A new type of amino amide organocatalyzed enantioselective crossed aldol reaction of ketones with aromatic aldehydes

A new type of amino amide organocatalysts was designed and synthesized from commercially available amino acids in easy steps. Their catalytic activities were examined in enantioselective crossed aldol reaction of various acyclic and cyclic ketones with aromatic aldehydes to afford the corresponding chiral anti-aldol adducts with good to excellent chemical yields, diastereoselectivities and enantioselectivities (up to 99%, up to syn:anti?=?1:99, up to 97% ee).     

Improving the photocatalytic performance of TiO2 via hybridizing with graphene

In this paper an improvement in the photocatalytic performance of TiO₂ was carried out via hybridizing with graphene. Graphene-TiO₂ (GR-TiO₂)nanocomposites with different weight addition ratios of graphene oxide (GO) have been prepared via a facile microwave irradiation of GO and tetrabutyl titanate in isopropyl alcohol. Raman spectroscopy (RS), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible spectroscopy (UV-vis), Fourier transform infrared spectra (FTIR), energy dispersive X-ray spectroscopy (EDX) and photoluminescence spectra (PL) are employed to determine the properties of the samples. Microwave irradiation can heat the reactant to a higher temperature in a short time, simultaneously GO is reduced to graphene and TiO₂ nanoparticles grown on the surface of GR. GR-TiO₂ nanocomposites synthesized via this approach have efficient electron conductivity in GR, resulting in a reduced electron-hole recombination rate. Among the synthesized nanocomposites, GT-8wt% exhibited the best photocatalytic activity toward photocatalytic degradation of MB. Our current work provides a new insight for the fabrication of GR-TiO₂ nanocomposites within a short reaction time and also explains the mechanism of photocatalysis employing radical and hole scavengers.     

An experimental study of decoupling sequences for multiple-quantum and high-resolution MAS experiments in solid-state NMR

Recently, a sequence for heteronuclear dipolar decoupling in solid-state NMR, namely SWf-TPPM, was introduced by us. Under magic-angle spinning (MAS), the decoupling efficiency of the sequence was unaffected over a range of values for various experimental parameters such as the pulse length, pulse phase, and 1H resonance offset. We here demonstrate its use in multiple-quantum (MQ) and high-resolution (HR) MAS experiments. This sequence further improves the MQMAS spectra compared to the earlier reported decoupling sequences with improved immunity to any missets of the pulse length, pulse phase and decoupler offset. In contrast, for HRMAS, the simple CW scheme is as efficient as any of the decoupling schemes that were studied.     

Infinite Polyiodide Chains in the Pyrroloperylene–Iodine Complex: Insights into the Starch–Iodine and Perylene–Iodine Complexes

We report the preparation and X‐ray crystallographic characterization of the first crystalline homoatomic polymer chain, which is part of a semiconducting pyrroloperylene–iodine complex. The crystal structure contains infinite polyiodide I_∞^δ?. Interestingly, the structure of iodine within the insoluble, blue starch–iodine complex has long remained elusive, but has been speculated as having infinite chains of iodine. Close similarities in the low‐wavenumber Raman spectra of the title compound and starch–iodine point to such infinite polyiodide chains in the latter as well.     

Physico-mechanical properties and biodegradation of oxo-degradable HDPE/PLA blends

Blends of high density polyethylene/poly(lactic acid) with/without compatibilizer and pro-oxidant (cobalt stearate) were prepared by melt blending technique. In ratio 80/20, the blend revealed a good combination of tensile properties and optimum poly(lactic acid) content. The improvement in mechanical properties of this blend was achieved by addition of 4 phr compatibilizer. Cobalt stearate (CoSt) was added to 80/20 blends in 0.1% and 0.2% (w/w) ratios. The obtained blends were characterized by DSC, SEM, FTIR spectroscopy, rheological study, etc. All the prepared blends were able to biodegrade in composting environment and the blend containing pro-oxidant was maximum degraded.     

