Administrative ethics Essay Example | Topics and Well Written Essays - 1000 words

Administrative ethics - Essay Example The article written by Mehnke (2010) entitled â€Å"Managing a breach in patient confidentiality† and published in the Nursing Critical Care journal proffered issues pertinent to the crucial importance of observing privacy and confidentiality when dealing with patients. In a scenario, a nurse accessing patient’s records for personal use emerged without thinking of the possible repercussions of her action to the patient and to herself. Mehnke (2010) revealed that â€Å"a nurse knowingly accessed a neighbor’s electronic medical record and acted on the information she found by confronting the patient. The nurse approached the patient in the perioperative waiting area before the surgery and asked what procedure she was undergoing† (1). As a consequence, the nurse’s action dealt with the utmost penalty of firing her from employment because of breach of confidentiality. The decision precludes other nurses and health care practitioners from repeating the s ame offense. The gravity of the issue was addressed by severing the employment from the health care institution to show other health care practitioners that there is no compromise to the issue. The issue’s impact on health care practitioners focused on giving primary importance and utmost care in adhering to the laws and regulations prescribed by Health Insurance Portability and Accountability Act (HIPAA), specifically on the protection of patient privacy rights.

Probation, Parole, and Intermediate Sanctions Essay

Probation, Parole, and Intermediate Sanctions - Essay Example Finally, the paper will close with a review on the ethical issues that surrounds the correction processes, approaches and facilities. Crime and community safety have been the most disturbing issues across the entire world since time immemorial. Criminal activities carried within communities have caused unrest and state of confusion as most people fear for the safety of their lives and property. It is due to adverse effects of crimes on communities that legal professionals and security personnel came up with strategies of arresting, examining, rehabilitating and incarcerating individual criminals to restore peace, sanity and confidence in particular communities. Historically, criminal activities were assumed to be caused by evil spirits and therefore, individual criminals were taken to the public for severe punishment as deterrence to other potential activities. Revolution took place in history of crime justice and community safety and gave rise to alternative models of discouraging and ending criminal activities. Among the notable revolutionized ways of handling criminal activities include parole, probation and in termediate sanctions. Schmalleger (2012) avers that the three methods of handling crime justice and community safety have been experiencing pendulum effects due back and forth review and exercise. Patersilia (1998) asserts that probation and parole have been misunderstood as the only approaches to ensuring community safety and criminal justice. Despite the similarities in the application of parole and probation modes of enforcing criminal justice, the difference occurs in the manner in which each is ignited and set to work. Probation according to Patersilia (1998) is an execution process involving the sentencing of criminal offenders to serve in the community projects as opposed to incarceration. Parole involves release of an offender from

Immune Deficiency Syndrome or AIDS Essay Example for Free

Immune Deficiency Syndrome or AIDS Essay This film is another campaign material of the Department of Health to , spread, publicize or publish information on the prevention of Human Immunodeficiency Virus or HIV and Acquired Immune Deficiency Syndrome or AIDS.It is based on the story and screenplay by the son of film director Peque Gallaga and a self-confessed HIV positive. He is Wango Gallaga. And it is a digital masterpiece by Neal â€Å"Buboy† Tan. This film is about a man named Gil Bustamante played by jake cuenca, He is a young documentary filmmaker. A job assigned to him by department of health to do a documentary about their HIV/AIDS awareness program. Bearing his video cam and an irritable, grumpy and snappy assistant played by candy pangilinan they go to the San Lazaro Hospital as a backdrop, they weaves a story that combines the numerous stories of people who are infected with the virus. In the process, he discovers so much about HIV/AIDS. Among those having their story told are heterosexuals, homosexuals, prostitutes, and intravenous drug users. The first victim he met is named Heidi, an ordinary housewife who contracted the virus from her philandering OFW husband. He died of AIDS three years ago, leaving her alone to care for their 9 year old son, Victor also an HIV patient. The second one is Ivy, a young call center agent who discovers she is HIV positive when she tries to apply for work abroad. Her plans for a new life abroad destroyed, she must now face the world – her work, family, and friends – with a mistake from her past And lastly, Vanessa a cheerful young gay and stand-up comedian who engages in different sexual pleasures with multiple partners. He, with his very supportive parents, are willing and eager to share his story for his own reasons, Gil is obsessed with finishing the documentary, even if some of his key subjects have either died or blacked-out of the project. He learns that the fight against HIV/AIDS is not solely the responsibility of the government – it is a fight that demands responsible action from every individual. In the end, he is triumphant in finishing the documentary as well as being able to face his own greatest fear. Heidi (Ma. Isabel Lopez) contracted the virus from her philandering OFW husband who died three years ago; Ivy (Iza Calzado), a call center agent who  was two years fresh from graduation when she applies for a job abroad and is discovered to have also contracted the virus. Vanessa (IC Mendoza) on the other hand, is a young cheery gay who’s a stand-up comedian and who engages in different sexual pleasures. He, with the support of his parents, is willing and eager to tell his story. Heidi, being an innocent victim, decides to tell her story in the hope that by coming out, less people will contract the virus. Ivy suspected she got the virus during their graduation party when everybody was intoxicated and drugged. She never had sex with anyone except her boyfriend, who luckily was HIV-negative. Vanessa continues his stint as an entertainer, and continues to have sex with different men until finally he was nabbed and almost got killed by a group of men he had sex with.

