Thursday, October 3, 2019
Multifunctional Porous Organics Synthesis
Multifunctional Porous Organics Synthesis TITLE OF WORK The synthesis and characterisation of functionalized porous organics Abstract Lophine based radicals have been studied for many years due to their photochromic nature, recent literature has seen attempts to connect two radicals to carbon based backbones. In this report we will discuss attaching six lophine molecules to a single backbone which is a phosphazene ring. Cyclophosphazene rings have a unique conformation allowing for supramolecular architectures to be formed by varying the substituents, these architectures range from 0-2D structures. The hexalophine molecule exhibits 1D channels due its unique conformation which leads to the formation of a porous material. Porous organics are of high interest in recent literature due to them being a cheaper, less toxic alternative to MOFs as well as having the ability to be modified and tailored easily due to the simple starting materials. In this report we shall state synthetic pathways from simple molecular building blocks to hexalophine (32%) and two derivatives, compound 4 (46%) and 5 (15%). These two derivatives have the potential to increase pore stability. This report will also include the oxidation of hexalophine to its radical species which were found to display photochromic properties and it is also believed that this material could contain light gated pores which are closed in the dimer form of the product but then open upon irradiation of UV of 365nm. 1. INTRODUCTION 1.0 Properties and potential uses of Lophine This report will feature chemistry based upon the triphenylimidazolyl based radicals (TPIRs) as well as the dimer form hexaarylbiimidazole (HABI). Lophine (2,4,5-triphenyl-1H-imidazole) is a heterocyclic imidazole derivative where three phenyl rings are attached to the imidazole ring (figure 1), these imidazole derivatives are an area of importance due to the many interesting properties it possesses. Lophine has been of interest to researchers for many years with its chemiluminescent properties being first discovered in 1877 by Radziszewski.1 The oxidation of the lophine molecule follows the reaction scheme below, where lophine is oxidised to the TPIR radical state via addion of base and treatment with Fe forming one of six dimers both in solution and the solid state (figure 2). These materials display photochromic, thermochromic and piezochromic properties. The mechanism of photochromism of the lophine dimer is the homolytic cleavage of the 2C-1N bond of the dimer by irradiation wit h light, forming two lophine radicals.2 The fast colour change associated with this dimer opening means there is a potential use in display screens or as the basis for molecular switches, where irradiation with light opens the dimer forming the radical in turn switching the external component On/Off. These possible applications have caused a focus on creating methods to manipulate and control the colour of these materials and as well as to increase the rate of switching.3 The colour of the radical form is dependent upon the substituents on the ring, the more conjugated the system the further toward the red side of the spectrum the colour.4 Lophine displays piezochromic properties in its solid state, upon applying pressure lophine crystals the colour change of yellow to blue/green has been observed, this occurs via the radical dissociation of the 1N-1N dimer bond.5 Other more unusual modes have been of dimerization such as the 2C-2C have now also been isolated, this mode features a u nusually long C-C bond.3 Figure 1 The structure of Lophine (2,4,5-triphenyl-1H-imidazole) Another interesting lophyl radical derivative is the 1,8-TPID-naphthalene radical which consists of 2 lophine radicals connected by a naphthalene ring. 1,8-TPID-naphthalene has been characterised in the solid state by Abe et al; who studied the photoreactivity of the compound. 1,8-TPID-naphthalene allowed the group to fix two radicals onto a backbone meaning that the radicals were in close proximity and could dimerise easily as opposed to two radicals not connected via a backbone which first need to find eachother in order for dimerization to occur (figure 3). They found that the dimer could be cleaved photochemically giving the diradical and then could be thermally converted back to the dimer.6 They also found that the formation of a peroxide bridge was much more common than previous literature had accounted for. This bridging occurred when the 1,8-TPID-naphthalene radical was placed under an O2 atmosphere.7 This peroxide bridge formation is very important as when oxygen quenches th e spin to form the closed shell peroxide it does so irreversibly meaning the material is no longer photochromic. It was then shown that this peroxide degradation pathway can be generalised for the chromic dimers of TPIR materials, with non-tethered TPIRs forming similar peroxide bridges.8 A recent development by the same research group has also shown how a thiophene substituted phenoxyl-imidazole radical complex (PIC) can generate two non-equivalent radical upon irradiation with UV light. The colour change can be fine-tuned from tens of seconds to nanoseconds, however a sensitivity to lower wavelengths of light meant that applications were limited. This problem was rectified by adding a phenyl group to the 5 position of the thiophene ring.9 Figure 2 The six potential dimerization modes of two lophyl radicals.3 Figure 3 Illustrates the reversible conversion of 1,8-TPID-naphthalene between its radical and dimer forms. 