999 resultados para C-2 oxygenates


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An immunohistochemical examination of guinea-pig taste buds in vallate papillae revealed gustducin-immunoreactive cells in the area of von Ebner’s glands, minor salivary glands. Since there have been no reports describing those cells in these locations for other species, we investigated these glands in order both to localize the cells and compare their immunoreactive characteristics with corresponding cells in the vallate taste buds. The gustducin-immunoreactive cells coincided with cells containing no secretory granules in the end portion of the glands, which was supported by the electron-microscopic immunocytochemistry. Double immunofluorescence microscopy confirmed these cells to be entirely immunopositive to type III inositol 1,4,5-triphosphate receptor (IP3R-3), phospholipase Cβ2 (PLCβ2), and villin and also partly immunopositive to neuron-specific enolase (NSE) and calbindin D-28K. The gustducin-immunoreactive cells in the vallate taste buds exhibited completely the same immunoreactivities for these five molecules. Accordingly, the present results give credence to a consideration that the gustducin-immunnoreactive cells in both locations are identical in function(s) e.g., chemo-reception.

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This study describes the sociolinguistic situation of the indigenous Hungarian national minorities in Slovakia (c. 600,000), Ukraine (c. 180,000), Romania (c. 2,000,000), Yugoslavia (c. 300,000), Slovenia (c. 8,000) and Austria (c. 6,000). Following the guidelines of Hans Goebl et al, the historical sociolinguistic portrait of each minority is presented from 1920 through to the mid-1990s. Each country's report includes sections on geography and demography, history, politics, economy, culture and religion, language policy and planning, and language use (domains of minority and/or majority language use, proficiency, attitudes, etc.). The team's findings were presented in the form of 374 pages of manuscripts, articles and tables, written in Hungarian and English. The core of the team's research results lies in the results of an empirical survey designed to study the social characteristics of Hungarian-minority bilingualism in the six project countries, and the linguistic similarities and differences between the six contact varieties of Hungarian and Hungarian in Hungary. The respondents were divided by age, education, and settlement group - city vs. village and local majority vs. local minority. The first thing to be observed is that Hungarian is tending to be spoken less to children than to parents and grandparents, a familiar pattern of language shift. In contact varieties of Hungarian, analytic constructions may be used where monolingual Hungarians would use a more synthetic form. Mr Kontra gives as an example the compound tagdij, which in Standard Hungarian means "membership fee" but which is replaced in contact Hungarian by the two-word phrase tagsagi dij. Another similar example concerns the synthetic verb hegedult "played the violin" and the analytic expression hegedun jatszott. The contrast is especially striking between the Hungarians in the northern Slavic countries, who use the synthetic form frequently, and those in the southern Slavic countries, who mainly use the analytic form. Mr. Kontra notes that from a structural point of view, there is no immediate explanation for this, since Slovak or Ukrainian are as likely to cause interference as is Serbian. He postulates instead that the difference may be attributable to some sociohistoric cause, and points out that the Turkish occupation of what is today Voivodina caused a discontinuity of the Hungarian presence in the region, with the result that Hungarians were resettled in the area only two and a half centuries ago. However, the Hungarians in today's Slovakia and Ukraine have lived together with Slavic peoples continuously for over a millennium. It may be, he suggests, that 250 years of interethnic coexistence is less than is needed for such a contact-induced change to run its course. Next Mr. Kontra moved on to what he terms "mental maps and morphology". In Hungarian, the names of cities and villages take the surface case (eg. Budapest-en "in Budapest") whereas some names denoting Hungarian settlements and all names of foreign cities take the interior case (eg. Tihany-ban "in Tihany" and Boston-ban "in Boston). The role of the semantic feature "foreign" in suffix-choice can be illustrated by such minimal pairs as Velence-n "in Velence, a village in Hungary" versus Velence-ben "in Velence [=Venice], a city in Italy", and Pecs-en "in Pecs, a city in Hungary" vs. Becs-ben "in Becs, ie. Vienna". This Hungarian vs. foreign distinction is often interpreted as "belonging to historical (pre-1920) Hungary" vs. "outside historical Hungary". The distinction is also expressed in the dichotomy "home" vs. "abroad'. The 1920 border changes have had an impact on both majority and minority Hungarians' mental maps, the maps which govern the choice of surface vs. interior cases with placenames. As there is a growing divergence between the mental maps of majority and minority Hungarians, so there will be a growing divergence in their use of the placename suffixes. Two placenames were chosen to scratch the surface of this complex problem: Craiova (a city in Oltenia, Romania) and Kosovo (Hungarian Koszovo) an autonomous region in southeast Yugoslavia. The assumption to be tested was that both placenames would be used with the inessive (interior) suffixes categorically by Hungarians in Hungary, but that the superessive suffix (showing "home") would be used near-categorically by Hungarians in Romania and Yugoslavia (Voivodina). Minority Hungarians in countries other than Romania and Yugoslavia would show no difference from majority Hungarians in Hungary. In fact, the data show that, contrary to expectation, there is considerable variation within Hungary. And although Koszovo is used, as expected, with the "home" suffix by 61% of the informants in Yugoslavia, the same suffix is used by an even higher percentage of the subjects in Slovenia. Mr. Kontra's team suggests that one factor playing a role in this might be the continuance of the former Yugoslav mentality in the Hungarians of Slovenia, at least from the geographical point of view. The contact varieties of Hungarian show important grammatical differences from Hungarian in Hungary. One of these concerns the variable use of Null subjects (the inclusion or exclusion of the subject of the verb). When informants were asked to insert either megkertem or megkertem ot - "I asked her" - into a test sentence, 54.9% of the respondents in the Ukraine inserted the second phrase as opposed to only 27.4% in Hungary. Although Mr. Kontra and his team concentrated more on the differences between Contact Hungarian and Standard Hungarian, they also discovered a number of similarities. One such similarity is demonstrable in the distribution of what Mr. Kontra calls an ongoing syntactic merger in Hungarian in Hungary. This change means effectively that two possibilities merge to form a third. For instance, the two sentences Valoszinuleg kulfoldre fognak koltozni and Valoszinu, hogy kulfoldre fognak koltozni merge to form the new construction Valszinuleg, hogy kulfoldre fognak koltozni ("Probably they will move abroad."). When asked to choose "the most natural" of the sentences, one in four chose the new construction, and a chi-square test shows homogeneity in the sample. In other words, this syntactic change is spreading across the entire Hungarian-speaking region in the Carpathian Basin Mr. Kontra believes that politicians, educators, and other interested parties now have reliable and up-to-date information about each Hungarian minority. An awareness of Hungarian as a pluricentric language is being developed which elevates the status of contact varieties of Hungarian used by the minorities, an essential process, he believes, if minority languages are to be maintained.

