207 resultados para asymmetric allylation


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A 12 V Substrate-Integrated PbO2-Activated Carbon hybrid ultracapacitor (SI-PbO2-AC HUCs) with silica-gel sulfuric acid electrolyte is developed and performance tested. The performance of the silica-gel based hybrid ultracapacitor is compared with flooded and AGM-based HUCs. These HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area activated carbon with dense graphite-sheet substrate as negative electrodes. 12 V SI-PbO2-AC HUCs with flooded, AGM and gel electrolytes are found to have capacitance values of 308 F, 184 F, and 269 F at C-rate and can be pulse charged and discharged for 100,000 cycles with only a nominal decrease in their capacitance values. The best performance is exhibited by gel-electrolyte HUCs.

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Multilevel inverters with hexagonal and dodecagonal voltage space vector structures have improved harmonic profile compared to two level inverters. Further improvement in the quality of the waveform is possible using multilevel octadecagonal (18 sided polygon) voltage space vectors. This paper proposes an inverter circuit topology capable of generating multilevel octadecagonal voltage space vectors, by cascading two asymmetric three level inverters. By proper selection of DC link voltages and the resultant switching states for the inverters, voltage space vectors, whose tips lie on three concentric octadecagons, are obtained. The advantages of octadecagonal voltage space vector based PWM techniques are the complete elimination of fifth, seventh, eleventh and thirteenth harmonics in phase voltages and the extension of linear modulation range. In this paper, a simple PWM timing calculation method is also proposed. Matlab simulation results and experimental results have been presented in this paper to validate the proposed concept.

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Direct asymmetric vinylogous Michael reactions of gamma-aryl-substituted deconjugated butenolides with nitroolefins and N-phenylmaleimide are described using bifunctional thiourea derivatives as the catalyst. The resulting butenolide derivatives containing adjacent quaternary and tertiary stereocenters are obtained in good yields (54-90%) and with excellent enantioselectivities (er up to 99:1) and high diastereoselectivities (dr up to > 20:1).

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For any n(t) transmit, n(r) receive antenna (n(t) x n(r)) multiple-input multiple-output (MIMO) system in a quasi-static Rayleigh fading environment, it was shown by Elia et al. that linear space-time block code schemes (LSTBC schemes) that have the nonvanishing determinant (NVD) property are diversity-multiplexing gain tradeoff (DMT)-optimal for arbitrary values of n(r) if they have a code rate of n(t) complex dimensions per channel use. However, for asymmetric MIMO systems (where n(r) < n(t)), with the exception of a few LSTBC schemes, it is unknown whether general LSTBC schemes with NVD and a code rate of n(r) complex dimensions per channel use are DMT optimal. In this paper, an enhanced sufficient criterion for any STBC scheme to be DMT optimal is obtained, and using this criterion, it is established that any LSTBC scheme with NVD and a code rate of min {n(t), n(r)} complex dimensions per channel use is DMT optimal. This result settles the DMT optimality of several well-known, low-ML-decoding-complexity LSTBC schemes for certain asymmetric MIMO systems.

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A space-time block code (STBC) is said to be multigroup decodable if the information symbols encoded by it can be partitioned into two or more groups such that each group of symbols can be maximum-likelihood (ML) decoded independently of the other symbol groups. In this paper, we show that the upper triangular matrix encountered during the sphere decoding of a linear dispersion STBC can be rank-deficient even when the rate of the code is less than the minimum of the number of transmit and receive antennas. We then show that all known families of high-rate (rate greater than 1) multigroup decodable codes have rank-deficient matrix even when the rate is less than the number of transmit and receive antennas, and this rank-deficiency problem arises only in asymmetric MIMO systems when the number of receive antennas is strictly less than the number of transmit antennas. Unlike the codes with full-rank matrix, the complexity of the sphere decoding-based ML decoder for STBCs with rank-deficient matrix is polynomial in the constellation size, and hence is high. We derive the ML sphere decoding complexity of most of the known high-rate multigroup decodable codes, and show that for each code, the complexity is a decreasing function of the number of receive antennas.