1.1 Hexa-substituted Phophazene Rings, Tectons and Crystal Engineering A key component of this project was the exploitation of the Phosphazene ring as soft tecton; a tecton is a molecular building block that interacts with sticky sites, formally known as supramolecular synthons, via spatial arrangements to induce the formation of supramolecular aggregates. The search for new tectons is a hot area of research due to the constantly growing field of crystal engineering where the aim is to produce functional single crystal materials using intermolecular interactions. The arrangement of molecules in solid state structures is largely dependent on striking a fine balance between intramolecular forces and packing interactions, knowledge of these forces is key to the field of crystal engineering.10 In general, hard tectons interact via more robust synthons than soft tectons and therefore usually crystallise with unambiguous geometries. Whereas soft tectons and less robust synthons allow for the formation of supramolecular isomers (figure 4).11 These tectons allo w for many functional materials to be formed in a one pot synthesis, they also have the ability to be carefully adjusted to alter and improve upon their functionality.12 Cyclophosphazenes are extremely soft tectons that interact with soft synthons to give a large variety of supramolecular architectures in the solid state. The conformation of the cyclophosphazenes is also very interesting as three substituents reside above the plane of the ring and three below (figure 5). It was found that small modifications to the substituents attached to the ring gave supramolecular architectures ranging from 0D to 2D structures (figure 6) such as include monomer, dimer, cyclic hexamer, zigzag chain, linear chain, double chain, graphite-type sheet, rectangular grid and hexagonal close-packed sheet. Such variety of structures came from the easy rotation about the exocyclic P-N bonds, which allowed variable directionalities for all of the N-H bonds. 11                          3a)                                                                  3b) Figure 4a) Shows benzene-1,4-dicarboxylic acid a classic example of a hard tecton. 4b) shows a silanetriol a classic soft tecton. Figure 5 Conformation of a Hexa-substituted Phosphazene Ring. Figure 6 Schematic representations of aggregation patterns of (RNH)6P3N3 in the solid state.11 1.2 Magnetism and Magnetic Frustration The materials we aim to make during this project once appropriately oxidised should go on to form dimers which when irradiated with UV light form discrete radicals containing unpaired electrons thus giving each radical an associated magnetic moment. Neutral organic radicals tend to be paramagnetic and exhibit Curie- Weiss behaviour, where the spin vectors of the unpaired electrons are randomly aligned above the Curie temperature (Tc), which is the critical temperature below which the long ordered state is established, unless a magnetic field is applied. If spin vectors are parallel to each other below the Curie temperature then the material is ferromagnetic, if the spin vectors are aligned antiparallel to one another the material is antiferromagnetic.13 Due to the geometry of the phosphazene ring (three substituents pointing up above the plane of the ring and three below) there is the possibility of forming a 2D triangular lattice of spins if the substituents are organic radicals. This could possibly lead to geometric magnetic frustration due to the fact that the two nearest neighbours to a spin are themselves nearest neighbours and therefore antiferromagnetic couplings cannot be satisfied (figure 7).14 This can lead to very interesting magnetic properties. Most solid state examples of this geometric frustration tend to be transition metal oxides, however, studies have been done on organic systems that also distribute geometric frustration.13 One example of this is m-MPYNNP+ which is a spin  ½ organic radical that upon dimerization forms a 2D triangular lattice which demonstrates the aforementioned geometric frustration.14 The issue of spin frustration has been around for a long time as Quantum spin liquids (QSL) were first theoretically proposed by Anderson many years ago which are now a hot topic of research due to the realisation of these QSLs in organic materials such as k-(ET)2-CH2(CN)3, which has a near perfect triangular lattice with angles very close to 120 °.15 A QSL is an exotic ground state where interacting spins continuously fluctuate with no formation of low range magnetic order even at sufficiently low temperatures.16 Figure 7 Antiferromagnetic coupling cannot be fulfilled causing geometric magnetic frustration. 1.3 Porous Materials Porous materials are as important as ever due to their wide spread use in several fields such as catalysis and gas absorption,17 meaning they can play a critical role in the route to solving our growing energy shortage problems. Porous materials are instantly associated with materials such as zeolites, metal organic framework (MOF) and organic polymers. MOFs are characterised by their tuneable pores and inherent flexibility which more classical carbon or oxide based structures do not possess, this gives a wide range of applications for MOFs such as gas storage, separation, drug delivery or catalysis.18 Porous organics have been discovered in nature but are largely created synthetically and approaches often need to be coupled with knowledge of crystal engineering. These materials are often held together by directional forces which form extended frameworks of noncovalent interactions such as À- À interactions, hydrogen bonding or coordinate bonding (figure 8).17 Like zeolites a nd MOFs porous organics have the ability to selectively absorb atoms and molecules in the gas phase.19 There are many positives to these porous organics, they are often cheaper to synthesise and less toxic as well as being far less dense than metal containing MOFs. Figure 8 One example of a Porous Organic by Sozzani et al. 1.4 P3N3 Hexalophine The chemistry of P3N3 Hexalophine incorporates much of the chemistry discussed above and has many interesting properties. The P3N3 Hexalophine molecule consists of six lophine substituents attached to the phosphazene ring via a P-O bond (figure 9). Previous work in the Robertson group found that the solid state structure of Hexalophine consisted of a pseudo hexagonal motif giving rise to 1D channels that run parallel to the stacking axis (figure 10). The molecule maintained its D3 symmetry in the solid state. The phenyl rings twist to maximise pi-stacking interaction and the 3 imidazole nitrogen atoms form hydrogen bonds to a central water molecule. There are 4 pi-pi interactions that stabilise this structure, the molecules are in a slipped conformation allowing the phenyl and imidazole to rings overlap. Other non-covalent interactions such as van der Waals interactions also help to stabilise the structure. The high symmetry of the structure which comes from the hexa substituted phos phazene ring (three above the plane of the ring and three below) gives an equal distribution of intermolecular forces giving a high probability of forming a stable porous structure. IGA measurements with CO2 loading at 195K shows a Type I isotherm with absorption reaching 8cm3g-1 at a pressure of 700mmHg confirming the materials microporosity. However only a small fraction of the void space contained CO2. Figure 9 The structure of Hexalophine. Figure 10 The crystal structure of Hexalophine, illustrating the 1D channels. 