916 resultados para Modification of the aromatic ring


Relevância:

100.00% 100.00%

Publicador:

Resumo:

Polychlorinated dibenzo-p-dioxins (PCDDs) and related halogenated aromatic hydrocarbons (e.g., PCDFs), often called "dioxins", are ubiquitously present environmental contaminants. Some of them, notably 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), are among the most toxic synthetic compounds known. The biological effects of dioxins are mediated via the aryl hydrocarbon receptor (AhR). Mutations in the AhR transactivation domain are linked to sensitivity to the acute lethality of TCDD. We present here a study of AhR gene polymorphism in normal and cancer human tissues affecting pre-mRNA splicing in the AhR gene-coding transactivation domain region (exon 10, intron 10, exon 11 region), previously shown to be associated with AhR dysfunction. We tested 126 pairs of normal and cancer tissue samples from liver, lung, stomach, kidney, mucous, breast, and pancreas of 49 males and 77 females (45-70 years of age). We used in vitro splicing assay, RT-PCR and sequencing methods. Our results showed that in an in vitro system it is possible to reconstitute cellular pre-mRNA splicing events. Tested cancer tissues did not contain mutations in the AhR transactivation domain region when the DNA sequences were compared with those from normal tissues. There were also no differences in AhR mRNA splice variants between normal and malignant breast tissues and no polymorphisms in the studied regions or cDNA.

Relevância:

100.00% 100.00%

Publicador:

Resumo:

Chlorella vulgaris has the gene of n-3 fatty acid desaturase (CvFad3), which can synthesize the precursor of n-3 polyunsaturated fatty acids (PUFAs) or convert n-6 to n-3 PUFAs. The objective of the present study was to examine whether the CvFad3 gene from C. vulgaris can be functionally and efficiently expressed in human breast cancer cells and whether its expression can exert a significant effect on cell fatty acid composition. We inserted the CvFad3 gene into the plasmid pEGFP-C3 to construct the eukaryotic expression vector pEGFP-C3-n-3 and to express the n-3 Fad gene in human breast cancer cells (MCF-7 cells). Transfection of MCF-7 cells with the recombinant vector resulted in a high expression of n-3 fatty acid desaturase. Lipid analysis indicated that the ratio of n-6/n-3 PUFAs was decreased from 6:1 in the control cells to about 1:1 in the cells expressing the n-3 fatty acid desaturase. Accordingly, the CvFad3 gene significantly decreased the ratio of n-6/n-3 PUFAs of the MCF-7 cell membrane. The expression of the CvFad3 gene can decrease cell proliferation and promote cell apoptosis. This study demonstrates that the CvFad3 gene can dramatically balance the ratio of n-6/n-3 PUFAs and may provide an effective approach to the modification of the fatty acid composition of mammalian cells, also providing a basis for potential applications of its transfer in experimental and clinical settings.

Relevância:

100.00% 100.00%

Publicador:

Resumo:

SRY-related high-mobility-group box 9 (Sox9) gene is a cartilage-specific transcription factor that plays essential roles in chondrocyte differentiation and cartilage formation. The aim of this study was to investigate the feasibility of genetic delivery of Sox9 to enhance chondrogenic differentiation of human umbilical cord blood-derived mesenchymal stem cells (hUC-MSCs). After they were isolated from human umbilical cord blood within 24 h after delivery of neonates, hUC-MSCs were untreated or transfected with a human Sox9-expressing plasmid or an empty vector. The cells were assessed for morphology and chondrogenic differentiation. The isolated cells with a fibroblast-like morphology in monolayer culture were positive for the MSC markers CD44, CD105, CD73, and CD90, but negative for the differentiation markers CD34, CD45, CD19, CD14, or major histocompatibility complex class II. Sox9 overexpression induced accumulation of sulfated proteoglycans, without altering the cellular morphology. Immunocytochemistry demonstrated that genetic delivery of Sox9 markedly enhanced the expression of aggrecan and type II collagen in hUC-MSCs compared with empty vector-transfected counterparts. Reverse transcription-polymerase chain reaction analysis further confirmed the elevation of aggrecan and type II collagen at the mRNA level in Sox9-transfected cells. Taken together, short-term Sox9 overexpression facilitates chondrogenesis of hUC-MSCs and may thus have potential implications in cartilage tissue engineering.