High-resolution solid-state NMR spectroscopy of protons with homonuclear dipolar decoupling schemes under magic-angle spinning

High-resolution NMR spectroscopy of ¹H spins in the solid state is normally rendered difficult due to the strong homonuclear ¹H–¹H dipolar couplings. Even under very high-speed magic-angle spinning (MAS) at ca. 60–70 kHz, these couplings are not completely removed. An appropriate radiofrequency pulse scheme is required to average out the homonuclear dipolar interactions in combination with MAS to get high-resolution ¹H NMR spectrum in solid state. Several schemes have been introduced in the recent past with a variety of applications also envisaged. Development of some of these schemes has been made possible with a clear understanding of the underlying spin physics based on bimodal Floquet theory. The utility of these high-resolution pulse schemes in combination with MAS has been demonstrated for spinning speeds of 10–65 kHz in a range of ¹H Larmor frequencies from 300 to 800 MHz.     

Why does PMLG proton decoupling work at 65 kHz MAS?

Schemes such as phase-modulated Lee–Goldburg (PMLG) for homonuclear dipolar decoupling have been shown to yield high-resolution ¹H spectra at high magic-angle spinning (MAS) frequencies of 50–70 kHz. This is at variance to the commonly held notion that these methods require MAS frequencies not comparable to the cycle frequencies of the pulse schemes. Here, a theoretical argument, based on bimodal Floquet theory, is presented to explain this aspect together with conditions where PMLG type of schemes may be successful at high MAS frequencies.     

Templated synthesis of silver nanowires based on the layer-by-layer assembly of silver with dithiodipropionic acid molecules as spacers

The layer-by-layer assembly of silver nanoclusters with 3,3'-dithiodipropionic acid (DTDPA) as spacers was prepared through self-assembly on a gold foil and has been characterized by cyclic voltammetric and AFM techniques. The DTDPA molecules acting as spacers between the layers of silver serve as molecular interconnects for the four layers prepared in this work. The organization of layers was found to decrease with an increase in the number of layers. The layer-by-layer assembly of silver clusters motivated us to prepare silver nanowires stabilized by the bifunctional molecules DTDPA through template synthesis using cellulose nitrate membranes. The nanostructures formed by this method were characterized by SEM, TEM, AFM, FTIR, CV, and photoluminescence studies. It is observed that the DTDPA molecules, instead of forming molecular interconnects, protect the structures by self-assembling themselves along the edges of the nanostructures. The concept of self-assembly protecting the nanostructures is demonstrated in this work.     

The composition dependence of electrical switching behavior of Ge7Se93−xSbx glasses

Bulk Ge₇Se_93?xSb_x (21 ? x ? 32) glasses are prepared by melt quenching method and electrical switching studies have been undertaken on these samples to elucidate the type of switching and the composition and thickness dependence of switching voltages. On the basis of the compressibility and atomic radii, it has been previously observed that Se-based glasses exhibit memory switching behavior. However, the present results indicate that Ge₇Se_93?xSb_x glasses exhibit threshold type electrical switching with high switching voltages. Further, these samples are found to show fluctuations in the current–voltage (I–V) characteristics. The observed threshold behavior of Ge₇Se_93?xSb_x glasses has been understood on the basis of larger atomic radii and lesser compressibilities of Sb and Ge. Further, the high switching voltages and fluctuations in the I–V characteristics of Ge–Se–Sb samples can be attributed to the high resistance of the samples and the difference in thermal conductivities of different structural units constituting the local structure of these glasses. The switching voltages of Ge₇Se_93?xSb_x glasses have been found to decrease with the increase in the Sb concentration. The observed composition dependence of switching voltages has been understood on the basis of higher metallicity of the Sb additive and also in the light of the Chemically Ordered Network (CON) model. Further, the thickness dependence of switching voltages has been studied to reassert the mechanism of switching.     

Nano Gd2O3 catalyzed synthesis and anti-oxidant activity of new α-aminophosphonates

A one pot three-component nano Gd₂O₃ catalyzed neat reaction of 2-morpholinoethanamine and dimethylphosphite with various salicylaldehydes under microwave irradiation afforded a series of new α-aminophosphonates in high yields. The synthesized compounds were characterized by FT-IR, (¹H, ¹³C, ³¹P)-NMR, and mass spectral methods. The antioxidant activity of these compounds was evaluated against DPPH, NO, and H₂O₂ methods and found that the compound Dimethyl (2-hydroxy-5-nitrophenyl) (2-morpholinoethylamino) methylphosphonate (4h) has higher antioxidant activity than the corresponding standards.