1.5 Aim of Project The aim of this project is to combine our knowledge of the chemistry of both lophine radical systems and cyclophosphazene rings to find elegant synthetic routes which will improve upon the porous properties of hexalophine. This will be done by varying the ring substituents to increase stability of the pores and to improve its gas absorption properties. Three lophine derivatives have been identified as plausible candidates for thid are where two of the phenyl groups on the lophine will be replaced by two thiophene rings and two pyridine rings respectively, with the position of the nitrogen in the pyridine ring being varied depending upon the synthetic pathway (figure 11). We wish to synthesise and fully characterise these derivatives including growing single crystals for structural studies via X-ray crystallography. Also a stoichiometric controlled oxidation of the hexalophine material to its neutral radical/dimer pair is required in order to further investigate the properties of hexa lophine such as the possibility of creating a photochromic material that has light gated pores that open on irradiation with UV light. R=                 or       or Figure 11 the synthetic targets of this project. 2. Results and discussion 2.0 Hexa-benzaldehyde Synthesis The first step in this synthetic project involved attaching six benzaldehyde units to the phosphazene ring via a P-O oxygen bond. This was achieved by reacting the phosphonitrillic chloride trimer along with 6 equivalents of 4-hydroxybenzaldehyde, potassium carbonate in dry THF (figure 12). The reaction was monitored with 31P NMR which showed completion when only a singlet was present in the spectra indicating full substitution. This produced the compound 1 which was the precursor for many of the subsequent reactions. The reaction gave the desired product in a fairly low yield (45%). Whilst the yield was slightly low the FT-IR showed all of the characteristic absorptions such as C=O (1697cm-1) and CAr-CAr (1585cm-1). 31P NMR was conducted and showed a sharp singlet at 7.08ppm which indicated full substitution on the phosphazene ring as all of the environments are equivalent. 1H NMR was also conducted and show a singlet at 9.87ppm with an integration of 6Hs which was as expected for t he 6 aldehyde protons, two doublets were found in the aromatic region and integrated to 12Hs each which was correct for the number of protons expected. The CHN analysis was almost perfect with less than 0.2% difference from the calculated values, this indicated that the product was of high purity. Mass spectometry also indicated that the desired product had been synthesized as a [M+Na]+ peak was detected at 884. Figure 12 The reaction scheme for the synthesis of 1. 2.1 Synthesis of Hexalophine and Hexalophine derivatives 2.1.0 Using Diketones The synthesis of hexalophine and hexalophine derivatives is important due to their porous properties which can be of great importance in fields such as gas storage and catalysis. The method for attaching six lophine units to the ring was a ring condensation of 1 on the six benzaldehyde units attached to the phosphazene ring using a synthesis based upon Radziszewskis synthesis.1 The product 2 was achieved by reacting 1 along with six equivalents of benzil, ammonium acetate in excess in glacial acetic acid (figure 13). The yield for 2 was quite poor (32%), the FT-IR showed all of the characteristic peaks such as CAr-H (3055cm-1), C=N (1604cm-1) and CAr=CAr (1538cm-1) indicating the desired product had been formed. This was further confirmed by both the 31P and 1H NMR, the 31P NMR showed a singlet at 8.36ppm which indicates full substitution on the phosphazene ring. The 1H NMR showed a singlet at 12.65ppm which had an integration equal to 6Hs which is representative of the 6 imidazole N -Hs, it also showed multiplets in the aromatic region with an integration of 84Hs which is exactly the number of aromatic hydrogens in the desired product. CHN analysis of the product correlated well with the desired structure, especially when three molecules of water were factored into the calculation. It is unsurprising that this compound also contained water due to its porous nature.                                    NH4OAc                                 Acetic acid (6eq.) Figure 13 The reaction scheme for the synthesis of 2. Another reaction designed based upon the ring condensation reaction was the synthesis of 4. This synthesis builds upon the diketone functionality as above, however, in this reaction the R groups of the diketone thenil were thiophene rings as opposed to the phenyl rings of benzil. Thenil like benzil was reacted with 1 and ammonium acetate in glacial acetic acid (figure 14). The yield for this compound, whilst better than 2, was still fairly low (46%). FT-IR showed the characteristic peaks such as CAr-H (3071cm-1), CAr=CAr (1643cm-1) and C=N (1607cm-1) indicating the target molecule had been synthesised. The 31P NMR showed a singlet at 8.26ppm again indicating full substitution. The 1H NMR showed a singlet 12.91ppm with an integration of 6Hs representative of the 6 imidazole N-H hydrogens, it also showed multiplets in the aromatic region with an integration of 60 which was again exactly what was required for the number of aromatic hydrogens, indicating the correct product had been synt hesised. The CHN analysis was close to the theorectical values required especially when four water molecules were factored in, again this is unsurprising as this material like 2 is also expected to be porous.                        NH4OAc                              Acetic acid (6eq.) Figure 14 The reaction scheme for the synthesis of 4. Like thenil and benzil, pyridil is also a diketone where the two R groups are heterocycles, in this case the two heterocycles are pyridine rings. Pyridil was used again with the classical Radziszewski based synthesis to synthesise the compound 5 (Figure 15). The yield for this compound was very low (15%) due to a lot of mass lost upon recrystallization and decomposition upon heating. The FT-IR showed the correct absorptions for the key functional groups such as C=N (1600cm-1) and P=N (1158cm-1) indicating that the target compound had been synthesised. However large OH absorption band (3349cm-1) was also present showing that the product contained a considerable amount of water or ethanol. CHN analysis of the compound showed a vast difference in carbon and nitrogen values when compared to the theoretical values indicating some impurities in the sample. The fact that the product contained considerable amounts solvent would also skew the result of the CHN analysis somewhat.                     