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The occurrence of degenerative spinal disease subsequent to dystonic movement disorders has been neglected and has received more attention only recently. Spinal surgery is challenging with regard to continuous mechanical stress when treatment of the underlying movement disorder is insufficient. To characterize better the particular features of degenerative spinal disease in patients with dystonia and to analyze operative strategies, we reviewed the available published data. Epidemiologic studies reveal that degenerative spinal disorders in patients with dystonia and choreoathetosis occur much earlier than in the physiological aging process. Dystonic movement disorders more often affect the spine at higher cervical levels (C(2-5)), in contrast to spinal degeneration with age which manifests more frequently at the middle and lower cervical spine (C(5-7)). Degenerative changes of the cervical spine are more likely to occur on the side where the chin is rotated or tilted to. Various operative approaches for treatment of spinal pathologies have been advocated in patients with dystonic movement disorders. The available data do not allow making firm statements regarding the superiority of one approach over the other. Posterior approaches were first used for decompression, but additional anterior fusion became necessary in many instances. Anterior approaches with or without instrumented fusion yielded more favorable results, but drawbacks are pseudarthrosis and adjacent-level disease. Parallel to the development of posterior fusion techniques, circumferential surgery was suggested to provide a maximum degree of cord decompression and a higher fusion rate. Perioperative local injections of botulinum toxin were used initially to enhance patient comfort with halo immobilization, but they are also applied in patients without external fixation nowadays. Treatment algorithms directed at the underlying movement disorder itself, taking advantage of new techniques of functional neurosurgery, combined with spinal surgery have recently been introduced and show promising results.

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BACKGROUND: Constipation is a significant side effect of opioid therapy. We have previously demonstrated that naloxone-3-glucuronide (NX3G) antagonizes the motility-lowering-effect of morphine in the rat colon. AIM: To find out whether oral NX3G is able to reduce the morphine-induced delay in colonic transit time (CTT) without being absorbed and influencing the analgesic effect. METHODS: Fifteen male volunteers were included. Pharmacokinetics: after oral administration of 0.16 mg/kg NX3G, blood samples were collected over a 6-h period. Pharmacodynamics: NX3G or placebo was then given at the start time and every 4 h thereafter. Morphine (0.05 mg/kg) or placebo was injected s.c. 2 h after starting and thereafter every 6 h for 24 h. CTT was measured over a 48-h period by scintigraphy. Pressure pain threshold tests were performed. RESULTS: Neither NX3G nor naloxone was detected in the venous blood. The slowest transit time was observed during the morphine phase, which was significantly different from morphine with NX3G and placebo. The pain perception was not significantly influenced by NX3G. CONCLUSIONS: Orally administered NX3G is able to reverse the morphine-induced delay of CTT in humans without being detected in peripheral blood samples. Therefore, NX3G may improve symptoms of constipation in-patients using opioid medication without affecting opioid-analgesic effects.

