Thane of Cawdor. Banquo didnââ¬â¢t seem displeased at the prophecies of Macbeth becoming Thane of Cawdor and King. If Macbeth was evil, Banquo would have been displeased with this.He can also be seen as not wholly evil because he is hesitant in his plot to kill the king. Lady Macbeth has to help to convince him to do it. If he was wholly evil, he would have had no hesitation in murdering someone for his own gain. Due to the mix of good and evil in the character of Macbeth, there is definitely some gray area to the play. I think this gray area adds depth to the play. Not everyone is interested in straight good and evil. Some prefer a round, conflicted character such as provided by the character of Macbeth.
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