NH4OAc                               Acetic acid (6eq.) Figure 15 The reaction scheme for the synthesis of 5. 2.1.1 Using Aldehydes for an alternative preparation The idea of using aldehydes such as pyridine carboxyaldehyde and benzaldehyde as opposed to the diketones used above was born when questioning on how we could stabilise the pores in the materials we wished to synthesise as larger groups could be added to these aldehyde starting materials. An alternative synthesis of 2 using twelve equivalents of benzaldehyde is illustrated in figure 16. The reaction was left to reflux for 7 days however the 31P NMR showed a multiplet indicating that full substitution had not occurred or a mix of products was present. Unfortunately, this was a reoccurring theme as the failed synthesis of 3 using twelve equivalents of pyridine carboxyaldehyde (figure 17) also showed a multiplet in the 31P NMR. Benzaldehyde (12 eq.) Figure 16 The reaction scheme for and alternative preparation of 2. Carboxyaldehyde (12 eq.) Figure 17 The reaction scheme for compound 3. 2.2 Oxidation of Hexalophine and its derivatives The oxidation of hexalophine is of great interest due to the potential properties it may possess, such as it possessing photochromic properties which may lead to light gated pores. For this oxidation an excess of potassium hydroxide was used to create the anion before 50 equivalents of the classical oxidising agent potassium ferrocyanide (III) were used to perform a one electron oxidation to the radical species 6, a yellow to orange colour change is associated with the formation of the radical species. This radical species quickly dimerises and an orange to yellow colour change is associated with this. Upon irradiation with UV light (365nm) the dimer opens to form two radicals, the colour change associated with this was yellow to purple displaying the photochromic behaviour of this compound (figure 18). The radical species is stable for a number of hours in the solid state unless gentle heating is applied which induces dimerization again and the colour change of purple to yellow is a ssociated with this. FT-IR showed characteristic absorbances of CAr-H (2955cm-1), C-N (1301cm-1) and P=N (1198cm-1) which are present in the desired product. The thiophene hexalophine derivative 4 was also oxidised using the same classical oxidation conditions as above to form its radical species 7. Upon separation the system formed 3 layers, an organic layer, an aqueous layer and a solid substance formed which was soluble in neither. Both the organic layer and solid substance were irradiated with UV light to test for photochromic properties however neither displayed a colour change and thus further testing of this material via UV/Vis spectroscopy is required to determine its nature. Figure 18 A RBF containing the hexalophine dimer and radical, the purple is the radical species, the yellow is the dimer species. 3. Conclusions and further work The aim of this project was to synthesise and characterise functionalised porous organics based upon hexalophine as well as to perform oxidations to the radical species and study their properties such as photochromism. For the most part the aim of the project has been met as two derivatives of hexalophine (4 and 5) and hexalophine (2) itself have been synthesised from simple molecular building blocks and characterised using a range of spectroscopic techniques such as NMR, FT-IR and CHN analysis. The next step in the characterisation of these materials would be to gain crystal structures via x-ray crystallography to show the packing arrangement of these molecules and to prove the existence of pores with in the molecule created from the unique conformation of the phosphazene ring. Additionally, once crystal structures have been gained gas absorption test should be taken to test both the gas uptake properties and selectivity of certain gases. Yields for these experiments were quite low and the aldehyde reactions did not demonstrate full substitution onto the ring, one possible solution would be to try the reaction in a Parr pressure reactor. The oxidation of hexalophine was carried out with great success as the experiment demonstrated the proposed photochromic nature of the material, also the stability of this material with respect to air was very surprising. If possible crystal structures for this material should be obtained in order to investigate further the possibility of light gated pores which when the molecule is in the dimer form are closed but once in the radical form are open. 4. Experimental details 4.0 Ma
Wednesday, October 2, 2019
The Good Earth in relation to food and culture :: essays research papers
     The following in a report on the themes and action of The Good Earth by Pearl S. Buck as it relates to food and culture. This novel tells the story of Wang Lung. He is a man who rises from being a poor farmer to a very wealthy man because of his faith in the good earth. In the beginning of the story Wang Lung tries to see as little water as possible because he feels safest with his land under his feet. His family is very poor so he must feed his father corn gruel and tea. Wang Lung needs a wife so saves up the little money he has and buys a woman who is a slave named O-lan. O-lan is sold to Wang Lung so she can take care of the home, cooking and bear children. Wang Lung is disappointed when he first sees O-lan because she does not have bound feet which was a desirable quality at that time but he does enjoy when O-lan has the food ready when he comes in a night from the land. Wang Lung is very proud when O-lan makes cakes that no one else in the village knows how to makes and when his family comes to feast for the new year at their house. As a humble farmer Wang Lung always pay his respects to the figures of the Earth god and his mistress when he passes. Wang Lung’s love for the earth is the chief driving force in his life. It is also the foundation of