Organopalladium Reagents and Intermediates

Organopalladium Reagents and Intermediates Joà £o T. V. Matos Table of contents Table of contents 1. Introduction 2. Organopalladium reagents and intermediates 2.1. The characteristic features for the use of palladium in organometallic chemistry 2.1.1. Oxidation States of Palladium 2.2. Preparation of organopalladium reagents and intermediates 2.2.1. Ï€-Ally Palladium Complexes 2.2.2. Cyclic aryl palladium complexes 2.2.3. Palladium Olefin and Diene Complexes 2.2.4. Palladium-TV-Heterocyclic Carbene Complexes 2.3. Methods for structural characterisation of organopalladium reagents 2.3.1. Nuclear Magnetic Resonance Spectroscopy 2.3.2. Infrared spectroscopy 2.3.3. X-Ray crystallography 3. Applications of palladium-catalysed organic reactions 3.1. Palladium-catalysed carbon-carbon cross coupling reactions 3.1.1. The Heck reaction 3.1.2. The Stille Reaction 3.1.3. The Suzuki reaction 3.1.4. The Negishi Reaction 3.1.5. The Sonogashira Reaction 3.1.6. The Tsuji–Trost Reaction 4. Final remarks Bibliography 1. Introduction Organometallic chemistry is discipline devoted to the study, not only of the compounds and intermediate species with metal-carbon bonds, but also the comprehensive study of all transformations and interaction between organic molecules and a inorganic metal from the main groups, transition series, lanthanides and actinides (Astruc, 2007; Crabtree, 2005). This interface discipline, between classical organic chemistry, coordination chemistry and inorganic chemistry, has proved, in the last decades, very useful to provide some important conceptual insights, new structures, and catalysts for different applications areas of organic synthesis, both in the academic and in the industrial fields (Crabtree, 2005). Organometallic chemistry also began to have a major impact on other areas such as: biochemistry with the discovery of enzymes that carry out organometallic catalysis; chemistry of materials due to the proprieties of some organometallic compounds to be used was precursors for depositin g materials on various substrates via thermal decomposition of the metal compound; nanoscience and nanotechnology due to the proprieties of some organometallic compounds to be used precursors for nanoparticles; and green chemistry by minimizing both energy use and chemical waste of several organic synthesis (Crabtree, 2005). The first organometallic substance to be prepared was synthesized in 1760, in a military pharmacy in Paris, by Louis Claude Cadet de Gassicourt. This French chemist, who was working on cobalt-containing inks, used arsenic-containing cobalt salts for their preparation. From this work was resulted the so-called â€Å"Cadet’s fuming liquid† which contains a mixture of tetramethyldiarsine and cacadoyl oxide (the first documented organometallic compound) by carrying out the following reaction (Equation (1)): (1) However, despise several organometallic compound discovered, along the eighteenth and nineteenth century’s, the truly â€Å"boom† of organometallic chemistry only occurred during the third quarter of the twenty century, in especially in countries like the United States of America, England and Germany (Astruc, 2007). One of the facts that contributed to this was the recognition of the potential of some d-block transition metals (i.e. nickel, palladium, platinum, rhodium, and ruthenium) organometallic reagents and intermediates as superior catalysts for new bond formation (i.e. carbon-carbon bonds) and their unique property to activate a wide range of organic molecules (Negishi, 2002; Schlosser, 2013). In this review, one of these d-block transition metals and their organometallic reagents based and intermediates will be put in broader perspective, the palladium. The use of this metal, has truly revolutionized the organic synthesis field over the last three decades, being nowadays, the most widely used element in organic synthesis (Crabtree, 2005). Probably the most notable example of its importance of the palladium intermediates as catalyst in organic synthesis is the attribution, by the Swedish Nobel Committee, of the 2010 Nobel Prize in Chemistry to Richard F. Heck, Ei-ichi Negishi, and Akira Suzuki for their work in palladium-catalysed cross couplings in organic synthesis (Nobelprize.org, 2013). This review will attempt to highlight some of the outstanding properties of the organopalladium reagents and intermediates, identifying the main ways of preparation of these components, some of the most important analysis procedures to obtain their structural characterization, and prese nt some of the numerous applications and reactions where these compounds play an important role. 2. Organopalladium reagents and intermediates 2.1. The characteristic features for the use of palladium in organometallic chemistry Palladium is a chemical element discovered and isolated in 1803 by William Hyde Wollaston who named it after the asteroid Pallas, which was discovered a year before. Is