Relevância:

100.00% 100.00%

Publicador:

Resumo:

O-GlcNAcylation is a modification that alters the function of numerous proteins. We hypothesized that augmented O-GlcNAcylation levels enhance myosin light chain kinase (MLCK) and reduce myosin light chain phosphatase (MLCP) activity, leading to increased vascular contractile responsiveness. The vascular responses were measured by isometric force displacement. Thoracic aorta and vascular smooth muscle cells (VSMCs) from rats were incubated with vehicle or with PugNAc, which increases O-GlcNAcylation. In addition, we determined whether proteins that play an important role in the regulation of MLCK and MLCP activity are directly affected by O-GlcNAcylation. PugNAc enhanced phenylephrine (PE) responses in rat aortas (maximal effect, 14.2±2 vs 7.9±1 mN for vehicle, n=7). Treatment with an MLCP inhibitor (calyculin A) augmented vascular responses to PE (13.4±2 mN) and abolished the differences in PE-response between the groups. The effect of PugNAc was not observed when vessels were preincubated with ML-9, an MLCK inhibitor (7.3±2 vs 7.5±2 mN for vehicle, n=5). Furthermore, our data showed that differences in the PE-induced contractile response between the groups were abolished by the activator of AMP-activated protein kinase (AICAR; 6.1±2 vs 7.4±2 mN for vehicle, n=5). PugNAc increased phosphorylation of myosin phosphatase target subunit 1 (MYPT-1) and protein kinase C-potentiated inhibitor protein of 17 kDa (CPI-17), which are involved in RhoA/Rho-kinase-mediated inhibition of myosin phosphatase activity. PugNAc incubation produced a time-dependent increase in vascular phosphorylation of myosin light chain and decreased phosphorylation levels of AMP-activated protein kinase, which decreased the affinity of MLCK for Ca2+/calmodulin. Our data suggest that proteins that play an important role in the regulation of MLCK and MLCP activity are directly affected by O-GlcNAcylation, favoring vascular contraction.

Relevância:

100.00% 100.00%

Publicador:

Resumo:

In this thesis the basic structure and operational principals of single- and multi-junction solar cells are considered and discussed. Main properties and characteristics of solar cells are briefly described. Modified equipment for measuring the quantum efficiency for multi-junction solar cell is presented. Results of experimental research single- and multi-junction solar cells are described.

Relevância:

100.00% 100.00%

Publicador:

Resumo:

The oil obtained from Brazilian roasted coffee by supercritical CO2 extraction shows considerable aromatic properties, mainly composed by five aromatic compounds, 2-methylpyrazine; 2-furfurylalcohol, 2,5-dimethylpyrazine; γ-butyrolactone and 2-furfurylacetate. Sensory analyses were used to verify the influence of a mixture of these important classes of aromatic coffee compounds (pyrazines, furans and lactones) and of the roasted coffee aromatic oil on the coffee aroma and flavour of black instant freeze and spray-dried coffee beverages. In the acceptance evaluation of the aroma, the samples prepared with freeze-dried instant coffee without the mixture of volatile compounds (sample 4) were not significantly different from the freeze-dried instant coffee in which the aromatic coffee oil was added (sample 5) and from the sample prepared with freeze-dried coffee in which the mixture of the five volatile was added (sample 3), coincidentally from the same drying process. Therefore, sample (3) did not differ from samples prepared with spray dried instant coffee without (sample 1) and to which (sample 2) the mixture of volatile was added. Therefore, with respect to this attribute, the addition of this mixture did not interfere in this drink acceptance. Taking into consideration the flavor, samples prepared with freeze-dried instant coffee in which the aromatic coffee oil was added (5) and the samples with (3) and without (4) the mixture of the five volatile was added did not differ significantly, however sample (4) did not differ from samples (1) and (2). Regarding this attribute, the addition of the aromatic oil of roasted coffee or a mixture of volatile in samples of freeze-dried instant coffee had a better acceptance than those dried by spray dryer (1) and (2). Thus, the enrichment of drinks with the aromatic oil of roasted coffee, or even with the mixture of the five components did not influence the consumer acceptance with respect to the aroma, but exerts influence with respect to flavour.