his family and the one he turns to when he has troubles. Land is a sign and a symbol to Wang Lung. When O-lan’s and Wang Lung’s first child is born they dye eggs red and distribute them to the village to shown their first born is a male. After a year of good rains Wang Lung begins to amass a good fortune so he hides the money that they make so people will not try to borrow it. Again, the produce from the year is good, and Wang Lung is able to hide more silver. He buy land from the great house in town and it is very fruitful, yielding more harvest than his own land. Now everyone in the village knows that Wang Lung is the owner of a piece of the Hwang land. His status rises in the village. The following year the rains don’t come and the land dries up. The Good Earth in relation to food and culture :: essays research papers      The following in a report on the themes and action of The Good Earth by Pearl S. Buck as it relates to food and culture. This novel tells the story of Wang Lung. He is a man who rises from being a poor farmer to a very wealthy man because of his faith in the good earth. In the beginning of the story Wang Lung tries to see as little water as possible because he feels safest with his land under his feet. His family is very poor so he must feed his father corn gruel and tea. Wang Lung needs a wife so saves up the little money he has and buys a woman who is a slave named O-lan. O-lan is sold to Wang Lung so she can take care of the home, cooking and bear children. Wang Lung is disappointed when he first sees O-lan because she does not have bound feet which was a desirable quality at that time but he does enjoy when O-lan has the food ready when he comes in a night from the land. Wang Lung is very proud when O-lan makes cakes that no one else in the village knows how to makes and when his family comes to feast for the new year at their house. As a humble farmer Wang Lung always pay his respects to the figures of the Earth god and his mistress when he passes. Wang Lung’s love for the earth is the chief driving force in his life. It is also the foundation of his family and the one he turns to when he has troubles. Land is a sign and a symbol to Wang Lung. When O-lan’s and Wang Lung’s first child is born they dye eggs red and distribute them to the village to shown their first born is a male. After a year of good rains Wang Lung begins to amass a good fortune so he hides the money that they make so people will not try to borrow it. Again, the produce from the year is good, and Wang Lung is able to hide more silver. He buy land from the great house in town and it is very fruitful, yielding more harvest than his own land. Now everyone in the village knows that Wang Lung is the owner of a piece of the Hwang land. His status rises in the village. The following year the rains don’t come and the land dries up.
Review Of the City Of Mexico In The Age Of Diaz Essays -- essays res
The Great Divide University of California-Berkley geographer and author Michael Johns argues in his novel, The City of Mexico in the Age of Diaz, that the central Zocalo of Mexico City does more than geographically segregate the East from the West, but Mexico’s national mentality as well. During the years of Diaz’s democratic faà §ade, the upper classes thrived upon plantation exports, feudalist economics and the iron fist of Diaz’s rurales while struggling to maintain European social likeness. East of the Zocalo, shantytowns housed thousands of poor pelados that served as societal blemishes of a suburbanite’s experience. In Johns’s work, the penniless and indigenous serve as the scapegoats for the priviledged and their obsession with grooming Mexico City to be a little Europe.      A growing affluent class called upon the Diaz regime and imported architects to construct buildings in the Zocalo to reflect a â€Å"proper†image that drew on influences from Europe and the United States. Johns recognizes the architectural dependence of the influential Mexicans constructing Mexico City when he states, â€Å"Mexican architecture, on the other hand, was an expression of a city run by a people who were looking to create their own culture while entirely dependent on the industry and ideas of Europe and America†(22). The same construction that the elite felt was a celebration of a newfound dignity in the Mexican people was criticized, by visitors and locals alike, as grandiose and a futile effort to shield the native roots of a circle of imposters. Johns’s argues that the â€Å"Mexicans knew little of their adopted European tradition, had acquired even less of its taste, and enjoyed none of its tranquility†(23). While the influence on the Westside led to development, the squalor and lack of authority of the peasants on the Eastside created mesones, or as Johns described them, â€Å"†¦a little more than ‘a bare spot to lie down in, a grass mat, company with (the) vermin that squalor breeds†¦Ã¢â‚¬â„¢Ã¢â‚¬ (48). Politics on the Westside of the Zocalo were concerned little with the living conditions of the majority. No one would undertake the unglamorous task of assisting the poor, but rather they attempted to veil the masses in the shadow of their refined buildings and recent assumption of culture.      Another shield of the upper classes was t... ...rural hamlets, many in the big city drowned their sorrows in pulque †¦ it accounted for over 90 percent of all the alcohol drunk in the capital †¦ The suggestive power of a bright scene or an exotic name painted on the faà §ade was at times enhanced by a slogan like ‘Drink Pulque, Be Happy†(50-51). The little solace the masses gained from their wages was usually happily wasted in one night after the paycheck had arrived. Aspiring to drown their social inferiority, pulque crippled the east side’s population. In essence, both rich and poor yearned to gain acceptance, at conscious or subconscious levels.      Mexico City in the Age of Diaz is a literary illustration of one country’s struggle to define itself as a modern, cultured nation. Written mainly in the upper class point of view, the poor masses are defamed as lesser, indigenous beings. This anxiety of the Westside population and â€Å"President†Diaz lead not to reform but to exploitation and ignorance of social dilemmas. Europe and the United States served as a model for these citizens who craved status and acceptance due to the inherent inferiority complex gained by a historically conquered people.