a transition metal and belong to the 10th group, 5 period, and d-block of the periodic table. This atom, with atomic number of 46 and average atomic weight of 106.4 could occur naturally in seven isotopes, which includes six stable isotopes. Palladium, is nowadays one of the most versatile, selective, ubiquitous and significant metals used for organic synthesis and had truly impacted this field in the last four decades (Negishi, 2002). This fact is mainly because no other transition metals can offer such versatile to the abundance of possibilities of carbon–carbon bond formation that the palladium reagents and intermediates can offer (Tsuji, 2004). Furthermore, despite the palladium complexes are, in several reactions, highly reactive are stable enough to be used as recyclable reagents and intermediates, in catalytic processes (Negishi, 2002). In this sense palladium-mediated processes have become essential in several applications, namely in the syntheses of natural products, polymers, agrochemicals, and pharmaceuticals (Caspi, 2008). Despite the palladium being a rare and very expensive noble metal, there are several characteristic features and chemical properties which make reactions involving palladium reagents and intermediates particularly suitable in organic synthesis. One of the most important characteristic feature appears to be its moderately large atomic size factor which contribute to the moderate stability of its compounds and their controlled but wide-ranging reactivity leading (Negishi, 2002; Tsuji, 2004). Furthermore, its moderated size associated with high d-electron count, and its relatively high electronegativity (2.20 and 1.57 in Pauling and Sanderson scales, respectively), classified this element as â€Å"soft† element, which makes it a real alternative to the more traditional and â€Å"hard† organometallic reagents, such as the magnesium (Grignard) and lithium compounds (Negishi, 2002). Other important characteristic features is the tolerance from the palladium reagents and inter mediates to several functional groups (i.e. carbonyl and hydroxy groups) and which means that the palladium-catalysed reactions can be carried out without protection of these functional groups (Tsuji, 2004). Furthermore, palladium reagents and intermediates have a low tendency to undergo one-electron or generate radical in the reaction processes, reducing the possibility of unwanted side reactions and making the palladium-catalysed reactions quite clean and selective. Finally, another important feature, especially in the green chemistry context is their lack of toxicity problems associated and therefore they do not require too many special handling cares (Negishi, 2002). 2.1.1. Oxidation States of Palladium The most common oxidation states of palladium are 0, +1, +2, +3, and +4 (Pd(0), Pd(I), Pd(II), Pd(III), and Pd(IV), respectively). The palladium oxidation states of +1, +2, +3, and +4 correspond to d9, d8, d7, and d6 electron configurations, respectively, as shown in Figure 1. Figure 1.Representative d electron configuration of Pd(I), Pd(II), Pd(III), and Pd(IV) oxidation states (based on reference (Mirica and Khusnutdinova, 2013)) The vast majority of palladium-catalysed reactions, until the beginning of the twentieth-one century, were only focused in the reactions involving Pd(0) and Pd(II) oxidation states, since Palladium strongly favours this two oxidation states (Mirica and Khusnutdinova, 2013; Negishi, 2002). Despite the bulk of the organopalladium literature is centered on the use of Pd(0) and Pd(II) oxidation states, already in 2002, in the Handbook of Organopalladium Chemistry for Organic Synthesis, Negishi point out that the utilization of other oxidation states (Pd(II), Pd(III), or Pd(IV)), although it is still very rare, could become o be very significant in the future (Negishi, 2002). More than ten years later, and with the rapid evolution in the organopalladium chemistry, complexes with palladium in these oxidation states, especially the Pd(IV), have demonstrated their potential and they improved significantly their role in organic synthesis. Although the development of Pd(IV) chemistry has just begun, this has already made possible the development of a number of significant new transformations. Pd(IV)-catalysed reactions usually show a high selectivity and synthetic robustness, and in almost all of them the use of catalysts are generated in situ from commercially available palladium salts, making them particularly attractive from the viewpoint of cost effectiveness (Muà ±iz, 2009). However, by comparison with the Pd(0), Pd(III), or Pd(IV), complexes of odd-electron Pd(I) and Pd(III) oxidation states are much less used. Yet, despite the study of this oxidation states remains in its infancy, Pd(I) complexes have already been employed as pre-catalysts in organic synthesis (Canty, 2011) and despite the potential role of Pd(III) intermediates in catalysis is currently more speculative, this subject beginning to emerge considerable interest, as can be highlighted by the different articles and reviews on the subject (Canty, 2011; Mirica and Khusnutdinova, 2013; Powers and Ritter, 2011). 