Do you have to believe in Reason to believe in Democracy Essay - 1

Do you have to believe in Reason to believe in Democracy - Essay Example As such, it is prudent to acquire â€Å"education and to work with dignity; to love our families, our communities, and our God† (Obama). Though some nations are not well developed, they have to make different approaches in strengthening their democracy. There are reasons why people should believe in democracy. â€Å"More recently, tension has been fed by colonialism that denied rights and opportunities to many† (Obama). Their rights were infringed as the colonial era was still ruling. With such instances, people felt that there was a need for another approach in salvaging the situation. This was an initiative that would bring a better solution to the people that felt they were infringed as they did not exercise their rights. This is the initial step in people believing in democracy. Democracy was the initial approach which enabled people to start advocating their rights. Without democracy, gender equality would have never been annihilated. Apparently, women are to be gi ven equal opportunities just as the male gender. Obama states that women should not be regarded as lesser human beings as they are equal to others. He states, â€Å"I do believe that a woman who is denied an education is denied equality† (Obama). As such, the president of the United States insists that there should be corporation and coexistence between the male gender and female gender. This is one of the fruits that have been achieved through democracy. Though colonialism instigated some tension on the rights of people, this is an era that has been alienated. Therefore, people should focus on giving others equal opportunities which will instill democracy and disciplined existence in the human fraternity. Democracy is a social way of expressing people’s views. Obama states that some relationships are strengthened by divergent views of people. He states that there is a need to empower people that embrace peace, as this will help solve conflicts. As such, there will be justice and prosperity. The society has a large number of people that had divergent views. As such, they will continue to express their divergent views in different places. Since the society has a large number of people, some people will be forced to have the same reaction with others. This creates a scenario where some communities in groups are of a similar opinion. Consequentially, Obama states that there is a need to seek reconciliation between the United States and the Muslim fraternity. A new beginning will enhance â€Å"principles of justice and progress; tolerance and the dignity of all human beings† which will pave the way for greater democracy (Obama). This stimulates their unity as they would wish to fight for their opinion. When a larger group of the community is in support of a particular opinion, it is evident that the larger community will push their opinion to greater heights. As such, their decision will be highly accepted. This is backed by the many supporter s that are of the same opinion. Therefore, believing in democracy is a good reason to push forward views that are acceptable by a larger number of people. If this is not done, the opinion of many people in society will not be adhered to. This limits the continuity of society especially in making vital decisions. Democracy is a way of enhancing progress and development. It helps people and the community to shape their lives. For instance, people that shape up the community are people in power. These are the people that have a mandate to control the

Importance of Book of Romans to the History of the Church Essay Example for Free

Importance of Book of Romans to the History of the Church Essay The Book of Romans is the one of the Letters in the New Testament of the Christian Bible.The Writing is   simply reffered as the Romans and is currently one of the undisputed work of Paul.The book has been described as a masterpiece which overwhelms the reader by the sublimity and the density of the topic which are discussed,the justification of the gospel and the revealing of the uprightness and the grace of God to all the people ,both Jews and the Gentiles. The book is a letter which is written in a Greek first century traditional letter writing style. During this time the writers started by identifying themselves and then names of the person they were sending the letter and then followed by the greetings. The letters usually closed with the final greeting and blessings. The book of Romans followed the same style (Barth, K 1968) There existed a group of believers in Rome who trusted in Jesus as Messiah long before Paul had planned to visit this town. There was a conflict between the Christian Jews and the new group up to the point that the Roman Emperor expelled them from Rome. More often there was a disagreement between the Jews and the gentiles concerning what made one an acceptable person to God and the way the followers of the Christ should conduct their lives. Having noticed the differences that characterized the church in Rome Paul decided to shed some light as far as the differences were concerned. There were people who were going from door to door teaching doctrines which were confusing and misleading to the faithful. There are some who were saying that for one to be accepted in the kingdom of God one has to refrain from eating particular kind of food and had to strictly follow the Law of Moses. These are issues that the book of Romans aimed at addressing so that this confusion that existed in the church can be cleared. Therefore to the church in Rome the book was basically a tool of reference as far as what was expected of them was concerned. One of the reasons for Paul writing this book was to answer some of the question that emerged between the two groups. He boldly put it out in the book that the word of God was for all whether Gentiles or Jews. (Moo, D1996) The book of Roman is basically a treatise which is addressed to the church in Rome where Paul was introducing himself before he made his visit. Justification of the faith was the central theme for his letter. He was delivering the message that it is only through salvation that a man can have a good relationship with God. Anything else did not matter. What was expected from every Christian whether Jews or Gentiles was the faith in God and through this salvation will be achieved. He explained that the Mosaic Law was not enough to make the Christian righteous. This works serves as an eye opener to the early church as some of the issues that were controversial at this time were clearly explained by Paul. The differences that threatened to tear apart the church were tackled in this writing. To the Jewish Christians Paul explained that God had not completely broken his promise with them but he was working towards redemption of all the people in the universe.   