In Book Two of Homer’s The Odyssey Telemakhos gains a significant amount :: Classics
In Book Two of Homer’s The Odyssey Telemakhos gains a significant amount of confidence and decides to call an assembly. At the assembly The Odyssey In Book Two of Homer’s The Odyssey Telemakhos gains a significant amount of confidence and decides to call an assembly. At the assembly a wise man Aigyptios presents the listeners with a rare introduction. He states that an assembly has not occurred for about twenty years and commends the individual that had the audacity to call one. At this assembly Telemakhos protests fervently that his mother’s suitors be expelled since they have no respect and appreciation for their generosity â€Å"these men spend their days around our house killing our beeves and sheep and fatted goats , carousing , soaking up our good dark wine, not caring what they do†. At the end of Telemakhos’s first battle to persuade the minds of the Akhaians against the suitors, a fellow leader named Antinoos decides to defend his fellow suitors. Antinoos counteracts Telemakhous claims informing everyone that the suitors should not be criticized since Penelope is the one to blame â€Å"you should know the suitors are not to blame but it is your own dear –incomparably cunning mother â€Å".He further adds that she has been deceiving them with her clever ability to avoid any decisions about marriage and gives the example of her unwoven loom. The suitors then commands that Telemakhos takes immediate action and either evict Miss Penelope from the house or compel her to marry the man her father suggests. Telemakhos makes a firm stance against the suitor’s suggestions and insists that he will never turn his mother out. During Telemakhos’s plead to save his mother; a pair of eagles appears in the sky. Another heated debate then rises between Halitherses and Eurymakhos in which Halitherses argues that the sighting of eagles foretells that Odysseus arrival is near and that the suitors will face grave danger if they don’t leave, while Eurymachus protests that the sighting of the birds are insignificant â€Å"Bird life aplenty is found in the sunny air, not all of it is significant†. Telemakhos concludes that he is finished with appeals and will let the Gods do the justice. All he desires is to locate a fast ship and a crew of men to carry out a voyage and arrive at a conclusion about his father whereabouts â€Å"If he’s alive and beating his way home you might hold out for another weary year;†¦..then I can come back to my own dear country and raise a mound for him†¦.†. After the assembly Telemakhos feels a sense of defeat and decides to
Tuesday, October 1, 2019
The Agricultural Adjustment Act :: essays research papers
The Agricultural Adjustment Act      During World War I, England’s agricultural economy was badly damaged. This inconvenience for the English was a blessing to American farmers. Since the invention of the combine, and various other mechanical harvesting machines, American farmers could increase their crop yield. In turn they could export the extra crops to England for more money. Once England got back on it’s feet, American farmers could not find any exports for their crops. As they continued to produce more than the American people could consume, the prices of agricultural goods dramatically dropped. By the 1930’s many farmers were in serious need of help, with heavy farm loans and mortgages hanging over their head’s. Nothing had been done to help the farmer’s during The Hoover Administration. So in 1933 as part of Roosevelt’s New Deal, the Secretary of Agriculture, Henry Wallace devised a plan to limit production and increase prices. Which came to be known as the Agricultural Adjustment Act of 1933, also known as the AAA. The AAA was established on May 12, 1933 it was the New Deal idea to assist farmers during the Great Depression. It was the first widespread effort to raise and stabilize farm prices and income. The law created and authorized the Agricultural Adjustment Administration to: Enter into voluntary agreements to pay farmers to reduce production of basic commodities ( cotton, wheat, corn, rice, tobacco, hogs, milk, etc..), to make advanced payments to farmers who stored crops on the farm, create marketing agreements between farmers and middlemen, and to levy processing taxes to pay for production adjustments and market development. Basically the AAA paid farmers to destroy their crops and livestock in return for cash. In 1933 alone cotton farmers were paid $100 million to plow over their cotton crop. Six million piglets were slaughtered by the government after they bought them from farmers. The meat was canned and given to p eople without jobs. In order for this new bill to work there needed to be money to pay the farmers, this money came from the companies that bought farm products in the form of taxes. While it seemed like a good idea to pay farmers to cut back on crops to lowering the surplus and boost the economy, The Supreme Court found the Act unconstitutional in 1936.
Environmental Impacts of a Cement Plant Unit
Decision The building activities will ensue in minimal loss of flora and surface soil in the works country. Maximum possible extent tree cutting would be avoided. No important inauspicious impact on the dirt in the encompassing country is anticipated. During building stage, dust will be the chief pollutant, which would be generated from the site development activities and vehicular motion on the route. The impact of such activities would be confined within the undertaking boundary and restricted to the building stage. To extenuate these impacts regular scattering of H2O will be done at the building site. The attack roads will be black carpeted and vehicles will be kept in good order to minimise car fumes. The coevals of domestic sewerage discharge from labour settlements and lavation of building stuffs stockpiled and concrete batching works will hold some impact on surface H2O and to a smaller grade on groundwater. To turn to possible impacts on H2O quality, disinfected latrines ( with regular liming ) will be used as chief constituent of the sanitation system.Construction procedure would include fiction of steel constructions, concrete and related H2O use. The possible impact is considered minor as it will be largely happening during building period and will hold no long term impact with position to relentless pollution. The overall impact on H2O environment during building stage due to the cement works would be of short term continuance and insignificant. The major beginnings of noise during the building stage are vehicular traffic, building equipment like dozers, scrapers, concrete misers, Cranes generators, pumps, compressors, stone drills, pneumatic tools, proverbs, vibrators etc.the operation of these equipment will bring forth noise runing between 70-85 dubnium ( A ) . The noise produced during the building will hold important impact on the bing ambient noise degrees. The major work will be carried out during the daylight. Most of the land identified for the bing undertaking contains bare land with limited figure of trees. Trees will be cut merely if required and as per functional demand. The remotion of flora from the dirt and relaxation