Relevância:

100.00% 100.00%

Publicador:

Resumo:

Phosphoserine aminotrasferase (PSAT: EC 2.6.1.52) is a vitamin B6-dependent enzyme and a member of the subgroup IV in the aminotransferase superfamily. Here, X-ray crystallography was used to determine the structure of PSAT from Bacillus alcalophilus with pyridoxamine 5′-phosphate (PMP) at high resolution (1.57 Å). In addition, analysis of active residues and their conformational changes was performed. The structure is of good quality as indicated, for example, by the last recorded Rwork and Rfree numbers (0.1331 and 0.1495, respectively). The enzyme was initially crystallized in the presence of substrate L-glutamate with the idea to produce the enzyme-substrate complex. However, the structure determination revealed no glutamate bound at the active site. Instead, the Schiff base between Lys196 and PLP appeared broken, resulting in the formation of PMP owing to the excess of the donor substrate used during co-crystallization. Structural comparison with the free PSAT enzyme and the PSAR-PSER complex showed that the aromatic ring of the co-factor remains in almost the same place in all structures. A flexible nearby loop in the active site was found in the same position as in the free PSAT structure while in the PSAT-PSER structure it moves inwards to interact with PSER. B-factors comparison in all three structures (PSAT-PMP complex, free PSAT, and PSAT-PSER complex) showed elevated loop flexibility in the absence of the substrate, indicating that loop flexibility plays an important role during substrate binding. The reported structure provides mechanistic details into the reaction mechanism of PSAT and may help in understanding better the role of various parts in the structure towards the design of novel compounds as potential disruptors of PSAT function. This may lead to the development of new drugs which could target the human and bacterial PSAT active site.

Relevância:

100.00% 100.00%

Publicador:

Resumo:

I will argue that the doctrine of eternal recurrence of the same no better interprets cosmology than pink elephants interpret zoology. I will also argue that the eternal-reiurn-of-the-same doctrine as what Magnus calls "existential imperative" is without possibility of application and thus futile. To facilitate those arguments, the validity of the doctrine of the eternal recurrence of the same will be tested under distinct rubrics. Although each rubric will stand alone, one per chapter, as an evaluation of some specific aspect of eternal recurrence, the rubric sequence has been selected to accommodate the identification of what I shall be calling logic abridgments. The conclusions to be extracted from each rubric are grouped under the heading CONCLUSION and appear immediately following rubric ten. Then, or if, at the end of a rubric a reader is inclined to wonder which rubric or topic is next, and why, the answer can be found at the top of the following page. The question is usually answered in the very first sentence, but always answered in the first paragraph. The first rubric has been placed in order by chronological entitlement in that it deals with the evolution of the idea of eternal recurrence from the time of the ancient Greeks to Nietzsche's August, 1881 inspiration. This much-recommended technique is also known as starting at the beginning. Rubric 1 also deals with 20th. Century philosophers' assessments of the relationship between Nietzsche and ancient Greek thought. The only experience of E-R, Zarathustra's mountain vision, is second only because it sets the scene alluded to in following rubrics. The third rubric explores .ii?.ih T jc,i -I'w Nietzsche's evaluation of rationality so that his thought processes will be understood appropriately. The actual mechanism of E-R is tested in rubric four...The scientific proof Nietzsche assembled in support of E-R is assessed by contemporary philosophers in rubric five. E-R's function as an ethical imperative is debated in rubrics six and seven.. .The extent to which E-R fulfills its purpose in overcoming nihilism is measured against the comfort assured by major world religions in rubric eight. Whether E-R also serves as a redemption for revenge is questioned in rubric nine. Rubric ten assures that E-R refers to return of the identically same and not merely the similar. In addition to assemblage and evaluation of all ten rubrics, at the end of each rubric a brief recapitulation of its principal points concludes the chapter. In this essay I will assess the theoretical conditions under which the doctrine cannot be applicable and will show what contradictions and inconsistencies follow if the doctrine is taken to be operable. Harold Alderman in his book Nietzsche's Gift wrote, the "doctrine of eternal recurrence gives us a problem not in Platonic cosmology, but in Socratic selfreflection." ^ I will illustrate that the recurrence doctrine's cosmogony is unworkable and that if it were workable, it would negate self-reflection on the grounds that selfreflection cannot find its cause in eternal recurrence of the same. Thus, when the cosmology is shown to be impossible, any expected ensuing results or benefits will be rendered also impossible. The so-called "heaviest burden" will be exposed as complex, engrossing "what if speculations deserving no linkings to reality. To identify ^Alderman p. 84 abridgments of logic, contradictions and inconsistencies in Nietzsche's doctrine of eternal recurrence of the same, I. will examine the subject under the following schedule. In Chapter 1 the ancient origins of recurrence theories will be introduced. ..This chapter is intended to establish the boundaries within which the subsequent chapters, except Chapter 10, will be confined. Chapter 2, Zarathustra's vision of E-R, assesses the sections of Thus Spoke Zarathustra in which the phenomenon of recurrence of the same is reported. ..Nihilism as a psychological difficulty is introduced in this rubric, but that subject will be studied in detail in Chapter 8. In Chapter 2 the symbols of eternal recurrence of the same will be considered. Whether the recurrence image should be of a closed ring or as a coil will be of significance in many sections of my essay. I will argue that neither symbolic configuration can accommodate Nietzsche's supposed intention. Chapter 3 defends the description of E-R given by Zarathustra. Chapter 4, the cosmological mechanics of E-R, speculates on the seriousness with which Nietzsche might have intended the doctrine of eternal recurrence to be taken. My essay reports, and then assesses, the argument of those who suppose the doctrine to have been merely exploratory musings by Nietzsche on cosmological hypotheses...The cosmogony of E-R is examined. In Chapter 5, cosmological proofs tested, the proofs for Nietzsche's doctrine of return of the same are evaluated. This chapter features the position taken by Martin ' Heidegger. My essay suggests that while Heidegger's argument that recurrence of the same is a genuine cosmic agenda is admirable, it is not at all persuasive. Chapter 6, E-R is an ethical imperative, is in essence the reporting of a debate between two scholars regarding the possibility of an imperative in the doctrine of recurrence. Their debate polarizes the arguments I intend to develop. Chapter 7, does E-R of the same preclude alteration of attitudes, is a continuation of the debate presented in Chapter 6 with the focus shifted to the psychological from the cosmological aspects of eternal recurrence of the same. Chapter 8, Can E-R Overcome Nihilism?, is divided into two parts. In the first, nihilism as it applies to Nietzsche's theory is discussed. ..In part 2, the broader consequences, sources and definitions of nihilism are outlined. My essay argues that Nietzsche's doctrine is more nihilistic than are the world's major religions. Chapter 9, Is E-R a redemption for revenge?, examines the suggestion extracted from Thus Spoke Zarathustra that the doctrine of eternal recurrence is intended, among other purposes, as a redemption for mankind from the destructiveness of revenge. Chapter 10, E-R of the similar refuted, analyses a position that an element of chance can influence the doctrine of recurrence. This view appears to allow, not for recurrence of the same, but recurrence of the similar. A summary will recount briefly the various significant logic abridgments, contradictions, and inconsistencies associated with Nietzsche's doctrine of eternal recurrence of the same. In the 'conclusion' section of my essay my own opinions and observations will be assembled from the body of the essay.

Relevância:

100.00% 100.00%

Publicador:

Resumo:

Two efficient, regio- and stereo controlled synthetic approaches to the synthesis of racemic analogs of pancratistatin have been accomplished and they serve as the model systems for the total synthesis of optically active 7-deoxy-pancratistatin. In the Diels-Alder approach, an efficient [4+2] cycloaddition of 3,4-methylenedioxyco- nitrostyrene with Danishefsky's diene to selectively form an exo-nitro adduct has been developed as the key step in the construction of the C-ring of the target molecule. In the Michael addition approach, the key step was a conjugate addition of an organic zinc-cuprate to the 3,4-methylenedioxy-(B-nitrostyrene, followed by a diastereocontroUed closure to form the cyclohexane C-ring of the target molecule via an intramolecular nitro-aldol cyclization on a neutral alumina surface. A chair-like transition state for such a cyclization has been established and such a chelation controlled transition state can be useful in the prediction of diastereoselectivity in other related 6-exo-trig nitroaldol reactions. Cyclization of the above products fi^om both approaches by using a Bischler-Napieralski type reaction afforded two lycoricidine derivatives 38 and 50 in good yields. The initial results from the above modeling studies as well as the analysis of the synthetic strategy were directed to a chiral pool approach to the total synthesis of optically active 7-deoxy-pancratistatin. Selective monsilylation and iodination of Ltartaric acid provided a chiral precursor for the proposed key Michael transformation. The outlook for the total synthesis of 7-deoxy-pancratistatin by this approach is very promising.A concise synthesis of novel designed, optically pure, Cz-symmetrical disulfonylamide chiral ligands starting from L-tartaric acid has also been achieved. This sequence employs the metallation of indole followed by Sfj2 replacement of a dimesylate as the key step. The activity for this Cz-symmetric chiral disulfonamide ligand in the catalytic enantioselective reaction has been confirmed by nucleophilic addition to benzaldehyde in the disulfonamide-Ti (0-i-Pr)4-diethylzinc system with a 48% yield and a 33% e.e. value. Such a ligand tethered with a suitable metal complex should be also applicable towards the total synthesis of 7-deoxy-pancratistatin.

Relevância:

100.00% 100.00%

Publicador:

Resumo:

To further understand in vivo localization and trafficking of a-tocopherol (a-Toe), the most biologically active form of vitamin E, between lipid environments, tocopherols are required that can be followed by teclu1iques such as confocal microscopy and fluorescence resonance energy transfer (FRET) assays. To this end, sixteen fluorescent analogues of a-tocopherol (la-d [(1)anthroy loxy -a-tocopherols, A O-a-Toes], 2a-d [w-nitro benzoxadiazole-a-tocopherols, NBD-aToes], 3a-d [w-dansyl-a-tocopherols, DAN-a-Toes], and 4a-d [w-N-methylanthranilamide-atocopherols, NMA-a-TocsD were prepared by substituting fluorescent labels at the terminus of w-functionalized alkyl chains extending from C-2 of the chroman ring while retaining key binding features of the natural ligand. These compounds were prepared starting from (S)-Trolox® acid VIa esterification, protection, and reduction producing the silyl-protected (S)-Trolox aldehyde that was coupled using Wittig chemistry to different w-hydroxyalkylphosphonium bromides. Reduction of the alkene generated the w-hydroxy functionalized 2-n-alkyl intermediates 9a-d having the necessary 2R stereochemistry. A series of functional group manipulations including mesylation, substitution with azide, and hydride reduction provided w-amino functionalized intermediates 12a-d as well. Coupling intermediates 9a-d and 12a-d with the selected fluorophores (9- anthracene carboxylic acid, 4-chloro-7-nitrobenz-2-oxa-l,3-diazole, 5- dimethylaminonapthalene-l-sulfonyl chloride, and I-methyl-2H-3,1-benzoxazine-2,4(1H)dione), followed by deprotection of the phenolic silyl group, gave the desired fluorescent ligands la-d, 2a-d, 3a-d and 4a-d in good yield. Assessment of their binding affinities with recombinant human a-tocopherol transfer protein (ha-TTP) utilizing fluorescent titration binding assays identified competent ligands for further use in protein studies. Compounds Id (C9-AO-a-Toc) and 2d (C9-NBD-a-Toc) both having nonyl alkyl chain extensions between the chromanol and fluorophore were shown to bind specifically to ha-TTP with dissociation constants (KdS) of approximately 280 nM and 55 nM respectively, as compared to 25 nM for the natural ligand 2R,4'R,^'R-a-tocophQxoL.