2.2. Preparation of organopalladium reagents and intermediates In the majority of the organic reactions that use palladium as catalyst, the organopalladium species are generated in situ during the course of the reaction, instead of a preparation of stoichiometric organopalladium reagents, ensuring that only a catalytic amount of palladium is used. In these cases, the reaction mechanisms should include a step were the organopalladium species are formed, the steps in which the formed species react with other reagents to generate a particular product(s), and the step in which organopalladium species are regenerated in a catalytically active form (Carey and Sundberg, 2007). There are several types of organopalladium intermediates extensively used in reactions with considerable importance in several synthetic applications. As reviewed by Schlosser (2013), more than 64000 entities with a palladium-carbon bond are known. Consequently, in this review, only the preparation of some of the most common organopalladium reagents and intermediates will be addressed. As special cares to have in the preparation of these complexes, palladium complexes, unlike the organometallics from the Group I and Group II, are not water sensitive. Consequently, in almost cases, strict exclusion of water is not necessary. Although, some reactions can beneficiate from the presence of water traces or can even be performed in water as solvent or co-solvent. Furthermore, palladium complexes could be quite to moderately air stable. Consequently, it is advised to conduct reactions using these complexes under an inert gas (i.e. argon or nitrogen) (Schlosser, 2013). 2.2.1. Ï€-Ally Palladium Complexes One of the most important organopalladium intermediates are Ï€-allyl complexes. The most common Ï€-allyl palladium complex, the dimer [(n3-C3H5)PdCl]2, was discovered more than 50 years, serves as starting material for a number of other complexes (Schlosser, 2013). Ï€-allyl complexes, can be synthesize from Pd(II) salts, allylic acetates, and other compounds with the potential of leaving groups in an allylic position, or can be prepared directly from alkenes by reaction with PdCl2 or Pd(O2CCF3)2. In this second scenario, the reaction occurs by electrophilic attack on the Ï€ electrons followed by loss of a proton, as represented in Scheme 1 (Carey and Sundberg, 2007). Scheme 1.Synthesize of Ï€-Ally Palladium Complexes by electrophilic attack on the Ï€ electrons (based on reference (Carey and Sundberg, 2007)). Due to the low electrophilic power, these complexes usually reacted with less-substituted allylic terminus of a variety of nucleophiles. After this reaction occurs, the resulting organopalladium intermediate breaks down by elimination of Pd(0) and H+, as described in Scheme 2 (Carey and Sundberg, 2007). Scheme 2.The overall transformation of the allylic substitution. (based on reference (Carey and Sundberg, 2007)). 2.2.2. Cyclic aryl palladium complexes Another important organopalladium intermediates are the cyclic aryl palladium complexes, or palladacycles (Schlosser, 2013). This complexes, are quite relevant role in cascade transformations leading to complex molecular architectures, in the proximally) directed arylation reactions, and in several intramolecular cross-coupling reactions (Beletskaya and Cheprakov, 2004). Palladacycles intermediates can easily be obtained by palladation reactions starting from Pd(II) salts and an arene having a directing group (Schlosser, 2013). Scheme 3.Palladacycles intermediates obtained by palladation reactions (R = NR2, PR2, etc., and Y = alkyl, aryl, etc.). Based on reference (Schlosser, 2013). In the cases where the directing group is an amine (e.g., benzyl or homobenzyl amines) or a phosphine (e.g., aryl phosphines), as represented in the Scheme 3A, the mechanism occurs by an electrophilic addition to the arene, and could include Pd(IV) intermediates. On the other hand, as represented in the Scheme 3B, Alkylarenes can also be substrates for palladacycles, in which, the activation of sp3-carbons next to an arene is presumably forced by agostic interactions (Schlosser, 2013). 2.2.3. Palladium Olefin and Diene Complexes The major group of organopalladium intermediates are the palladium Olefin and Diene Complexes. Pd(II) complexes having olefin ligands (i.e. 1,5-cyclooctadiene (COD), norbornene, or norbornadiene) can be obtained by reaction of Pd(II) chloride in the presence of the appropriate alkene (Carey and Sundberg, 2007; Schlosser, 2013). In this reaction the alkenes react with Pd(II) to give Ï€ complexes that are subject to nucleophilic attack. However, the products formed from the resulting intermediates are depending of the specific reaction conditions used. In the first case, represented in Scheme 4 as the path a, palladium can be replaced by hydrogen under reductive conditions. On the other hand, in the absence of a reducing agent occurs the obliteration of the Pd(0) and a proton, leading to the substitution of a vinyl hydrogen by the nucleophile, as represented in path b of the Scheme 4. (Carey and Sundberg, 2007). Scheme 4.Synthesize of the Palladium Olefin complexes. Based on reference (Carey and Sundberg, 2007). However, it is important to note that several of these palladium Olefin and Diene complexes are already commercially available (Schlosser, 2013). 