For a long time Paul was planning to visit Rome but he was hindered from making such a move. Now he was determined to do it, he wanted to greet them and introduce himself before he made that journey. This visit was very important to him and the church in Rome as both were anxious. Paul was not sure how he was going to be received in this city and the some people there had criticized him before as they did not think he can be the leader of the church which was led by the Gentiles. The book of Romans serves as the assurance to the church in Rome that they are accepted in the kingdom of God like any other group despite them being Gentiles. Therefore Paul was mainly writing this book to assure this group that they also had a right and a share in the kingdom of God. He assures them that Jesus died for all regardless of their status. The most important thing for any Christian was repentance and acceptance of Jesus Christ and leading a holy life. (Moo, D1996) Paul believed that the culture of Romans was very important as far as the church was concerned. It was the most powerful empire in the world and was located in the middle of the world at the time of Paul evangelism. This fact made the Church of Rome very important to the world at large. He understood the great effect this church would have on the rest of the world especially the so called civilized world of that time. He clearly saw the need of systematic and full presentation of the good news in this city. The people in Rome were looking forward to Paul visit in Rome as it would serve a great role as far as their church was concerned. This visit was taken as a formal recognition that a church that was led by the Gentiles. They had for a long time wondered how he can be an apostle of the church yet he fail to visit their church in Rome. This gave the church leaders an opportunity to gauge and judge his courage and honesty as far as the church was concerned. The book of Romans clearly explains the doctrines of the Christian faith. Paul in this book defended the gospel from those people who were claiming that salvation was for a chosen group. The church in Rome was to serve as a pillar where the Christianity would be spread to other regions in the world. The book clearly assures that the Roman church was as legitimate as the other despite the fact that it was led by gentiles. This served as a boost to this church as Paul was taken as the messenger of God and he was presenting the God word to the people who had chosen to follow Christ yet the society was not keen to respect them. Paul addresses them as his brethrens a clear indication that he had accepted them as one of them and they were on the right track as far as faith was concerned. (Moo, D 2002) The book of Romans had a great impact on the early church and the western civilization at large.Scholars has argued that the book is the most influential in Christian history. It is in this book that Paul gives a detailed exposition of the word of God. It is the most fundamental and systematic discussion as far as the whole plan of salvation is concerned. To the Romans the book touched on what they were supposed to do so that they can be saved. This applies to all the Christians and was largely quoted by the protestant reformers as they assured the faithful that the kingdom of god was reserved for all those who had faith in Him and they did not need the blessing of any man on earth for them to be allowed access into this Kingdom. The book was universal in application despite the fact that it was directed to the Church in Rome. (Moo, D1996) The book of Romans had greatly influenced many people in the history of the church. The prominent theologians like Martin Luther had studied the book making them aware of what God expected from them. Martin Luther found the teaching of salvation by the grace clear and he used it to spearhead the reforms in the church where he assured the faithful that it was through faith and grace alone that they were to be saved not from paying indulgences and other kind of injustices that existed in the church during the middle ages. (Dillenberger, J 1961) The protestant reformation was basically a recovery of the right and pure gospel which resulted in the increased gospel spread to the different parts of the world. It was a revival of the Apostle’s Paul work where he made a journey to various parts of the world taking the good news. Through studying the book of Romans Martin Luther’s life was completely changed and so is the history of the church. The protestant reformation was as a result of this great theologian reading the book as the teaching was made available to the public. Lives were changed as the message of hope and righteousness was spread far and wide. The book clearly states that there is no Christianity without Jesus, he who comes to know him shall be saved. Martin preached the same message that Paul wrote to the people of Rome and the early church. Martin Luther described the book of Romans as the purest gospel which is worth and every Christian should understand it clearly. He advises the believers not to take the word law in human terms as through doing this they will be confused as the people in the early church and they will be serving the church rather than living according to the will of God. He teaches them that God judges his people according to the heart. His law can not be satisfied by the works but rather on the inner most heart. He got these ideas from reading the work of Paul to the Romans. A book that he describes as full of inspiration to him and his search for the truth .Paul says that all people are sinners in the eyes of God and for us to be saved we have to seek the kingdom of God through following his teachings rather than following the law or the traditions as was the custom with the Christian Jews. If believers accustom themselves to the language described by Paul in the book of Romans Martin Luther says that they will find that there exists a difference between what the traditions of the church prescribe and what God really expects. (Dillenberger, J 1961) Through the inspiration he received from the book of Romans Luther was able to challenge the church. The evils that characterized the church at this time has made him very disturbed and he set out on a mission to discover what can bring him close to God. The message he got was derived from the book of Romans where he realized that it was only through the grace of God that all will be brought close to God. The church was extremely corrupt where things that were going on were contrary to God’s expectation. Through the inspiration he was able to revolutionize the church and brought the light just as Paul shed the light to the people of Rome concerning what God expected from them. Martin Luther described Romans as the main book in the New Testament .His wish is for every Christian to use the book as a guide in our daily lives. As the systems are bound to confuse them as far as their faith is concerned just like it happened during his time when the Roman Catholic Church used the teachings to justify some of the evil things that were happening. The letter of Paul to the Romans would serve as the guide to the church and the believers if they are interested in the righteousness. Luther says that people should be ready to confess Jesus with their mouth and in such a deed they will lead a righteous life as they will always aspire to do what God expects from them. Good deeds alone do not make a man righteous rather he should have faith in God. The book of Romans has been described as the one that changed the course of the church history right from the early church to the protestant reformation. Therefore it is in order to say that this book contains message which are inspirational and can bring a complete change in ones life. It changed the life of the Augustine together with John Wesley people who had led a life that was not pleasant before the eyes of God. They had struggled with the evils ways up to a point when the word was revealed to them changing their lives completely. John Wesley had set out to preach without being converted, after some years of struggling