Relevância:

100.00% 100.00%

Publicador:

Resumo:

The Impact of the Multicolor Asian Lady Beetle (Harmonia axyridis) on Niagara Wine Quality The possible influence of Harmonia axyridis (the Multicolored Asian Lady Beetle) on the sensory properties of wine was investigated. H. axyridis beetles were added to white and red grape musts at a rate of 0, 1 or 10 per L, and a trained panel evaluated the finished wines using flavor-profiling techniques. Significant modification of both wine aroma and flavor characteristics were observed in the 10 beetlelL treatments, with smaller effects noted at the 1 beetlelL rate. Vinification in the presence of H. axyridis gave higher intensity scores for peanut, bell pepper and asparagus aromas and flavors in the white wines, and peanut, asparagus/bell pepper, and earthy/herbaceous aromas and flavors in the red wines. In addition, sweet, acid and bitter tastes were affected in red wines, and a general trend of decreasing fruit and floral intensities with increasing beetle rate was observed in both white and red wines. 15 ngIL Isopropylmethoxypyrazine was added to control wines and sensory profiles similar to high beetle treatments were obtained, supporting the hypothesis that methoxypyrazines from beetles are implicated in the taint. A trained panel evaluated the treated wines after 10 months of aging using the same sensory methods described above. Sensory profiles were very similar. Fennenting in the presence of Harmonia Axyridis (HA) had little influence on the chemical composition of the ftnished wine. The notable exception IS Isopropylmethoxypyrazine content, which was assessed usmg GC-MS analysis and showed increased concentration with increasing beetle nwnber for both white and red wmes. The influence of potential remedial treatments on the sensory properties of white and red wines tainted by Harmonia axyridis were also investigated. Bentonite, activated charcoal, oak chips, de-odorized oak chips, and UV or light irradiation were applied to tainted wine, and these wines evaluated chemically and sensorially. Both white and red wines treated with oak chips had strong oak characteristics, which masked the Harmonia axyridis-associated aroma and flavour attributes. In red wine, asparagus/bell pepper characteristics were decreased by bentonite and charcoal treatments. Only activated charcoal significantly decreased methoxypyrazine levels and only in white wine.

Relevância:

100.00% 100.00%

Publicador:

Resumo:

The peripheral circulating erythrocytic system of the rainbow trout, l3 almo gairdner , was examined in vitro in relation differences in the morphology and multiple hemoglobin system organization of adult and juvenile red cells. Cells were separated by velocity sedimentation under unit gravity, a procedure requiring red cell exposure to an incubation medium for periods of at least three hours. Therefore , this must provide an environment in which red cells remain in a condition approximaing normalcy. Previous studies having demonstrated commonly employed media to be ineffective in this regard , a medium was developed through modification of Cortl and saline. One of the principal additions to this me dium , norepinephrine, altered cell regulation of intracellular calcium, magnesium and chloride concentrations. Catecholamine involvement was also suggeste d in the synthes is of hemoglobin . The procedure was found to separtate cells primarily by density and, to a lesser extent, by shape. Characterization of red cells revealed two subpopulations to exist . The first comprised the bulk of the cell population, and were of greater l ength, width, volume and major:minor axis ratio than the smaller population; these were adult cells. The later, juvenile cells were of smaller overall size and were more spherical in shape . Juvenile cells also possessed fewer electrophore tpically distinguishable isomorphs than did adults with only eight of eleven hemoglobin component s typically found With maturation,hemoglobin complement with the development of three more bands. The total complement of the adult cell contained 7 cathodal bands and four anodal hemoglobin isomorphs. Bands acquired with maturation comprised the smallest percentage of the cells hemoglobin. each averaging less than one-percent of the total. Whether these additional bands are derived through degradation and reaggregation of existing components or are the product of pe gQy2 synthesis is not yet known.

Relevância:

100.00% 100.00%

Publicador:

Resumo:

This work contains the results of a series of reduction studies on polyhalogenated aromatic compounds and related ethers using alkali metals in liquid ammonia. In general, polychlorobenzenes were reduced to t he parent aromatic hydrocarbon or to 1 ,4-cyc1ohexadiene, and dipheny1ethers were cleaved to the aroma tic hydrocarbon and a phenol. Chlorinated dipheny1ethers were r eductive1y dechlorinated in the process. For example, 4-chlorodipheny1- ether gave benzene and phenol. Pentach1orobenzene and certain tetrachlorobenzenes disproportionated to a fair degree during the reduction process if no added proton source was present. The disproportionation was attributed to a build-up of amide ion. Addition of ethanol completely suppressed the formation of any disproportionation products. In the reductions of certain dipheny1ethers , the reduction of one or both of the dipheny1ether rings occurred, along with the normal cleavage. This was more prevalent when lithium was the metal used . As a Sidelight, certain chloropheno1s were readily dechlorinated. In light of these results, the reductive detoxification of the chlorinated dibenzo-1,4-dioxins seems possible with alkali metals in l iquid ammonia.