2.2.4. Palladium-TV-Heterocyclic Carbene Complexes Palladium-TV-Heterocyclic Carbene (NHC) complexes have been recently introduced as powerful ligands for palladium. These NHC complexes have as main advantage the fact that they are quite stable, easy to handle, air-stable and can be easily be prepared from the ligand and palladium precursors (Chartoire et al., 2012; Schlosser, 2013). The NHC-based palladium complexes have been used very successfully for a series of different reactions, namely some cross-coupling reactions and aryl amination (Chartoire et al., 2012; Schlosser, 2013). In Figure 2 are shown some examples of these NHC-palladium catalysts, already used to ensure the efficiency of those reactions. Figure 2.Examples of NHC-palladium complexes: A) [Pd(NHC)(R-allyl)Cl] developed by Nolan; B) [Pd-PEPPSI-NHC] developed by Organ; and C) [Pd(IPr*)(cinnamyl)Cl] developed by Chartoire et al.. Figure adapted from the reference (Chartoire et al., 2012). 2.3. Methods for structural characterisation of organopalladium reagents The identification and structural characterization of the organopalladium reagents and intermediates, is of utmost importance in organic synthesis field, to understand the behaviour and proprieties of these compounds. However, it can be quite challenging and somewhat tricky task to accomplish. To achieve the identification and structural characterization of the organopalladium reagents and intermediates, the main analytical methods used rely on the complementarity of information provide from spectroscopic and crystallographic techniques, such as multinuclear nuclear magnetic resonance (NMR) spectroscopy, infrared spectroscopy, and x-ray crystallography. 2.3.1. Nuclear Magnetic Resonance Spectroscopy Multinuclear NMR spectroscopy is certainly the key methodology to elucidate molecular structures in solution. Consequently, just as has already happened in organic chemistry or biochemistry, it is now routine to measure NMR spectra of diamagnetic organometallic and coordination compounds. Nowadays, on a routine basis, organometallic chemists daily measure hundreds or even thousands NMR spectra, not only to identify and characterize the molecular structure of a given organometallic but also to verify if a reaction has taken place (Pregosin, 2012). The most investigated active nuclei in organometallic chemistry are, by far, 1H and 13C. However, there are several others readily measurable spin =  ½ nuclei, such as 15N, 19F and 31P, that provide structurally valuable chemical shifts and a diagnostic spin-spin coupling constants. Furthermore, often the measure of 1H and 13C NMR spectra alone may not be sufficient, especially when it is necessary understand the immediate environment of the metal canter and these probes are spaced apart from the metal (Pregosin, 2012). NMR is therefore widely applied for analysis to organopalladium reagents. For example, 1H NMR is the most reliable characterization technique which can be used on hydridopalladium complexes (Negishi, 2002). Moreover, there are several examples in the literature of the application of multinuclear NMR to organopalladium complexes (Leznoff et al., 1999; Paà ±ella et al., 2006; Satake et al., 2000; Schlosser, 2013). Even the 15N, and 31P NMR methodologies, are also are widely used in the characterization of organopalladium reagents, being possible to find studies in this field with more than thirty years (Motschi et al., 1979). 2.3.2. Infrared spectroscopy Infrared (IR) spectroscopy provides the spectral information corresponding to vibrational modes of a molecule. The position of the bands in the Infrared (IR) spectrum depends mainly of the on the strength of the bond(s) involved as measured and the reduced mass of the system calculated using the atomic weights of the atoms involved in the molecule (Crabtree, 2005). Consequently, IR spectroscopic are very useful to obtain a fast confirmation of the presence of some functional groups (i.e. C=O, C=N). However, this method should not be used as a sole characterization technique, since, for example, although the hydride ligands from the hydridopalladium complexes are expected to have Ï…(Pd-H) stretches occurring in the distinctive region of 1950–2060 cm-1 in the infrared spectrum, they are often very weak signals and are also rather dependent on the trans effect of the opposite ligand (Negishi, 2002). 