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Chiral 2-pyridylsulfinamides were shown to be effective catalysts in the alkylation of aryl and alkyl aldehydes with diethylzinc providing the corresponding alcohols in excellent enantioselectivity. Sulfinamide catalysts possessing solitary chirality at the sulfur center produced the product phenethyl alcohol in good enantioselectivity. Diastereomeric sulfinamides possessing chirality at the carbon-bearing nitrogen and at the sulfur of the sulfinamide increased the enantioselectivity of the product alcohols up to >99%. However, there is no effect of the match-mismatch pair of sulfinamide diastereomers on the outcome of the chiral induction of the product phenethyl alcohols. It was conclusively proved that chirality at the sulfur center is mandatory for obtaining good enantioselectivity in the reaction.

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Single-stranded DNA (ssDNA) is a prerequisite for electrochemical sensor-based detection of parasite DNA and other diagnostic applications. To achieve this detection, an asymmetric polymerase chain reaction method was optimised. This method facilitates amplification of ssDNA from the human lymphatic filarial parasite Wuchereria bancrofti. This procedure produced ssDNA fragments of 188 bp in a single step when primer pairs (forward and reverse) were used at a 100:1 molar ratio in the presence of double-stranded template DNA. The ssDNA thus produced was suitable for immobilisation as probe onto the surface of an Indium tin oxide electrode and hybridisation in a system for sequence-specific electrochemical detection of W. bancrofti. The hybridisation of the ssDNA probe and target ssDNA led to considerable decreases in both the anodic and the cathodic currents of the system's redox couple compared with the unhybridised DNA and could be detected via cyclic voltammetry. This method is reproducible and avoids many of the difficulties encountered by conventional methods of filarial parasite DNA detection; thus, it has potential in xenomonitoring.

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Waters, in 2009, introduced an important technique, called dual system encryption, to construct identity-based encryption (IBE) and related schemes. The resulting IBE scheme was described in the setting of symmetric pairing. A key feature of the construction is the presence of random tags in the ciphertext and decryption key. Later work by Lewko and Waters removed the tags and proceeding through composite-order pairings led to a more efficient dual system IBE scheme using asymmetric pairings whose security is based on non-standard but static assumptions. In this work, we have systematically simplified Waters 2009 IBE scheme in the setting of asymmetric pairing. The simplifications retain tags used in the original description. This leads to several variants, the first one of which is based on standard assumptions and in comparison to Waters’ original scheme reduces ciphertexts and keys by two elements each. Going through several stages of simplifications, we finally obtain a simple scheme whose security can be based on two standard assumptions and a natural and minimal extension of the decision Diffie-Hellman problem for asymmetric pairing groups. The scheme itself is also minimal in the sense that apart from the tags, both encryption and key generation use exactly one randomiser each. This final scheme is more efficient than both the previous dual system IBE scheme in the asymmetric setting due to Lewko and Waters and the more recent dual system IBE scheme due to Lewko. We extend the IBE scheme to hierarchical IBE (HIBE) and broadcast encryption (BE) schemes. Both primitives are secure in their respective full models and have better efficiencies compared to previously known schemes offering the same level and type of security.

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Surface-functionalized multiwall carbon nanotubes (MWCNTs) are incorporated in poly(methyl methacrylate)/styrene acrylonitrile (PMMA/SAN) blends and the pretransitional regime is monitored in situ by melt rheology and dielectric spectroscopy. As the blends exhibit weak dynamic asymmetry, the obvious transitions in the melt rheology due to thermal concentration fluctuations are weak. This is further supported by the weak temperature dependence of the correlation length ( approximate to 10-12 angstrom) in the vicinity of demixing. Hence, various rheological techniques in both the temperature and frequency domains are adopted to evaluate the demixing temperature. The spinodal decomposition temperature is manifested in an increase in the miscibility gap in the presence of MWCNTs. Furthermore, MWCNTs lead to a significant slowdown of the segmental dynamics in the blends. Thermally induced phase separation in the PMMA/SAN blends lead to selective localization of MWCNTs in the PMMA phase. This further manifests itself in a significant increase in the melt conductivity.