Relevância:

100.00% 100.00%

Publicador:

Resumo:

The work described in this thesis has been divided into seven sections. The first section involves the preparation of N'-acyl-N'-arylN- benzothiohydrazides by the acylation of N'-aryl-N-benzothiohydrazides and is followed by a brief discussion of their possible conformation in solution. The second section deals with the preparation of 1,3,4-thiadiazolium salts by the action of perchloric acid/acetic anhydride on N'-acylN'- aryl-N-benzothiohydrazides and also by the reaction of N'-arylN- benzothiohydrazides with nitriles in an acidic medium. The preparation of 2-methylthio-I,3,4-thiadiazolium methosulfate by methylating the corresponding thione is also described. The third section deals with the reaction of 2-phenyl- and 2-methyl-I,3,4-thiadiazolium salts with alcohols in the presence of base. The stability and spectra of these compounds are discussed. Treatment of the 2-methyl-I,3,4-thiadiazolium salt with base was found to give rise to a dimeric anhydrobase and evidence supporting its structure is given. The anhydrobase could be trapped by a variety of acylating and thioacylating agents before dimerization occurred. In the fourth section, the reaction of N'-acyl-N'-aryl-N-benzothiohydrazides with a variety of acid anhydrides is described. These compounds were found to be identical with those obtained by acylating the anhydrobase. The mass spectral fragmentation of these compounds is described and the anomolous product obtained upon thiobenzoylation of 3-methyl-l-phenyl-pyrazal-5-one is also discussed. The fifth section deals with thioacyl derivatives of the anhydrobase which were prepared by the action of phosphorus pentasulfide upon the oxygen analogues and also obtained as the major product of the reaction of thioacetic acid with compounds related to N'-aryl-N-benzothiohydrazides. The mass spectra and p.m.r. spectra of these compounds are discussed. In the sixth section, the reaction of the 2-methylthio-l,3,4- thiadiazolium salt with active methylene compounds to give acyl and diacyl derivatives of the anhydrobase is described. Some aspects of these compounds are discussed. The seventh section describes the synthesis of ncyanine~' type dyes incorporating the l,3,4-thiadiazole ring and their spectra are briefly discussed.

Relevância:

100.00% 100.00%

Publicador:

Resumo:

The crystal structure of Cu(PM)2(N03hoH20 (where PM is pyridoxamine, CSHI2N202) has been determined from three dimensional x-ray diffraction data. The crystals are triclinic, space group pI, a = 14.248 (2), b = 8.568 (1), c = 9.319 (1) 1, a = 94.08 (1), e = 89.73 (1), y~~ 99.18 (1)°, z = 2, jl(MoK) = 10.90 em-I, Po = 1.61 g/cm3 and Pc = 1.61 g/em3• The structure a was solved by Patterson techniques from data collected on a Picker 4-circle diffractometer to 26max = 45°. All atoms, including hydrogens, have been located. Anisotropic thermal parameters have been refined for all nonhydrogen atoms. For the 2390 independent reflections with F ? 3cr(F) , R = 0.0408. The results presented here provide the first detailed structural information of a metal complex with PM itself. The copper atoms are located on centres of symmetry and each is chela ted by two PM zwitterions through the amino groups and phenolate oxygen atoms. The zwitterionic form found in this structure involves the loss of a proton from the phenolate group and protonation of the pyridine ring nitrogen atoms. The two independent Cu(PM)2 moieties are symmetrically bridged by a single oxygen atom from one of the nitrate groups. The second nitrate group is not coordinated to the copper atoms but is central to an extensive hydrogen bonding network involving the water molecule and uncoordinated functional groups of PM.