2.3.3. X-Ray crystallography The structural characterization in the solid state, namely that provided by X-ray crystallography is an extremely important part of organometallic chemistry. In the method, a beam of monochromatic X-rays pass through a single crystal of the sample. Consequently, this beam is diffracted in the crystal in various angles, providing in photography the pattern of the crystal spots. The intensity of this set of diffracted beams will depend on the nature and arrangement of the atoms in the unit cell. Thus, the intensities provide the information about the locations of the atoms in the unit cell, while the relative positions of the spots on the photography film carry the information about the arrangement of the unit cells in space (Negishi, 2002). The results of an X-ray structural determination should be represented as a diagram showing the positions of all the atoms in the molecule, as represented in the Figure 3 for two different organopalladium complex (i.e.{Pd[(p-(Noxyl-tert-butylamino- 2-)phenyl)diphenylphosphine]2Cl2}, and{(ÃŽ ·-C3H5)Pd [(p-(Noxyl-tert-butylamino-2-)phenyl)diphenylphosphine](Cl)}) (Leznoff et al., 1999). Figure 3.A typical X-ray crystallographic characterisation of two different organopalladium complex (from the reference (Leznoff et al., 1999)) However, in addition to being assured that organometallic compounds (i.e. organopalladium complex) allow the growth of crystals to be used in this technique, there are some limitations than need to be overcome. First of all, since the X-ray diffraction results are usually based on one only crystal, is necessary to ensure that this crystal is representative of the bulk and free of impurities. One way to check that each crystal is the same material as the bulk of the sample is using the information from the IR spectrum. Furthermore, it is necessary to ensure that the solid state is really the same as the structure of the same material in solution, since several organometallic complexes exist as one isomer in solution but as another in the solid state. This point is especially relevant when the solid state X-ray results are compared with the solution NMR data. Again, in this aspect IR spectroscopy can be also very useful because we can obtain a spectrum both in solution and in the solid state, which emphasizes the need for the information complementarity of these characterization techniques (Negishi, 2002). 3. Applications of palladium-catalysed organic reactions As already pointed out, since the second half of the twenty century, palladium had increased its relevance and role in organic chemistry, in particular in metal-catalysed reactions. Palladium, together with some other transition metals, have the unique property to activate a wide range of organic molecules and thus to catalyse various bond formations. This metal, by far is the most commonly used metal, is thus of utmost importance in a wide range of applications, not only in academic circles but also in industry (Schlosser, 2013). An example of this application is the Wacker process. This reaction, discovered in the 1960s, uses catalytic amounts of palladium to oxidize ethylene to acetaldehyde, and is still widely used in industrial applications (in 2007, was generating four million tons of acetaldehyde per year (Astruc, 2007)). Another factor that has emphasized the importance of using palladium as a catalyst of organic reactions in academic and industrial applications was the introduction of several palladium-catalysed carbon-carbon cross coupling reactions. This fact can easily be verified by more than 200 natural products and biologically active molecules synthesized making use of the Heck reaction (section 3.1.1) and the â€Å"ton scale† fine chemicals produced in the industry using the Suzuki reaction (section 3.1.3) (Schlosser, 2013). Furthermore, these reactions also allowed the total syntheses of molecules used in the in the production of several medical drugs such as Naproxen (anti-inflammatory drug), Taxol (anti-cancer drug), (Z)-tamoxifen (anti-cancer drug), and morphine (Carey and Sundberg, 2007; Schlosser, 2013). 3.1. Palladium-catalysed carbon-carbon cross coupling reactions The introduction, in the last quarter of the twenty century, of palladium as catalyst in carbon-carbon cross coupling reactions, a new paradigm for carbon–carbon bond formation has emerged allowing the assembly of highly complex molecular structures and completely changed how the chemical synthesis is performed (Nicolaou et al., 2005). The capability of this reactions to forge carbon–carbon bonds between or within functionalized and sensitive substrates have received an enormous amount of attention among the synthetic chemists, and their scope has been very significantly expanded during the last several years, not only in not only in total synthesis but also in medicinal, biology and nanotechnology (Nicolaou et al., 2005). In general, the palladium-catalysed carbon-carbon cross coupling reactions can be represented by the Scheme 5. However, in this equation, for any given combination of R1 