of the surface soil by and large causes dirt eroding. However such impacts will be confined to the works site and will be minimized through pavement and H2O scattering. Therefore no major loss of biomass is envisaged during building stage. The non workers in the constitute more than 60 % of the entire population in 10 kilometers radius survey area.This indicates the handiness of ample work force required for the building activity in the vicinity. The works will supply either direct or indirect occupation chances to the local population every bit far as possible. There will be some migration of labour force from outside the survey country during building stage, which may set some force per unit area on the local colonies and resources. So the demographic impact is envisaged to be fringy and impermanent in nature. However, the flow of work forces, money and stuff will impact the socio-economic position of the people in the country. The positive impact may be the addition of employment chances for unskilled and semi-skilled workers. Ancillary development such as stores, hotels and other allied services will besides open up avenues for employment. The subsequent betterment in the position of the people will besides assist in increasing the wellness and instruction position of the people. Diseases matching to labour influex and their impact on local community will be regulary monitored. Health position monitoring of labors and its environing population shall be carried out with the nomadic wellness attention installations. During building of any big undertaking, there is ever opportunity of traffic congestion on nearby roads due to heavy vehicular motion. However it was observed that the route web next to the cement works has medium traffic and have a mix of fast moving and decelerate traveling traffic. Thus add-on of the awaited vehicles during building stage will non hold much impact on the traffic scenario. Literand demand for the cement works is 120.626 hour angle, which is already in ownership of the company. With execution of the works, the land usage at the site will be for good changed to industrial class. Impacts on dirts will be restricted during building stage, which will acquire stabilized during operational stage. The impact on the top dirt will be confined to the chief works country. The air borne fleeting dust from the works is likely to be deposited on the surface soil in immediate locality of the works boundary. However, the fleeting emanation are likely to be controlled to a great extent through control steps such as H2O sprinkler systems and dust extraction and dust suppression systems shall be installed. All the solid waste generated will be to the full re-used either in the procedure or in accessory activities ; therefore no impact of solid waste is envisaged on dirt quality of the country. Adequate stack highs have been provided to scatter gaseous emanations over a broad country. In order to command emanations of particulates adequate control equipment are installed.Prediction of impacts on air environment has been carried out by utilizing land degree concentration at a distance of 1.0 kilometers on southeast way. The impact on air quality is assessed based on emanation of the cement works. Particulate affair will be the of import pollutant breathing from the cement works, the maximal attendant land degree concentration that the maximal short term 24 hourly land degree concentrations for PM, SO2and NOx during normal operations of the works composite are likely to be 2.48 & A ; micro ; g/m3, 12.85 & A ; micro ; g/m3and 9.75 & A ; micro ; g/m3 severally occuruing at a distance of 1.0 to 1.5 kilometers during station monsoon season. Fleeting dust emanations from the bing works would be important as there will be air pollution due to activities like conveyance of limestone, coal handling, cinder handling, and oppressing unit and by and large due to the motion of vehicles on the roads. The limestone conveyance is being carried out by covered conveyer system from the limestone crusher unit to the works, therefore fleeting dust in non envisaged. Number of smaller sized bag dust collectors/bagfilters for de-dusting at tasfer points and other fleeting dust emanation countries are installed. Hence the impact due to fleeting emissuions would be undistinguished. All the internal roads within the works premises will be metalled ; hence dust originating from the internal roads will be in important. The greenway and regular H2O sprinking will foster aid decrease in fleeting emanations. The bing cement works contains figure of points of heavy equipment such as fans, engines, generators and cement grinding works. There will be associated route or rail traffic including truck motion and loading equipment. Consequently cement fabrication is likely to bring forth noise and quiver. Noise and quiver is greater from heavy truck traffic associated with quarry operations and conveyance of natural stuffs and finished merchandise. The chief noise bring forthing beginnings from the cement works will be crushers, ball Millss, ice chest fans, pumps, compressors, turbines along with chilling tower and boilers. The noise degrees at the beginning for these units will be maintasined below 85 dubnium ( A ) . Hazardous waste in the signifier of used and godforsaken oil is generated from autoworkshop, different subdivision of cement works. No risky waste will be generated either in the procedure or pollution control equipment installations. There is no solid waste generated from the cement works. All the dust collected in air pollution control equipment ( APCEs ) will automatically be recycled into the procedure. Flyash use will be as per MoEF flyash use presentment. Flyash will be 100 % for production of pozzolona cement devising by the cement works. Solid waste in the signifier of sludge is generated from the sewerage intervention works. The waste will be used for maintain the assorted lequire suspended solids ( MLSS ) in the activated sludge procedure of STP and the balance waste is used as manure for greenway development. Since the unit will be runing on zero discharge procedure, no inauspicious impact on surface H2O organic structures is envisaged. The works drainage system will be ap propriately designed such that the storm H2O does non transport any pollutants. The impact from the air emanation is non expected to be important since the stack tallness design and the atmosphereic conditions are such that the ambient air quality at present every bit good as in hereafter after the present installation will be within the prescribed ambient air quality bounds set Forth by CPCB. Comprehensive control steps have been incorporated as elaborated under Environment direction program ( EMP ) . The discharge of waste stuffs ( stack emanation, waste H2O and solid wastes ) from works operations potentially could hold impact on public safety ad wellness if proper extenuation steps are non taken. The impact from the discharge of waste merchandises is non expected to be important since, the inauspicious impacts on ambient air, H2O and dirt quality are predicted to be low. It is predicted that the impacts on public safety will be really low, due to the effectuive safety system and safety