and failing he heard the teaching of Martin Luther describing the book of Romans. Listening to the true words of Luther the man was inspired and he was converted. He went to preach in many corners and has been described in the history of the church to have played a great role in the evangelical work of awakening the believers. (Moo, D 2002) The kind of life that God expects from every person is what has touched many people in the course of the church history. From martin Luther to John Wesley there was realization that God expects us to be righteous before his eyes as Paul maintained in the book. On the same line God’s wrath does not discriminate, it is expressed impartially to all the sinners neither does He discriminate between the Christian Jews and the gentiles. Before Paul sent the letter to the church in Rome the Jews prided to be the privileged people in the eyes of God but this notion was clearly explained by the book that set out to put the facts straight. On the same line the book of Romans came to be used in the protestant Reformation showing clearly that no one was too holy before the eyes of God to help in pardoning of the sins. Only God had the power to forgive the sins. The book as described by Luther addressed the issue clearly stating that no amount of payment towards indulgences was enough to forgive ones sins. (Moo, D1996) The book of Romans influence to the church has been enormous right from the time Paul wrote the letter to clear the differences that existed in the Church of Rome. It is as a result of that explanation that the Gentiles faith was strengthened after understanding what God stood for as far as righteousness was concerned. The book deals with the issues of sin, progressive sanctification, practical service and the gracious salvation issues that could have divided the church in Rome as Christian Jews and the Gentiles had different views regarding these issues. The book addresses God great plan for saving mankind by his grace. It clearly states that it is only through the grace of God that all those who believe in Him shall acquire this salvation. The book has been described as the comprehensive statement of faith and Christianity as a whole. It has been used by many believers to show what is expected of us and the church in general. The basis of the Christian faith is based on this book and this explains why the book has in many cases changed the course of the church history especially when some people are out to mislead the believers in the matter of faith. Martin Luther used the book to show how the church had turned to be evil and led a revolution that came to bring openness in the church allowing people to read the word for themselves. (Hodge, C 1994) The book of Romans importance to the Christian faith can not be underestimated; it has been relied on several occasions to shed light where misunderstandings have existed. The book has shaped the church making more responsive to the needs of a believer, trying as much as possible to reconcile the two issues of law and righteousness. The strong foundation of the Christian faith is found in this letter of Saint Paul to the people of Rome. Reference Dillenberger, J (1961) Martin Luther: Selections from His Writings, New York, Doubleday and CO Moo, D(1996)The Epistle to the Romans. Wm. B. Eerdmans Publishing Company Moo, D (2002) Encountering the Book of Romans: A Theological Exposition, Michigan, Baker Academic Barth, K (1968) The Epistle to the Romans. Oxford University Press, 1968. Hodge, C(1994) Commentary on Epistle to the Romans. Wm. B. Eerdmans Publishing Company

DBQ- minorities in world war II Essay Example for Free

DBQ- minorities in world war II Essay The following question requires you to write a coherent essay incorporating your interpretation of the documents and your knowledge of the period specified in the question. To earn a high score you are required to cite key pieces of evidence from the documents and draw on your knowledge of the period. It is often claimed that the major American wars of the last 150 years have resulted in the most important social and political gains of minorities and women. Evaluate this statement with regard to the experience of minorities and women during World War II. Use evidence from the documents and your knowledge of the period from 1941 to 1945 to compose your answer. Brigadier General B. 0. Davis to General Peterson, 9 November 1943 (Brigadier Davis had just completed an inspection of military bases in Massachusetts, New York, New Jersey and Michigan): â€Å"I was deeply impressed with the high morale and attitudes of the colored officers and soldiers stationed in the states visited in the past two months. They were so different from those of the colored officers and soldiers located in the Southern states. While there has been an improvement in general conditions, there is still great dissatisfaction and discouragement on the part of the colored people and the soldiers. They feel that, regardless of how much they strive to meet War Department requirements, there is no change in the attitude of the War Department. The colored officers and soldiers feel that they are denied the protection and rewards that ordinarily result from good behavior and proper performance of duty†¦.. The Press news items and reports of investigations show that there has been little change in the attitudes of civilian communities in Southern states. The colored man in uniform receives nothing but hostility from community officials. The colored man in u niform is expected by the War  Department to develop a high morale in a community that offers him nothing but humiliation and mistreatment. Military training does not develop a spirit of cheerful acceptance of Jim-Crow laws and customs. The War Department has failed to secure to the colored soldier protection against violence on the part of civilian police and to secure justice in the courts in communities near-by to Southern stations. In the areas recently inspected, the colored soldier feels that he can secure justice in the civil courts. He has not been set upon by the civilian police. He has not been denied the privilege of occupying empty seats in public buses, street cars, etc. taxicabs to serve him. This is not so in Southern communities.† President Roosevelt, Executive Order 9066, February 25, 1942: Whereas the successful prosecution of the war requires every possible protection against espionage and against sabotage to national-defense material, national-defense premises, and national defense utilities. I hereby authorize and direct the Secretary of War, and the Military Commanders whom he may from time to time designate, whenever he or any designated commander deems such action necessary or desirable, to prescribe military areas in such places and of such extent as he or the appropriate Military Commander may determine, from which any or all persons may be excluded, and with respect to which, the right of any person to enter, remain in, or leave shall be subject to whatever restrictions the Secretary of War or the appropriate Military Commander may impose in his discretion.