Organocatalytic asymmetric direct vinylogous Michael addition of α,β-unsaturated γ-butyrolactam to nitroolefins

The first organocatalytic enantioselective direct vinylogous Michael reaction of α,β-unsaturated γ-butyrolactam to nitroolefins is developed using cinchona alkaloids as the catalysts. Both product enantiomers are accessible with moderate to good enantioselectivity.

Organocatalytic asymmetric direct vinylogous Michael addition of alpha,beta-unsaturated gamma-butyrolactam to nitroolefins

The first organocatalytic enantioselective direct vinylogous Michael reaction of alpha,beta-unsaturated gamma-butyrolactam to nitroolefins is developed using cinchona alkaloids as the catalysts. Both product enantiomers are accessible with moderate to good enantioselectivity.

Asymmetric forced convection of nanofluids in a channel with symmetrically mounted rib heaters on opposite walls

Laminar forced convection of nanofluids in a vertical channel with symmetrically mounted rib heaters on surfaces of opposite walls is numerically studied. The fluid flow and heat transfer characteristics are examined for various Reynolds numbers and nanoparticles volume fractions of water-Al2O3 nanofluid. The flow exhibits various structures with varying Reynolds number. Even though the geometry and heating is symmetric with respect to a channel vertical mid-plane, asymmetric flow and heat transfer are found for Reynolds number greater than a critical value. Introduction of nanofluids in the base fluid delays the flow solution bifurcation point, and the critical Reynolds number increases with increasing nanoparticle volume fraction. A skin friction coefficient along the solid-fluid interfaces increases and decreases sharply along the bottom and top faces of the heaters, respectively, due to sudden acceleration and deceleration of the fluid at the respective faces. The skin friction coefficient, as well as Nusselt numbers in the channel, increase with increasing volume fraction of nanoparticles.

Catalytic Asymmetric Direct Vinylogous Michael Addition of Deconjugated Butenolides to Maleimides for the Construction of Quaternary Stereogenic Centers

Competition under control: A practical and efficient direct asymmetric vinylogous Michael reaction of deconjugated butenolides has been developed (see scheme). The products of this reaction, highly functionalized chiral succinimides, are obtained in excellent yield with high diastereoselectivity (up to d.r.=18:1) and outstanding enantioselectivity (up to e.r.=99.5:0.5).

DMT-optimal, Low ML-Complexity STBC-Schemes for Asymmetric MIMO Systems

For an n(t) transmit, nr receive antenna (n(t) x n(r)) MIMO system with quasi- static Rayleigh fading, it was shown by Elia et al. that space-time block code-schemes (STBC-schemes) which have the non-vanishing determinant (NVD) property and are based on minimal-delay STBCs (STBC block length equals n(t)) with a symbol rate of n(t) complex symbols per channel use (rate-n(t) STBC) are diversity-multiplexing gain tradeoff (DMT)-optimal for arbitrary values of n(r). Further, explicit linear STBC-schemes (LSTBC-schemes) with the NVD property were also constructed. However, for asymmetric MIMO systems (where n(r) < n(t)), with the exception of the Alamouti code-scheme for the 2 x 1 system and rate-1, diagonal STBC-schemes with NVD for an nt x 1 system, no known minimal-delay, rate-n(r) LSTBC-scheme has been shown to be DMT-optimal. In this paper, we first obtain an enhanced sufficient criterion for an STBC-scheme to be DMT optimal and using this result, we show that for certain asymmetric MIMO systems, many well-known LSTBC-schemes which have low ML-decoding complexity are DMT-optimal, a fact that was unknown hitherto.

Thermal degradation kinetics of thermoresponsive poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers prepared via RAFT polymerization

Reversible addition-fragmentation chain transfer polymerization at 70 A degrees C in N,N-dimethylformamide was used to prepare poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers in various compositions to afford well-defined polymers with pre-determined molecular weight, narrow molecular weight distribution, and precise chain end structure. The copolymer compositions were determined by H-1 NMR spectroscopy. The reactivity ratios of N-isopropylacrylamide (NIPAM) and N,N-dimethylacrylamide (DMA) were calculated as r (NIPAM) = 0.838 and r (DMA) = 1.105, respectively, by the extended Kelen-Tudos method at high conversions. The lower critical solution temperature of PNIPAM can be altered by changing the DMA content in the copolymer chain. Differential scanning calorimetry and thermogravimetric analysis at different heating rates were carried out on these copolymers to understand the nature of thermal degradation and to determine its kinetics. Different kinetic models were applied to estimate various parameters like the activation energy, the order, and the frequency factor. These studies are important to understand the solid state polymer degradation of N-alkyl substituted polymers, which show great potential in the preparation of miscible polymer blends due to their ability to interact through hydrogen bonding.

A 12 V Substrate-Integrated PbO2-Activated Carbon Asymmetric Hybrid Ultracapacitor with Silica-Gel-Based Inorganic-Polymer Electrolyte

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.

Multilevel octadecagonal space vector generation for induction motor drives by cascading asymmetric three level inverters

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.

Dynamics and Regulation of RecA Polymerization and De-Polymerization on Double-Stranded DNA

The RecA filament formed on double-stranded (ds) DNA is proposed to be a functional state analogous to that generated during the process of DNA strand exchange. RecA polymerization and de-polymerization on dsDNA is governed by multiple physiological factors. However, a comprehensive understanding of how these factors regulate the processes of polymerization and de-polymerization of RecA filament on dsDNA is still evolving. Here, we investigate the effects of temperature, pH, tensile force, and DNA ends (in particular ssDNA overhang) on the polymerization and de-polymerization dynamics of the E. coli RecA filament at a single-molecule level. Our results identified the optimal conditions that permitted spontaneous RecA nucleation and polymerization, as well as conditions that could maintain the stability of a preformed RecA filament. Further examination at a nano-meter spatial resolution, by stretching short DNA constructs, revealed a striking dynamic RecA polymerization and de-polymerization induced saw-tooth pattern in DNA extension fluctuation. In addition, we show that RecA does not polymerize on S-DNA, a recently identified novel base-paired elongated DNA structure that was previously proposed to be a possible binding substrate for RecA. Overall, our studies have helped to resolve several previous single-molecule studies that reported contradictory and inconsistent results on RecA nucleation, polymerization and stability. Furthermore, our findings also provide insights into the regulatory mechanisms of RecA filament formation and stability in vivo.

Catalytic Asymmetric Direct Vinylogous Michael Addition of gamma-Aryl-Substituted Deconjugated Butenolides to Nitroolefins and N-Phenylmaleimide

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).

Enhanced DMT-optimality criterion for STBC schemes for asymmetric MIMO systems

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.

On the sphere decoding complexity of high-rate multigroup decodable STBCs in asymmetric MIMO systems

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.

2-Pyridylsulfinamides as effective catalysts in the asymmetric alkylation of aldehydes with diethylzinc

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.

Optimisation of an asymmetric polymerase chain reaction assay for the amplification of single-stranded DNA from Wuchereria bancrofti for electrochemical detection

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.