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We herein describe in full detail the first total synthesis of the antitumor agents neolaulimalide and isolaulimalide as well as a highly efficient route to laulimalide. A Kulinkovich reaction followed by a cyclopropyl-allyl rearrangement is used to install the exo-methylene group. The C(2)-C(16) aldehyde fragment is coupled with the C(17)-C(28) sulfone fragments by a highly (E)-selective Julia-Lythgoe-Kocienski olefination to deliver the key intermediates of all three syntheses. Various conditions for the Yamaguchi macrolactonization are applied to close the individual macrocycles. Finally a carefully elaborated endgame was developed to solve the problem of acyl migration in the case of neolaulimalide. All compounds were tested against several cell lines. The cytotoxicity of neolaulimalide could be confirmed for the first time since its original isolation and it could be shown that it induces tubulin polymerization as efficiently as laulimalide.

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Although the nature of the blood groups A and B has been comprehensively studied for a long time, it is still unclear as to what exactly is the epitope that is recognized by antibodies having AB specificity, i.e. monoclonal and polyclonal antibodies which are capable of interacting equally well with the antigens GalNAcalpha 1-3(Fucalpha 1-2)Gal (A trisaccharide) and Galalpha 1-3(Fucalpha 1-2)Gal (B trisaccharide), but do not react with their common fragment Fucalpha 1-2Gal. We have supposed that besides Fucalpha 1-2Gal, A and B antigens have one more shared epitope. The trisaccharides A and B are practically identical from the conformational point of view, the only difference being situated at position 2 of Galalpha residue, i.e. trisaccharide A has a NHAc group, whereas trisaccharide B has a hydroxyl group (see formulas). We have hypothesized that the AB-epitope should be situated in the part of the molecule that is opposite to the NHAc group of GalNAc residue. In order to test this hypothesis we have synthesized a polymeric conjugate in such a way that de-N-acetylated A-trisaccharide is attached to a polymer via the nitrogen in position C-2 of the galactosamine residue. In this conjugate the supposed AB-epitope should be maximally accessible for antibodies from the solution, whereas the discrimination site of antigens A and B by the antibodies should be maximally hidden due to the close proximity of the polymer. Interaction with several anti-AB monoclonal antibodies revealed that a part of them really interacted with the synthetic AB-glycotope, thus confirming our hypothesis. Moreover, similar antibodies were revealed in the blood of healthy blood group 0 donors. Analysis of spatial models was performed in addition to identify the hydroxyl groups of Fuc, Galalpha, and Galbeta residues, which are particularly involved in the composition of the AB-glycotope.

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A novel class of phospholipase-resisting phosphatidylcholine analogs, in which the C-2 ester group or both C-1 and C-2 ester groups have been replaced by carbamyloxy functions (-NH-C-O-), have been synthesized. These lipids were not degraded by phospholipase A2 while complete hydrolysis occurred with phospholipase C. Ultrasonic irradiation of the aqueous dispersions of the phospholipids in the presence as well as in the absence of cholesterol resulted in the formation of closed bilayer structures as evidenced by negative staining electron microscopy and also by their ability to entrap [14C]glucose. The leakage rates of glucose at 37°C from liposomes of these compounds have also been measured. Liposomes consisting of 1,2-dipentadecanylcarbamyloxy-sn-glycero- 3-phosphorylcholine were found to be more leaky (2.1 %/h) as compared to the liposomes of 1-palmitoyl-2-pentadecanylcarbamyloxy-sn -glycero-3-phosphoryl- choline (O.5%/h). Moreover, inclusion of cholesterol (33 mol%) into the bilayers of the former phospholipid had no effect on the leakage rate (2.4%/h) while it effectively reduced permeability of the latter (O.22%/h). These phosphatidylcholines are useful for studying the possible role of phospholipases in the capture and lysis of liposomes in vivo.

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Replacement of the C-2 ester group in phosphatidylcholine by the carbamyloxy function rendered its liposomes completely stable and longer living in the circulation of rats.