† Korematsu v. United States, 1944. Mr. Justice Murphy, dissenting: â€Å"This exclusion of `all persons of Japanese ancestry, both alien and non-alien, from the Pacific Coast area on a plea of military necessity in  the absence of martial law ought not to be approved. Such exclusion goes over `the very brink of constitutional power and falls into the ugly abyss of racism. Individuals must not be left impoverished of their constitutional rights on a plea of military necessity that has neither substance nor support. Being an obvious racial discrimination, the order deprives all those within its scope of the equal protection of the laws as guaranteed by the Fifth Amendment. It further deprives these individuals of their constitutional rights to live and work where they will, to establish a home where they choose and to move about freely. In excommunicating them without benefit of hearings, this order also deprives them of all their constitutional rights to procedural due process. Yet no reasonable relation to an `immediate, imminent, and impending public danger is evident to support this racial restriction which is one of the most sweeping and complete deprivations of constitutional rights in the history of this nation in the absence of martial law† Congressman Rankin, Mississippi, February 18, 1942: â€Å"I know the Hawaiian Islands. I know the Pacific coast where these Japanese reside. Even though they may be the third or fourth generation of Japanese, we cannot trust them. I know that those areas are teeming with Japanese spies and fifth columnists. Once a Jap always a Jap.You cannot change him. You cannot make a silk purse out of a sows ear. Do not forget that once a Japanese always a Japanese. I say it is of vital importance that we getrid of every Japanese whether in Hawaii or on the mainland. They violate every sacred promise, every canon of honor and decency. This was evidenced in their diplomacy and in their bombing of Hawaii. These Japs who had been there for generations were making signs, if you please, guiding the Japanese planes to the objects of their inequity in  order that they might destroy our naval vessels, murder our soldiers and sailors, and blow to pieces the helpless women and children of Hawaii. Damn them! Let us get rid of them now!† Franklin D. Roosevelt, Fireside Chat on the Home Front, October 12, 1942: â€Å"In order to keep stepping up our production, we have had to add millions of workers to the total labor force of the Nation. And as new factories come into operation, we must find additional millions of workers. This presents a formidable problem in the mobilization of manpower. It is not that we do not have enough people in this country to do the job. The problem is to have the right numbers of people in the right place at the right time. In some communities, employers dislike to employ women. In others they are reluctant to hire Negroes. In still others, older men are not wanted. We can no longer afford to indulge such prejudices or practices. Women are welders [sic] discuss the production of motor mounts and welded parts in a welding booth at the Inglewood, Calif., plant of North American Aviation, Inc. 1942. National Archives and Records Administration. President Roosevelt, Executive Order 8802, June 25, 1941: WHEREAS it is the policy of the United States to encourage full participation in the national defense program by all citizens of the United States, regardless of race, creed, color, or national origin, in the firm belief that the democratic way of life within the Nation can be defended successfully only with the help and support of all groups within its borders; WHEREAS there is evidence that available and needed workers have been barred from employment in industries engaged in defense production solely because of considerations of race, creed, color, or national origin, to the detriment of workers morale and of national unity; NOW, THEREFORE, by virtue of the authority vested in me by the Constitution and the statutes, and as a prerequisite to the successful conduct of our national defense production effort, I do hereby reaffirm the policy of the United States that there shall be no discrimination in the employment of workers in defense industries or government because of race, creed, color, or national origin, and I do hereby declare that it is the duty of employers and of labor organizations, in furtherance of said policy and of this order, to provide for the full and equitable participation of all workers in defense industries, without discrimination because of race, creed, color, or national origin;

Strategies for Small Molecule Activation

Strategies for Small Molecule Activation Introduction Developing novel strategies for small molecule activation is the core aim of catalysis reasearch. One approach that recently gained prominence in catalytic activation of organic molecules is photoredox catalysis. Visible light photoredox catalysis has risen to the interface of current organic chemistry as a remarkable way to facilitate single electron transfer (SET) processes with organic substrates upon photoexcitation1. This technique relies on the property of metal complexes and organic dyes to undergo SET with visible light2. The commonly employed transition metal based photocatalyst used to harness the packets of energy carried by visible light are polypyridyl complexes of ruthenium and iridium, named as tris(2,2-bipyridine)ruthenium (II) or Ru(bpy)32+ (Figure 1). Figure 1. Structures of common transition metal photocatalysts. These complexes give stable, long-lived excited states (for Ru (bpy)32+*, à Ã¢â‚¬Å¾ = 110 ns)3 when irradiated with visible light of electromagnectic spectrum4. This relatively long lived excited state may allow bimolecular electron-transfer reactions through outer sphere transfer, both by the quenching of excited state photocatalyst and deactivation pathways5. The quenching can be accomplished in both oxidative and reductive ways (Figure 2), which offers this mode of catalysis flexibility. Figure 2. Oxidative and reductive quenching cycles within photocatalysis. Moreover, varying the metal (Ru, Ir, Cu, Cr,etc.) or ligands steer to foreseeable changes in redox potentials, enabling customization of the catalyst to ones needs. In contrast to classical approaches these photochemical methods offer surprisingly mild conditions to radical reactions, as they typically operate at ambient temperature, utilize bench-stable reagents and display high degree of functional group tolerance.6 The extensive application of visible light photocatalysts have been recognized in the field of inorganic and materials chemistry. In particular, these catalysts have been found to be actively decomposing water into hydrogen and oxygen7 and reducing carbon dioxide to methane.8 Also, they have been employed in (i) as components in dye sensitized solar cells9 and organic light-emitting diodes,10 (ii) in polymerization reactions,11 and (iii) in photodynamic therapy.12 Until recently the reports of using these complexes as photocatalysts in organic synthesis were scarce. Their limited investigation was very surprising, as single electron, radical processes offer   a unique pathway and reactivity to form C-C bond which are complementary to the closed shell, two electron processes.13 In the last decade detailed studies form the Yoons , MacMillan sand Stephensons groups have shown the application of Ru(bpy)32+ as photoredox catalyst to perform crucial C-C bond forming reactions such   as [2+2] cycloaddition,14 ÃŽÂ ±-alkylation of aldehydes15 and reductive dehalogenation of activated aryl halides.16 These quality work of above groups have   rejuvenated the interests of many researchers in this field, triggering the diverse ideas into the utility of photoredox catalysis as conceptually novel approach to synthetic organic reaction development. The application of visible light photoredox catalysis in organic synthesis revolves around its ability to engineer unusual bond constructions which are not easily formed by established protocols.   