direction available in the works. Overall, the impact on public safety and wellness from the cement works activities are likely to be undistinguished. Govindgarh modesty wood is 0.2 km north-northeast waies 10 kilometers radius survey country. But there are no ecologically sensitive countries like wildlife sanctuaries within 10 kilometers radius from the works and besides no migration path to avi zoology is observed or recorded in the survey country. Son gharihal sanctuary is located at a distance of 9.0 kilometer towards south east direction.similarlly as per the wood section, no endangered or rare species of vegetations and zoologies are reported or observed in the survey country. Development of a thick greenway and besides application of limestone injection in AFBC ( Atmosphric fluidized bed burning ) boilers, transit of stuff through closed conveyer system still further cut down of pollution tonss in the environing countries and contain the negative impact on wood and tellurian ecology. Hence the impacts on the tellurian ecology will be undistinguished. The wastewaters are non envisaged to be discharged into any watercourses. Hence no impact is envisaged from the bing works on aquatic organic structures. The impacts on the ecology will be due to the incremental gaseous concentrations and noise generated during operation of the bing power works. The demand of unskilled work force will be met from nearby small towns during building and operation stage. The works will besides assist in coevals of indirect employment apart from direct employment. This will be a positive socio-economic development for the part. There will be a general upliftment of criterion of life in the part. The discharge of waste stuffs ( stack emanation, effluent and solid wastes ) from procedure operations is expected to be undistinguished and may non hold possible impact on public safety and wellness. The inauspicious impacts on ambient air and dirt quality are predicted to be undistinguished. Primary wellness study was carried out to measure the wellness position of the people in the survey country in the small towns of Majhigawan, Sarda, Jurmani, Hinauti and Gorhatola small towns which are autumn in 2 kilometers radius from mines lease boundary. The survey reveals that in general the country is prone to malaria in monsoon season and icterus before and after monsoon season. Therefore is no disease form which can be attributable to any industrial pollution. The incidence of any lungs related wellness upset are chiefly due to the wonts such as smoke. The cement works unit together with confined power works will ensue in betterment of substructure every bit good as upliftment of societal construction in the surrounding small towns. The people shacking in the nearby countries will be benefited indirectly. The major benefit due to the cement works will be in the domain of bring forthing impermanent employment for significant figure of forces. During the enlargement of building stage about 1000 people on an norm will be employed. The work force during operational period is estimated to be about 350 individuals. Employment will be provided to eligible undertaking affected individuals both during building and operational stage. Impermanent employment for people from the adjacent small towns during building stage. The instruction and substructure installations such as development of ply land for childrens, noon repasts, computing machine preparation for the children/youth of weaker subdivision, scholarship for pupils of college/ITI, upg radation/renovation of bing schools, H2O supply, furniture, computing machines, library, books, school bags, athleticss kits, healthful installations etc. will be provided. Supplying primary wellness centres and ambulance installation. Conduction of vaccination/immunization programmes including infantile paralysis cantonments, oculus cantonments and medical assistance, reding and rehabilitation installations for drug addicts.Assistance/encouragement to self aid groups and income coevals strategies. Community development activies such as building of new community/panchayat halls. Provision of solar energy to community/panchyat edifice. Rennovation and modernisation of bing community/panchyat halls. The budget estimated under CSR activies is about Rs. 55 crores as on one clip capital outgo and Rs. 11 crores as repeating outgo per annum for 10 old ages.
Lewis Binford Essay
Only child Mother from well to do family who lost $ Dad electrician laborer Josef lewis binford mother(Eoline Roberts Binford) was descended from Virginia Tidewater high society,by birth no money scout learning by doing skilled in construction laborer helped with field work later years enrolled 1948 Virinia Polytech instutte under athlete scholarship foot ball forestry biology Married Jean mock two children $ problems 1952 enrolled army GI Bill to Okinawa, where he worked with native Ryukyuan peoples. Dischared 1954 interest anthplogy UNC 1957 B. A. That turned his interests to archaeology. Under the tutelage of Joffre Coe, Binford gained valuable field experience, read the literature, and began to question the conceptual underpinnings of the discipline. Armed with the belief that archaeology could and should do far more than merely situate ancient cultures in time and space, and keen to bring it into the mainstream of anthropology, Binford went to the University of Michigan for graduate work. Influential in his education there were. White, Albert Spaulding (from whom Binford learned analytical methods), and James Griffin, the quintessential culture historian, dean of eastern North American archaeology, and for Binford graduate adviser and symbol of all that was (and was wrong with) traditional archaeology (Sabloff, 1998, p. 13). Binford earned his M. A. in 1958 and Ph. D. in 1964 at Michigan, though Griffin did not last as his adviser. After teaching at Michigan for a year, Binford joined the University of Chicago anthropology faculty in 1961. Binford left Chicago four years later, still brash though unbowed despite having been denied tenure. By then, at least, he had received his Ph. D. but only after Griffin was persuaded to resign from his dissertation committee (Binford, 1972, p. 11). It was the first overt breach of what was a long, acidic relationship. It was at Chicago that Binford launched what came to be called the â€Å"New Archaeology†(later, â€Å"Processual Archaeology†) with hi s landmark article â€Å"Archaeology as Anthropology†(1962). After travelling to several univ. and being fired from what he called the best uni In 1968 Binford was hired at the University of New Mexico, Still, Binford gave no quarter to postprocessualists In 1991 Binford retired from the University of New Mexico and accepted a faculty appointment at Southern 20 BIO G RA PHICAL MEMOIRS Methodist University in Dallas. There he could teach less and have more time to devote to a project he had started in the 1970s (previews of which appeared as Binford [1990, 1997]), which would become his last major book: Constructing Frames of Reference: An Analytical Method for Archaeological Theory Building Using Ethnographic and Environmental Data Sets (Binford, 2001).
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