and R2, several parameters should be changed or optimized, namely the metal countercation M, the leaving group X, the palladium catalyst, the introduction of some additives or co-catalysts, the solvent, and even others parameters such as temperature, time, concentration, and mode of addition (Schlosser, 2013). Scheme 5.Geral model of the palladium-catalysed carbon-carbon cross coupling reactions (based on reference (Schlosser, 2013)). The characteristics of an ideal palladium-catalysed cross-coupling reaction can be listed as follows (Schlosser, 2013): Varied and inexpensive methods to set up the coupling substrate functionality from commercially available starting materials Easily activated high-yielding coupling under mild conditions; Generation of the minimal amount of by-product preferably by employing low-molecular-weight donors; Excellent functional group compatibility; General stability of the cross-coupling substrates; Low toxicity of precursors, substrates, and generated by-products. In this review, despite the extremely long list of all the possible carbon-carbon cross coupling reactions involving Palladium as catalyst, it will focus on the reactions that embody several of the above mention characteristics and are most commonly used namely, the Heck, Stille, Suzuki, Sonogashira, Tsuji–Trost, and the Negishi reactions. These reactions, have truly revolutionized the organic synthesis field (Nicolaou et al., 2005), and, as already mentioned, should be noted that the authors and works that gave birth to three of these reactions (Heck, Negishi, and Suzuki) were recently awarded the Nobel Prize in chemistry 2010 (Nobelprize.org, 2013), which emphasizes even more the importance of these reactions. 3.1.1. The Heck reaction The Heck cross coupling reaction has been developed independently by Mizoroki, (Mizoroki et al., 1971), and improved by Heck (Heck and Nolley, 1972) in the early seventies of the twentieth century. However, it took more than a decade for the potential of this reaction, be explored by the wider synthetic organic community, namely with the development of catalytic asymmetric Heck reactions (Nicolaou et al., 2005). The Heck reaction, as presented in Scheme 6, can be broadly defined as the palladium-catalysed coupling of a vinyl, aryl, benzyl halide or a trifluoromethanesulfonate (OTf) group with an olefin to yield products which result from the substitution of a the hydrogen atom in the olefin coupling partner (Nicolaou et al., 2005). Scheme 6.The overall mechanism of the Heck reaction (R4 = aryl, benzy

Pain - No Redeeming Social Value :: Psychology Essays Research Papers

Pain - No Redeeming Social Value No better person exemplifies the ill than in-hospital patients, trapped against their will by both doctors and physical pain. They experience a variety of negative traits, such as being self-absorbed. An excellent example of a person’s self-absorption occurs in life and death situations. In lifeguard training, one of the first things that is taught was never to directly approach someone who is drowning. When someone is drowning they are panicking, the pain that is inflicted on them in this instance will cause them to do anything, however irrational, in order to save their lives. If a lifeguard attempts to rescue a person who is panicking it is very likely that they will be inadvertently drowned. Another mental affliction is selfishness. When a person is experiencing a large amount of pain, their concern is only for making it go away, unconcerned with its consequences, even of an emotional toll on family. A situation of this type could occur at a child’s birthday party, in which one of the children is hurt. His pain inspires a selfishness that prompts the parents to bring the party to a halt in order to find some sort of relief. Indeed, physical pain does little to ease the mind; rather one becomes more tense and querulous, ready to spark like a wildfire at the slightest chance. There is no better example than the old grouch on the geriatrics ward of a small town, dying from skin cancer. The lesions in his skin continue to grow and multiply, despite all the care given by the hospital staff. This great discomfort only hardened his heart, and he became more and more difficult to please. He often called upon the nurses at odd hours of the day to demand attention. When they did not come to him with whatever he wanted on command, he would throw his bedpan out into the hallway. Neither did he have a problem with defecating all over the room when they could not please him. Yet when the janitors would come in to clean up his mess, he would yell at them as if they were the cause behind all this. Even the doctors would dread their daily confrontations with him where he would blame them for all his discomfort. One can also see that being stuck in the gloomy hospital environment, surrounded by the ill and the dying, does little to help one's impatient nature when cloaked by the searing pain with little if any aid.