For instance, overall neutral redox reactions can be performed by photoredox catalysis, as both the oxidant and reductants can be generated within the same reaction vessel. Visible light photoredox catalysis has been proved to be convenient in designing reactions, which needs gain and removal of electrons at disparate centres in a reaction mechanism. In contrast to these methods, others require stoichiometric quantity of both oxidant and reductants, which many times are incompatible with each other. Radical intermediates generated from single electron transfer (SET) events have been shown to have different reactivity patterns fundamentally different from those accessed through the ground state of catalyst.17 Harnessing   these intermediates by means other than photoredox cata lysis are often challenging or requires conditions which are incompatible with substrates. It is noteworthy to mention, Ru (II) and Ir (III) based photocatalysts are widely used to generate radicals for use in a diverse range of radical reactions, and most of these reactions occur under mild conditions such as room temperature without the need of reactive radical generators (e.g., azobisisobutyronitrile (AIBN), BEt3), and toxic reagents (e.g., Bu3SnH), and in many cases, high temperature. The source of irradiation typically used are commercially available household light bulbs, which has significant advantage over specialized equipment employing high-energy ultraviolet (UV) light. Moreover, organic molecules generally do not show absorbance in visible region, so there is little probability of unwanted side reactions that might occur from the photoexcitation of the substrate itself. Even, the low photocatalyst loading of 1 mole % or less is sufficient enough to achieve high conversions. These all collectively have proven that visible light mediated photoredox catalysis to b e a uniquely well-suited in designing safer and more sustainable strategies for synthesising more efficient materials and reducing waste streams. Further incentivizing the design and application of novel visible light-mediated methodologies toward both natural and non-natural scaffolds of interest to pharmaceutical and agrochemical domains.18 This review highlights the earlier work done on the use of Ru (II) and Ir (III) transition metal complexes as photoredox catalysts to promote C-C bond forming reactions in organic synthesis. Specifically, there is great emphasis on the applications of visible light photoredox catalysis which have enabled the total synthesis of natural products and related molecules, focusing on a range of powerful transformations that include: reductive coupling, indole functionalization, radical cascades, ATRA reactions, trifluoromethylation and selective C-O bond cleavage. Reductive Dehalogenation Reductive deahalogenation refers to process in which a C-X bond is reduced to a C-H bond where X denotes halogens. These classes of reactions have attracted attention of organic chemists all over the world due to its prime importance in rational organic synthesis. For instance a significant number of examples of these reactions can be found in nature, where enzymatic dehalogenation is performed by microorganism present in soil to check the concentration of lipophilic halogenated species.19 There has been a whole library of reducing systems developed to carry out reductive dehalogenation successfully, which practically guarantees the existence of specific reagents for specific substrate. Organo-tin hydride has been the most used reagent in the past to perform reductive dehalogenation in laboratory as well as in field of synthesis, as it has been proven capable for both radical generation and kinetic radical trapping.20 By far, the system of tin hydride is tributyltin hydride (TBTH) (AIBN) is the most utilized for radical-promoted dehalogenations of organic halides.21 However, there are three main problems in use of TBTH. First, toxicity of tin rule out its use in pharmaceutical synthesis. Second, there are lots of problem associated with the purification of reaction mixture from tributyltin residues. Third, TBTH is not a stable compound, even after careful storage it is likely to steadily decompose.22 It is the toxicity, that has almost precluded its use in a wide range of useful radical reactions in organic synthesis. In recent years, the search for superior alternatives to TBTH has been the central goal of radical chemists. A replacement reagent needs to overcome all three problems mentioned above while at the same time an exhibiting similar reactivity and an ease of use. Earlier work of Fukuzumi and Tanaka focused on use of Ru(bpy)32+ as a photo redox catalyst to promote the reductive dehalogenation of phenacyl bromides23 and reductive dimerization of benzyl bromide24 respectively (Scheme 1), has shown that the application of visible light photoredox catalysis to access radicals can offer a promising solution to this problem. Scheme 1. Reductive dehalogenation of phenacyl bromide (A) and reductive dimerization of benzyl bromide (B). But, it was the efforts of Narayanam and co-workers, focussed on developing the novel means for accessing radical chemistry while avoiding the toxicity and problems associated with tin hydride, has laid a milestone in development of a tin-free reductive dehalogenation systems (Scheme 2.).25 Scheme 2. Photoredox catalytic reduction and potential C-C bond formation. In their primary investigation, Narayanam et al. used a system consisting Ru(bpy)32+ as a photocatalyst, iPr2NEt as major hydrogen atom source and visible light to successfully perform the reductive debromination. In the net transformation, the 3-bromopyrroloindoline (7) was reduced to pyrroloindoline (8) as single product, with the addition of Hantzsch ester or formic acid to the catalytic system produced debrominated product in >90% yield (Scheme 3). Scheme 3. Initial attempt for reductive dehalogenation. In further development of general tin-free visible light mediated dehalogenation protocol, a range of different activated alkyl bromides and chlorides were tested which afforded the corresponding dehalogenated product in good to excellent yield. Although, the un-activated aryl and alkenyl iodides were completely unreactive, as it was expected due to their exceptional negative reduction potentials  Ãƒâ€šÃ‚   (-2.24 V Vs SCE for iodobenzene).26 The solution to this problem lied in the use of Ir(III) based   photo-catalysts instead of   Ru(II), which offered more reducing power than Ru(bpy)32+,and the dehalogenation of less activated alky, vinyl and aryl iodides with good functional group tolerance was achieved using oxidative quencing cycle of fac-Ir(bpy)3 (Scheme 4).27   Scheme 4. Reductive dehalogenation of activated and unactivated halides. Furst et al. used this practical strategy for reductive dehalogenation for a further development of more challenging intermolecular C-C bond forming protocols, which demonstrated an efficient way to promote intermolecular additions using visible light mediated photoredox catalysis. Furst et al. reported a facile coupling of indole with malonate radicals, as malonate-like motifs are common C2-subsitutents in bioactive indole based alkaloids such as actinophyllic acid (9) and undulifoline (10). Using this procedure, an extensive range of indole and pyrrole derivatives were synthesized in good yields by employing (1) as the photocatalyst and N,N-diphenyl-4-methoxyaniline