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Recently, several reports showed that about 80 % of mid-log phase Mycobacterium smegmatis, Mycobacterium marinum, and Mycobacterium bovis BCG cells divide symmetrically with 5-10 % deviation in the septum position from the median. However, the mode of cell division of the pathogenic mycobacterial species, Mycobacterium tuberculosis, remained unclear. Therefore, in the present study, using electron microscopy, fluorescence microscopy of septum- and nucleoid-stained live and fixed cells, and live cell time-lapse imaging, we show the occurrence of asymmetric cell division with unusually deviated septum/constriction in 20 % of the 15 % septating M. tuberculosis cells in the mid-log phase population. The remaining 80 % of the 15 % septating cells divided symmetrically but with 2-5 % deviation in the septum/constriction position, as reported for M. smegmatis, M. marinum, and M. bovis BCG cells. Both the long and the short portions of the asymmetrically dividing M. tuberculosis cells with unusually deviated septum contained nucleoids, thereby generating viable short and long cells from each asymmetric division. M. tuberculosis short cells were acid fast positive and, like the long cells, further readily underwent growth and division to generate micro-colony, thereby showing that they were neither mini cells, spores nor dormant forms of mycobacteria. The freshly diagnosed pulmonary tuberculosis patients' sputum samples, which are known for the prevalence of oxidative stress conditions, also contained short cells at the same proportion as that in the mid-log phase population. The probable physiological significance of the generation of the short cells through unusually deviated asymmetric cell division is discussed.

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G-Quadruplexes occupy important regulatory regions in the genome. DNA G-quadruplexes in the promoter regions and RNA quadruplexes in the UTRs (untranslated regions) have been individually studied and variously implicated at different regulatory levels of gene expression. However, the formation of G-quadruplexes in the sense and antisense strands and their corresponding roles in gene regulation have not been studied in much detail. In the present study, we have elucidated the effect of strand asymmetry in this context. Using biophysical methods, we have demonstrated the formation of stable G-quadruplex structure in vitro using CD and UV melting. Additionally, ITC was employed to demonstrate that a previously reported selective G-quadruplex ligand was able to bind and stabilize the G-quadruplex in the present sequence. Further, we have shown using reporter constructs that although the DNA G-quadruplex in either strand can reduce translation efficiency, transcriptional regulation differs when G-quadruplex is present in the sense or antisense strand. We demonstrate that the G-quadruplex motif in the antisense strand substantially inhibits transcription, while when in the sense strand, it does not affect transcription, although it does ultimately reduce translation. Further, it is also shown that the G-quadruplex stabilizing ligand can enhance this asymmetric transcription regulation as a result of the increased stabilization of the G-quadruplex.

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An enantiospecific total synthesis of polyhydroxy delta-pyrone natural product (+)-anamarine is accomplished. The main features of the synthesis include the stereoselective reduction of the ketone obtained by the desymmetrization of the bis-dimethyl amide of tartaric acid and further elaboration involving asymmetric Brown's allylation and ring closing metathesis. (C) 2014 Elsevier Ltd. All rights reserved.

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The first organocatalytic asymmetric reaction of 3-isothiocyanatooxindoles with nitro olefins has been developed by using a cinchonidine-derived bifunctional catalyst. The resulting products, highly functionalized 3,2-pyrrolidinyl-substituted spirooxindole derivatives, were obtained in high yields with good diastereo- and enantioselectivities (up to dr >20:1 and er = 96:4). This Michael addition/cyclization cascade reaction employs monosubstituted nitro olefins and complements the Zn-II-catalyzed variant, which is only applicable to disubstituted nitro olefins.

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Catalytic asymmetric desymmetrization represents an excellent strategy for accessing highly functionalized chiral building blocks. However, the application of desymmetrization for the synthesis of enantio-enriched cyclopentane derivatives remained limited, when compared to chiral cyclohexanes. We have recently developed a desymmetrization protocol for prochiral 2,2-disubstituted cyclopentene-1,3-diones by direct catalytic asymmetric vinylogous nucleophilic addition of deconjugated butenolides. In this perspective, we give an overview of asymmetric desymmetrization reactions leading to enantioenriched cyclopentanes and their derivatives. The focus is kept confined to the diverse nature of reactions used for this purpose. A brief discussion on the potential future directions is also provided.