Policies Affecting Indigenous Australians Essay -- Aboriginal, Australi

Indigenous Australians have faced many changes to their original life style, with numerous policies being brought in. These policies had an incredible affect on how the indigenous Australians lived. The policies inflicted on the indigenous Australians varied widely and had numerous impacts. The policies of assimilation, protection and integration had mainly negative impacts on the community, causing loss of identity, language and religion. The policies of self-determination and reconciliation, had mostly positive effects to the indigenous Australian community, creating a stronger bond between black and white Australians, encouraging the concept of closing the gap between indigenous Australians and non-indigenous Australians. These policies had an incredible influence on the indigenous Australians life, changing many ways they lived. The policies changed the path of history for all Australians. The protection policy the first policy and had serious affects on the aboriginals of Australia. Violence against aboriginal people had been at a high rate, the white Australians felt it their duty to protect the aboriginals, the policy aimed to separate aboriginals from white Australians. They were removed and put into government reserves and church missions, where they were forced to become Christians. The aim of the policy and missions was to eradicate all aboriginals’ languages, religions and spirituality, In 1883 a protection board was set up to run the missions. The missions and camps had a paternalistic approach, treating the aboriginals the way a parent would treat a small child. The impact from this policy was horrific, with the mission being similar to a prison. Aboriginals lost their independence and became extremely reliant o... ... community and live along side white Australians, while other aboriginals happily moved in to the community and came to live a more civilised life. The next policy brought in was the policy of self determination this, was very welcomed by the aboriginal community, as it gave the aboriginals back some of their rights. As the relationship between non-indigenous Australians and indigenous Australians improved, there was a high demand for reconciliation. With many opinions including why the people of today should say sorry for the past Australians injustices. The affects from reconciliation were caused by the controversial approach; there have been numerous speeches, activities and ‘sorry days’. The affects from all the policies varied greatly, due to the differences in the policies. The affects caused change the path of history and have gotten us where we are today.

From 1600 †1763

From 1600 – 1763, several European nations vied for control of the North American continent. Why did England win the struggle? Support your answer with details of each nation's successes and failures. From the early 1600’s to the mid 1700’s, several European nations vied to control North America. Spain, Great Britain, and France were all powerhouses trying to colonize the free world and create a massive empire. Out of the three, England won the struggle because of failures made by the Spanish and French in the years before the American Revolution.The Spanish were the most powerful nation before the colonizing of the West Indies began. They had the Spanish Armada who was known for never losing a single battle. They also had all the riches in the world from all of their explorations. Unfortunately, during the early 1600’s, the Spanish began to experience fatigue from overextension with their army. The Spanish had to take care of problems in their Dutch terri tories causing them to leave the West Indian Islands and Jamaica open for grabs.Great Britain would eventually claim it and they began to work with sugar, the rich man’s crop. One difference between the British and Spanish motives for colonizing was that the Spanish based part of their time converting people to Catholic. The British were not concerned with religion, but more concerned with expanding their empire and making a profit. So by now, the British had colonized most of the Atlantic coast from Maryland down to Georgia. Another nation that wanted to have control over North America was the French.The French owned land from Quebec all the way down to the end of the Mississippi River in New Orleans. They basically controlled â€Å"middle† America. The French were in the business of trapping and fur trade. A very profitable business, but not a very sustainable one on its own. The French never really had a chance to control the New World because they were not as power ful as the Spanish or the British. France lost their hopes of having control in North America when they lost the French and Indian War with Great Britain.Great Britain’s victory over the French caused them to give up most of the land that they claimed and now half of the United States was in control of the British. England won the struggle for control of North America because when they saw a chance to pick up more land from another country, they would grab it. They had the army power to go to war with France and the Spanish had too much on their plate which weakened them. The English controlled the east coast of North America and had many profitable industries such as tobacco, sugar, and indigo. England won based on their power and strategy.