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Determining the impact of insect herbivores on forest tree seedlings and saplings is difficult without experimentation in the field. Moreover, this impact may be heterogeneous in time and space because of seasonal rainfall and canopy disturbances, or ‘gaps’, which can influence both insect abundance and plant performance. In this study we used fine netting to individually protect seedlings of Microberlinia bisulcata, Tetraberlinia bifoliolata and Tetraberlinia korupensis trees (Fabaceae = Leguminosae) from insects in 41 paired gap-understorey locations across 80 ha of primary rain forest (Korup, Cameroon). For all species, growth in height and leaf numbers was negligible in the understorey, where M. bisulcata had the lowest survival after c. 2 years. In gaps, however, all species responded positively with pronounced above-ground growth across seasons. When exposed to herbivores their seedling height growth was similar, but in the absence of herbivores, M. bisulcata significantly outgrew both Tetraberlinia species and matched their leaf numbers. This result suggests that insect herbivores might play an important role in maintaining species coexistence by mitigating sapling abundance of the more palatable M. bisulcata, which in gaps was eaten the most severely. The higher ratio in static leaf damage of control-to-caged M. bisulcata seedlings in gaps than understorey locations was consistent with the Plant Vigour Hypothesis. This result, however, did not apply to either Tetraberlinia species. For M. bisulcata and T. korupensis, but not T. bifoliolata (the most shade-tolerant species), caging improved relative seedling survival in the understory locations compared to gaps, providing restricted support for the Limiting Resource Model. Approximately 2.25 years after treatments were removed, the caged seedlings were taller and had more leaves than controls in all three species, and the effect remained strongest for M. bisulcata. We conclude that in this community the impact of leaf herbivory on seedling growth in gaps is strong for the dominant M. bisulcata, which coupled to a very low shade-tolerance contributes to limiting its regeneration. However, because gaps are common to most forests, insect herbivores may be having impacts upon functionally similar tree species that are also characterized by low sapling recruitment much more widely than currently appreciated. An implication for the restoration and management of M. bisulcata populations in forests outside of Korup is that physical protection from herbivores of new seedlings where the canopy is opened by gaps, or by harvesting, should substantially increase its subcanopy regeneration, and thus, too, its opportunities for adult recruitment.

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The synthesis and characterisation of copper(I) complexes of chiral pyridine-containing macrocyclic ligands (Pc-L*) and their use as catalysts in asymmetric cyclopropanation reactions are reported. All ligands and metal complexes were fully characterised, including crystal structures of some species determined by X-ray diffraction on single crystals. This allowed characterising the very different conformations of the macrocycles which could be induced by different substituents or by metal complexation. The strategy adopted for the ligand synthesis is very flexible allowing several structural modifications. A small library of macrocyclic ligands possessing the same donor properties but with either C-1 or C-2 symmetry was synthesized. Cyclopropane products with both aromatic and aliphatic olefins were obtained in good yields and enantiomeric excesses up to 99%.

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Phase stability, elastic behavior, and pressure-induced structural evolution of synthetic boron-mullite Al5BO9 (a = 5.6780(7), b = 15.035(6), and c =7.698(3) Å, space group Cmc21, Z = 4) were investigated up to 25.6(1) GPa by in situ single-crystal synchrotron X-ray diffraction with a diamond anvil cell (DAC) under hydrostatic conditions. No evidence of phase transition was observed up to 21.7(1) GPa. At 25.6(1) GPa, the refined unit-cell parameters deviated significantly from the compressional trend, and the diffraction peaks appeared broader than at lower pressure. At 26.7(1) GPa, the diffraction pattern was not indexable, suggesting amorphization of the material or a phase transition to a high-pressure polymorph. Fitting the P–V data up to 21.7(1) GPa with a second-order Birch–Murnaghan Equation-of-State, we obtained a bulk modulus KT0 = 164(1) GPa. The axial compressibilities, here described as linearized bulk moduli, are as follows: KT0(a) = 244(9), KT0(b) = 120(4), and KT0(c) = 166(11) GPa (KT0(a):KT0(b):KT0(c) = 2.03:1:1.38). The structure refinements allowed a description of the main deformation mechanisms in response to the applied pressure. The stiffer crystallographic direction appears to be controlled by the infinite chains of edge-sharing octahedra running along [100], making the structure less compressible along the a-axis than along the b- and c-axis.

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We have determined the flux of calcium, chloride and nitrate to the McMurdo Dry Valleys region by analysing snow pits for their chemical composition and their snow accumulation using multiple records spanning up to 48 years. The fluxes demonstrate patterns related to elevation and proximity to the ocean. In general, there is a strong relationship between the nitrate flux and snow accumulation, indicating that precipitation rates may have a great influence over the nitrogen concentrations in the soils of the valleys. Aeolian dust transport plays an important role in the deposition of some elements (e.g. C(2+)) into the McMurdo Dry Valleys' soils. Because of the antiquity of some of the soil surfaces in the McMurdo Dry Valleys regions, the accumulated atmospheric flux of salts to the soils has important ecological consequences. Although precipitation may be an important mechanism of salt deposition to the McMurdo Dry Valley surfaces, it is poorly understood because of difficulties in measurement and high losses from sublimation.

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par James Darmesteter

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von Max Doctor