A flexible organocatalytic enantioselective synthesis of heptadeca-1-ene-4,6-diyne-3S,8R,9S,10S-tetrol and its congeners

A unified enantioselective route is developed for the synthesis of heptadeca-1-ene-4,6-diyne-3S,8R,9S,10S-tetrol and its synthetic congeners. A proline-catalyzed aminoxylation, cross-metathesis, Wittig reaction, and catalytic dihydroxylation are key steps of this synthesis. This new approach is envisioned to facilitate the synthesis of every representative member of the family with skeletal and stereochemical variation.     

Influence of sintering temperature on microstructure,critical current density and pinning potential of superconducting Bi1.6Pb0.5Sr1.8Dy0.2Ca1.1Cu2.1O8+δ ceramics

The influence of sintering temperature on the microstructure, critical current density (J_C), pinning potential values (U₀) and flux pinning properties of Bi_1.6Pb_0.5Sr_1.8Dy_0.2Ca_1.1Cu_2.1O_8+δ superconductor has been investigated. The samples are prepared by the solid-state route and sintered at temperatures ranging from 846 to 860 °C. A systematic correlation between the sintering temperature, Lotgering index, J_C, U₀ and flux pinning properties has been found. The samples sintered at lower sintering temperature (846 °C) have more grain boundaries with smaller grains while those sintered at a higher temperature (856 °C) contain larger grains with good texturing. The flux pinning force (F_P) calculated from the field dependent J_C values shows that the irreversibility lines (IL) of the Dy-doped samples shift towards higher fields to different extents depending on the sintering temperature. The maximum value of F_P = 1697 kN m^?3 is obtained for the sample sintered at 846 °C and the peak position of F_P is obtained at 0.96 T as against 616 kN m^?3 and 0.52 T for the sample sintered at 856 °C. The U₀ values calculated by Anderson's function is maximum for the sample sintered at 846 °C. But the self-field J_C value of this sample is lower than that of the samples sintered at 856 °C. The samples sintered at 856 °C show best self-field J_C due to the improved microstructure. The changes in microstructure followed by very high enhancement of self-field J_C, J_C(B) characteristics, F_P and U₀ values within a narrow temperature range, are of great scientific and technological significance and the results are explained on the basis of microstructural variation with respect to sintering temperature, hole optimization and formation of point defects due to the doping of Dy atoms in Bi_1.6Pb_0.5Sr_1.8Dy_0.2Ca_1.1Cu_2.1O_8+δ system.     

Synthesis of functional hybrid silica scaffolds with controllable hierarchical porosity by dynamic templating

We report a facile one-pot synthesis of hierarchically porous scaffolds, with independent control over nanoparticle mesoporosity and scaffold macroporosity. Our technique combines the chemistry of mesoporous silica nanoparticles with the control afforded by dynamic templating of surfactant mesophases. These materials are readily functionalizable and allow controllable spatial variation in macroporosity.     

Highly Diastereoselective Total Syntheses of (+)‐7‐Epigoniodiol, (−)‐8‐Epigoniodiol,and (+)‐9‐Deoxygoniopypyrone

An expedient concise total synthesis of (+)‐7‐epigoniodiol, (?)‐8‐epigoniodiol, and (+)‐9‐deoxygoniopypyrone is accomplished. The key transformations include a catalytic hydroxylation and base‐mediated N‐(acetyl)oxazolidinone addition reactions, which could set the consecutive OH motif that is either syn,syn or syn,anti with high diastereoselectivity. Moreover, this approach envisioned to facilitate the synthesis of other representatives of the family with structural and stereochemical variation.     