as the reductive quencher (Scheme 5).28 Further, this protocol was extended by Stephenson et al. to synthesize quaternary carbon centres adjacent to C2 of indole based alkaloids by employing more challenging tertiary malonate radicals.29 This transformation was accomplished by directly reducing bromomalonate (11) via oxidative quenching of more reducing fac-Ir(bpy)3 photocatalyst, providing targeted quaternary carbon centres in good to high yields (Scheme 6). Scheme 5. Intermolecular radical addition of secondary radicals to electron-rich heterocycles Scheme 6. Intermolecular radical addition of tertiary radicals to electron-rich heterocycles. Atom Transfer Radical Addition (ATRA) These transformations was first observed by Kharasch30 in 1940s, over the time atom transfer radical addition sparked the interest of organic chemists, as it offers the potential for uniquely efficient and economical approach for dual functionalization of olefins. This functionalization leaved a tremendous impact in organic chemistry, and have also found wide applications in industry and academic research. Similar to the intermolecular malonate-indole coupling mentioned above, these transformations are redox neutral, theoretically eliminating the need for additives, which in terms, reduces the likelihood of deleterious off-target reactivity. The most important application of atom-transfer radical addition reactions is inclusion of fluorinated functional groups into molecules, as the addition of these groups has a strong impact on biological properties and bioavailability of bioactive compounds.31 In 2011 Stephenson, et al. for the first time reported visible light mediated ATRA reactions, proving this methodology as an efficient way to improve the overall performance of this kind of reaction compared to classic radical initiation conditions. This synthetic approach was effective for the preparation of a wide range of perflourohalogenated substrates from unactivated alkenes by using Ru(bpy)32+ as the photocatalyst combined with sodium ascorbate as an electron donor (Scheme 7).32 Scheme 7. Atom transfer radical addition mediated by photoredox catalyst. A similar kind of transformation also providing halotrifluoromethylated product was reported by Han et al. (Scheme. 8)33 using triflouromethanesulfonyl chloride as the triflouromethyl source and visible light in presence of Ru (II) photocatalyst (1). Using this protocol, the variety of substrates including mono, di-, and tri-substituted unactivated alkenes went under trifluoromethylation in excellent yields. Scheme 8. Trifluoromethyl chlorination of disubstituted and internal alkenes. Radical Cascades Radical cascades are one of the most powerful tools for accessing complex structures in single step if substrate is stable under the for radical initiation conditions.34 One of the earliest examples of radical cascade was reported by Stokes et al.35 is intermolecular addition of Sn-radical to alkynes, he also studied the regioselectivity of vinyl radical cyclizations onto C=C double bond (Scheme 9). Cyclization cascades initiated by intermolecular addition of Sn radical to alkyne can be distinguished between reactions where tin-moiety retained in the final product with those where Sn radical essentially acted as a catalyst, which was later removed by the homolytic cleavage of labile C-Sn bond. Scheme 9. Radical cyclization sequence, triggered by regioselective addition of tin radical. Nowadays, because of the recognized toxicity associated with organotin compounds, the focus has been shifted toward the development of alternative tin-free and less environmentally problematic methods for radical cyclizations. Visible light photocatalysis has offered a powerful and sustainable tool for the development of new catalytic radical cascade reactions due their unique ability to facilitate formation of various reactive radicals and radical ions in mild and environmental friendly conditions. Various structurally diverse carbocycles and heterocycles from basic and readily available materials have been synthesis by using this protocol. The augmentation of radical cascade cyclization and visible light photoredox catalysis approach has inspired   radical chemists   around the world to develop novel and efficient methods for synthesis of important heterocyclic motif that are prevalent in nature products exhibiting a wide range of bioactivites. One highly   effective method for radical cascade, generating tetracyclic fused ring was reported by Furst et al. where they used visible light mediated protocol to synthesize tetracycle   from bromomalonate and tricyclic compound from alkyne in good yields as a single diastereomers36 (Scheme 10.). Scheme 10. Intramolecular radical cascades. Xiao et al. further extended the application of visible light mediated radical cascade reactions in synthesis chromam-2ones and dihydroquinoline-2-ones based scaffolds, as these are omnipresent components in biologically active natural products and pharmaceutical drugs37. They reported a new type of radical cascade reaction between photogenerated ÃŽÂ ±-amino radicals and acyloyl ester- and acrylamide-tethered aroylhyrazones.38 (Scheme 11). Scheme 11. Photoredox catalyzed radical cascade reaction of ÃŽÂ ±-amino radicals. In addition, they developed an oxidant free N-radical cascade reaction of ÃŽÂ ², ÃŽÂ ³-unsaturated hydrazones by incorporating visible light photoredox and cobalt catalysis to obtain dihydropyrazole-fused benzosultams (Scheme 12),39 that has never been reported previuosly. Scheme 12. Visible light photocatalytic N-radical cascade reaction of benzosultam synthesis. Recently, Xu et al. devised a valuable cascade annulation by generating acyl radicals from abundant acyl chlorides under visible light mediated photoredox catalysis which then started a cascade cyclization of 1,7 enynes (Scheme 13).40 Scheme 13. Visible light induced cascade cyclization of 1,7-eynes with acyl chlorides. Applications in Total Synthesis In the history of organic synthesis, indole based alkaloids grabbed much more attention because of their abundance in natural products and biologically active compounds, and they have always been interesting and challenging synthetic targets. The unique ability of visible light mediated photoredox catalysis in forming key C-C bond granted access to numerous applied intermediates that facilitated synthesis of these diverse natural products. In 2011, Stephenson and co-workers reported the asymmetric synthesis of (+)-gliocladin C (21), a natural product with interesting cytotoxic activity (Scheme 14.)41 starting from L-tryptophan, the important intermediate C3 bromopyrroloindoline (17) was synthetically prepared by standard transformations using Boc-D-tyrptophan methyl ester (16). The vital step in the synthesis was the formation of C-C coupled intermediate (18), which was accomplished by reductive dehalogenation-arylation process triggered by blue light irradiation on substrate in the presence of aldehyde (22), photocatalyst (1) and NBu3 as a quencher. This intermediate was converted into natural product in 7 high-yielding steps, which was more efficient than the previous reported 21-step structural synthesis of (21) starting isatin with and overall yield of ~ 4%.42 Scheme 14. Total synthesis of (+)-gliocladin C. Another more recent example is the synthesis of biologically active alkaloids drimentines A, F and G (Scheme 15.).43 by Li and co-workers utilising reductive C-C bond forming strategy. In this example, the heterocycle (25) was coupled with acceptor (24) by intermolecular radical 1,4-addition to generate the important intermediate (26), which facilitated the product (27) -(29) in good yields. Scheme 15. Total synthesis of drimentines A, F, G Targeting Pharmaceutically Relevant Scaffolds The unique capabilities of photoredox catalysis is an access to variety of fluoroalkyl radical species at late stage modification of therapeutic leads. Fluorinated functional groups (trifluoromethyl group in particular) have become increasingly popular over the decades44, because these motifs have dramatic on the molecules physiochemical properties, making them more selective, increasing their efficacy, or making them easier to adminster. Photoredox catalysis can provide an approach tailored on industrial scales by using abundantly available CF3 sources and eliminating the need of pre-functionalized substrates. This chemistry was readily translated to multigram scales for a number of substrates, one most important example of this strategy is the synthesis of trifluoromethylated 2-chloropyridine (32) (Scheme. 