Effect of barium chloride doping on PVA microstructure: positron annihilation study

Microstructural studies on BaCl₂ doped polyvinyl alcohol (PVA) polymer films were carried out using density, PAL and dielectric measurements at room temperature. The positron annihilation studies on these samples shows considerable effect on the PVA microstructure due to doping and is understood by invoking the chemical reaction between Ba²⁺ ions of BaCl₂ with OH groups of PVA via intra/inter molecular hydrogen bonding, which forms the complex. This complex formation modifies the free volume content in the amorphous fraction, and results in an enhancement of the polymer crystallinity. At higher dopant concentrations, the number of such complexes increases, and ends up with the formation of dopant aggregates or agglomerates leading to certain phase separation into a polymer-rich phase and a dopant-rich phase. These phase separations are thought to be due to the existence of two or more crystalline phases within the polymer matrix. The XRD study also supports this enhancement of PVA crystallinity due to doping. The electrical studies on the doped PVA reflects that the complex formation due to doping affects the microstructure and hence the dielectric properties including the dc and ac conductivities of the polymer. All of these observed results were analyzed and understood based on the microstructural modification of PVA as a function of dopant concentrations. PACS 78.70.Bj; 73.61.Ph; 77.84.Jd     

Stereoselective total synthesis of (+)-oploxyne A, (-)-oploxyne B, and their C-10 epimers and structure revision of natural oploxyne B

The first total synthesis of recently isolated diacetylene alcohols oploxyne A, oploxyne B, and their C-10 epimers was accomplished. The structure of natural oploxyne B has been revised. The key steps involved are base-induced double elimination of a carbohydrate-derived β-alkoxy chloride to generate the chiral acetylenic alcohol and Cadiot-Chodkiewicz cross-coupling reaction. The target compounds displayed potent cytotoxicity against neuroblastoma and prostate cancer cell lines.     

Modification in the transport and morphological properties of solid polymer electrolyte system by low-energy ion irradiation

The poly(ethylene oxide) (PEO)-based solid polymer electrolyte (SPE) systems consisting of NaBr as a dopant salt are prepared. The stable PEO:NaBr system with 3 wt% of NaBr was subjected to low-energy ion beam irradiation to bring in morphological modification. The irradiated samples are studied using complex impedance spectra to evaluate electrical conductivity and relaxation process in the system. The studies show an increase in conductivity by one order magnitude in the irradiated systems. The dielectric loss tangent (tanδ) curves show a single peak due to strong coupling of ion transport with segmental motion. The resultant relaxation time τ exhibits a continuous decrease indicating increase in segmental dynamics as a result of increased amorphous content in the system. The temperature-dependent studies also indicate that the irradiated systems are more disordered/amorphous compared to pure systems. This fact is further supported by XRD, by observing an increase in peak width associated with reduction in peak intensity. The Raman spectra also support the change in morphology of the system by the appearance of disordered-longitudinal acoustic mode band.     

Studies on vibration of some rib-stiffened cantilever plates

An experimental study was carried out to determine the resonant mode shapes and frequencies of some rib-stiffened skew cantilever plates by holographic interferometry. The influences of varying the sweep back angle, the rib stiffness and the aspect ratio, and the effect of varying the boundary conditions at the root chord, on the frequencies and mode shapes were also investigated. Results of the above investigation and also those of a comparative study with the finite element solution obtained for some of the cases studied are presented and discussed.     

Elastic piezoelectric aerogels from isotropic and directionally ice-templated cellulose nanocrystals: comparison of structure and energy harvesting

We report the preparation of highly compressible and elastic piezoelectric aerogels of carboxylated cellulose nanocrystals (CNCs). Aqueous CNC dispersions containing polyethyleneimine and crosslinker were frozen isotropically to yield isotropic aerogels, while oriented aerogels were prepared by directional freezing. These aerogels were highly flexible and porous (~?85% void fraction), exhibiting greater than 90% recovery at 50% compressive strain even after 100 compression–decompression cycles. Since such aerogels with low bulk modulus and high anisotropy would be an ideal platform for leveraging the piezoelectric properties of CNCs, we used them to prepare piezoelectric nanogenerator devices and determined their energy transduction behavior. Anisotropic aerogels led to an enhanced open-circuit voltage of 840 mV (at ~?8 N applied force), which is over 2.6 times higher than isotropic aerogels (320 mV). The energy density of anisotropic aerogels was around 52 nW/cm², representing outstanding piezoelectric performance for cellulose-based aerogels. Such aerogels with high compressibility, elastic recovery and exceptional piezoelectric performance could have potential applications in sensors, wearable electronics, etc.