16) a vital synthon in production of anti-infective agents at Boehringer Ingelheim Pharmaceuticals Inc.45 Scheme 16. Preparation of Boehringer-Ingelheim intermediate. A novel redox system comprising pyridine N-oxide and trifluoroacetic acid was designed by Beatty at el. where C-C activation was achieved by pyridine N-oxide, a redox trigger, which could in situ generate modified trifluoroacetate shifting the redox potential of trifluoroacetate lower, within the reach of Ru(bpy)32+ photoredox catalyst.46 ORL-1 Antagonist Intermediate Opioid receptor-like 1 (ORL-1) antagonist which is currently under the development for the cure of depression and obesity,47 has a gem-difluorobenzyl functional group around the spirocyclic piperidine (34), the earlier synthetic route consisted a total of   8 steps starting from (33) with an overall yield of 28%.48 Futhermore, this sequence included AIBN initiated radical bromination, and most challenging step was the benzylic fluorination by using 2.6 equiv. of Deoxo-Fluor 9 (specialised fluorinated reagent) as a fluoride source, which remained problematic as it required the use of pre-functionalized substrates through classical nucleophilic or electrophilic fluorination. Radical rearrangements reactions have demonstrated the strategic benefits in its synthesis when compared to this method.49 Visible light mediated radical Smiles rearrangement was developed to address the challenging synthesis of gem difluoro group ORL-1 antagonist from fluorinated thiophene (35), which could be produced from difluoro-ethanol from readily available corresponding ethyl ester (Scheme 17) reported by Douglas et al.50 This strategy has solved the problem of high number of steps and overcome the overall low yield and use of specialized fluorinated reagents. This new 5-step synthetic route eliminated the undesirable feature of previous synthetic route, the challenging benzylic defluorination could be accomplished by switching a key transformation to a C-C bond instead of a C-F bond formation. Scheme 17. Previously reported route towards ORL-1 antagonists and new photochemical radical smiles rearrangement route. Biofeedstock Processing Biomass set itself aside from other renewable resources, since the energy it contains is stored in the form of chemical bonds, which allow biomass to be used for several purposes other than generating electricity and heat, such as liquid fuel and value-added chemicals. In particular, depolymerisation of lignin50, one of the most abundant feedstock for aromatic commodity compounds, which has attracted a lot of attention in recent years. Lignin is a stable, branched biopolymer which is a part of the plant cell wall and is primarily responsible for providing rigidity and protection against environmental conditions. Primarily, it is composed of three different types of cinnamyl alcohols coupled together to produce a various array of motifs inside of the polymer chain (Scheme 18). The multiple connectivity and stability has hindered attempts to efficiently isolate value compounds through the degradative processing.51 The most sensible point of start in lignin degradation is ÃŽÂ ²-O-4 linkage, as this is the most abundant (45-65%). Photoredox catalysis provides mild means of cleaving these critical bonds by a two-step procedure, which includes the selective oxidation of the alpha carbon followed by photochemical reductive cleavage.52 Scheme 18. Two steps protocol for degradation of lignin model system. This strategy could be used for efficient degradation of a range of lignin model systems, isolation of the fragmentation products in excellent yields by employing photocatalyst 3 under the reductive quenching conditions. Conclusions. Photoredox catalysis with Ru (II) and Ir (I) metal complexes has recently received widespread attention as a tool for synthetic chemists, and it has been applied to the development of wide range of new C-C bond forming reactions. The utility of photoredox catalysis arises not form its ability to promote C-C bond formation, but rather from its ability to generate a diverse array of reactive via single-electron transfer. As shown, these species include electrophilic ÃŽÂ ±-carbonyl radicals, tert-malonate radicals, ÃŽÂ ±-amino radicals, acyl radicals and trifluoromethyl radicals. These intermediates have been used to develop reactions as varied as reductive dehalogenation, indole functionalization, atom transfer radical additions, radical cascades and Smiles rearrangement. Also, photoredox catalysis has been proved as valuable tool for the synthesis of various biologically active compounds and their derivatives, as demonstrated by its application in the total synthesis of gliocladin C, drimenties A, F, G, and pharma relevant scaffolds. In each of these syntheses, simple and typically inert functionalities in the starting materials are transformed into reactive intermediates upon single electron transfer. These powerful transformations are not only redefining the synthetic strategies, but it has also changed the face of radical chemistry; a fundamental area in organic chemistry which mostly accessible using hazardous radical reagents. These robust class of reactions have inspired many researchers in designing and developing novel approaches to synthetic targets. The growth of visible light phototredox catalysis is not only significant on its own right, also bodes well for the future of organic synthesis. References: Nicholls, T. P.; Leonori, D.; Bissember, A. C., Applications of visible light photoredox catalysis to the synthesis of natural products and related compounds. Natural Product Reports 2016, 33 (11), 1248-1254. James J. Douglas, J. D. N.; Kevin P. C., Enabling Novel Photoredox Reactivity via Photocatalyst Selection. Aldrichimica 2014, 47, 15-25. Kalyanasundaram, K., Photophysics, photochemistry and solar energy conversion with tris(bipyridyl)ruthenium(II) and its analogues. Coordination Chemistry Reviews 1982, 46, 159-244. Juris, A.; Balzani, V.; Barigelletti, F.; Campagna, S.; Belser, P.; von Zelewsky, A., Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence. Coordination Chemistry Reviews 1988, 84, 85-277. Juris, A.; Balzani, V.; Belser, P.; von Zelewsky, A., Characterization of the Excited State Properties of Some New Photosensitizers of the Ruthenium (Polypyridine) Family. Helvetica Chimica Acta 1981, 64 (7), 2175-2182. Tucker, J. W.; Stephenson, C. R. J., Shining Light on Photoredox Catalysis: Theory and Synthetic Applications. The Journal of Organic Chemistry 2012, 77 (4), 1617-1622. (a) Graetzel, M., Artificial photosynthesis: water cleavage into hydrogen and oxygen by visible light. Accounts of Chemical Research 1981, 14 (12), 376-384. (b) Meyer, T. J., Chemical approaches to artificial photosynthesis. Accounts of Chemical Research 1989, 22 (5), 163-170. Takeda, H.; Ishitani, O., Development of efficient photocatalytic systems for CO2 reduction using mononuclear and multinuclear metal complexes based on mechanistic studies. Coordination Chemistry Reviews 2010, 254 (3-4), 346-354. Kalyanasundaram, K.; Grà ¤tzel, M., Applications of functionalized transition metal complexes in photonic and optoelectronic devices. Coordination Chemistry Reviews 1998, 177 (1), 347-414. Lowry, M. S.; Bernhard, S., Synthetically Tailored Excited States: Phosphorescent, Cyclometalated Iridium(III) Complexes and Their Applications. Chemistry A European Journal 2006, 12 (31), 7970-7977. (a) Lalevà ©e, J.; Blanchard, N.; Tehfe, M.-A.; Morlet-Savary, F.; Fouassier, J. P., Green Bulb Light Source Induced Epoxy Cationic Polymerization under Air Using Tris(2,2à ¢Ã¢â€š ¬Ã‚ ²-bipyridine)ruthenium(II) and Silyl Radicals. Macromolecules 2010, 43 (24), 10191-10195. (b) Fors, B. P.; Hawker, C. J., Control of a Living Radical Polymerization of Methacrylates by Light. Angewandte Chemie International Edition 2012, 51 (35), 8850-8853. Howerton, B. S.; Heidary, D. K.; Glazer, E. C., Strained Ruthenium Complexes Are Potent Light-Activated Anticancer Agents. Journal of the American Chem

The Ontological Argument Essay -- Philosophy Religion

The Ontological Argument In Anselm's ontological argument he is trying to prove the existence of God, his argument is an argument purely based on the mind and does not require the moral agent to venture into the real of the senses. Ontology is to do with being, or what something is. Anselm's ontological argument concerns existence and whether it is an attribute of God in the same way omnipotence, omniscience and benevolence are believed to be. The argument is an a priori argument. It does not rest on proving God's existence by relying on experimental knowledge but on showing that God must exist logically, or that God's non-existence is illogical. The main idea behind Anselm’s argument is that if I can think X to exist X must exist because it is possible to conceive it. As such the central premise of the ontological argument is: 'God is that than which nothing greater can be conceived' In other words it is better for something to exist in reality that in the mind, or to exist is the best quality something can poss...

Great Auntie Anne’s House :: essays papers

Great Auntie Anne’s House There are many thoughts and memories that I still retain from my childhood. Many have given me new experiences and taught me lessons that have helped me grow. My great Auntie Anne has provided me with several memories, which I still recall occasionally. What are most difficult to forget are the memories of the times in her home. I have never found a home like hers. The memories I obtained outside of the cottage, in the main entrance, in the old library, and in the secret room are the memories most difficult to forget. The small white cottage sat upon a large green field. My Auntie believed in allowing nature rule. A thick terra cotta wall kept the home safe from the outside world surrounded the cottage. Wild flowers grew around the cottage and grew along the surrounding walls of the wild garden. These gave the impression the cottage grew up from flowers. She did not have trimmed green grass or any type of man made landscape. She allowed the green and white wild flowers to grow where they pleased. The field also had many trees that reached high above and branched widely. I remember climbing those trees with my brother and cousins. A dirt road flowed up through the fields into the small garage. As I walked through the thin dirt path I anxiously awaited the adventures found inside the house. Her home was a magical place where my cousins, my brother, and I could run wild. Auntie, as she preferred to be called, was not a strict disciplinarian, so we were free to do what we wished. She resolved that her niece and nephews must learn to enjoy life as she did. We often visited her white cottage while on vacations. The front door of the house was a large wooden door with black iron strips running across. The handle was also made in the shape of a serpent, which symbolizes wisdom and the Earth spirit. Auntie always opened the door with her smiling wrinkled face greeting us as we walked through. As we entered the house we were led into a main room. It was simple and relaxing. To the right was a large window that overlooked the cobblestone driveway and entrance to the garage. To the left were two sectional floral Victorian couches that connected together in the corner of the room with a small square wooden table.

Intrinsic Motivation Essay -- essays papers

Intrinsic Motivation Sometimes a student can be fascinated in a subject and are eager to learn more without outside influence or help. This kind of a situation is when there exists a large amount of intrinsic incentive to motivate a child. It is when a student enjoys an aspect of an activity enough to be motivated within. An intrinsic incentive could arise in any subject of interest such as dinosaurs, famous people, or far off places. However, topics that are learned in schools today do not arouse children since they find the information useless in their everyday lives (Slavin, 2000). The role of personal interest is crucial in a learning situation. It has been proven that a child who is intrinsically motivated tend to make use of strategies that require a larger amount of effort and that allow them to develop more intensely. They prefer tasks of higher levels than an extrinsically motivated child (Lumsden, 1994). Internal motivation is longer lasting that external motivation. When students achie ve a feeling of satisfaction, learning occurs more successfully (HCC Intranet, 2001). In order to ensure students are intrinsically motivated, teachers must use certain strategies to encourage this type of learning. Praise One of the ways to engage children in intrinsic motivation is by praising the students for the efforts they make in the classroom and encouraging more positive learning. It is important to praise a child for small improvements along with large improvements. Some educators with high expectations forget to commend their students along the way as they progressively achieve the desired goal (Palardy, 1997). Praise does not necessarily mean tangible rewards. It is more of a pat on the back, a positive ... ... learn. ERIC Digest, 92. Retrieved November 5, 2001 from http://www.kidsource.com/kidsource/content2/Student_Motivation.htm. -The article talks about what influences student motivation and the advantages of it. It offers intrinsic ideas to help develop student motivation. Also explains why children are unmotivated. Cooper, H. (2001, April). Homework for all-in moderation. Educational Leadershiip, 58,pp. 34-38. -Explains the advantages and disadvantages of homework, and if it works. This relates to motivation. Teachers use homework at times to motivate their students. Palardy, J. (1997, March). 15 strategies for motivating students. NAESP. Retrieved November 2, 2001 from http://www.naesp.org/comm/p0397b.htm. -Lists fifteen strageties to use in a classroom to help motivate children. After each suggestion, a detailed description is given.