Powder MAS NMR lineshapes of quadrupolar nuclei in the presence of second-order quadrupole interaction

We derive a complete analytical solution for the powder magic angle spinning (MAS) nuclear magnetic resonance (NMR) lineshape in the presence of second-order quadrupole interaction, considering a radiofrequency (rf) pulse of finite width, a finite MAS frequency, and a non-zero asymmetry parameter. I_x is calculated using two approaches. The first applies time-dependent perturbation theory in the presence of the rf pulse and stationary perturbation theory (SPT) in its absence. The second is based on the Magnus expansion of the density matrix in the interaction representation during the pulse and SPT in its absence. We solve the problem in the laboratory frame using the properties of the Fourier transform and spin operators. Diagonalisation is not required. Both approaches agree well with each other under all conditions and also with the transition probability approach for the central transition. The Magnus expansion exists at all times and the effect of the non-secular terms is negligible. We describe an analytical method of averaging I_x over the Euler angles and simulate the ¹¹B MAS NMR lineshapes for crystalline and vitreous B₂O₃. A critical analysis is given of all earlier calculations of the MAS NMR lineshape.     

Preparation and characterization of transparent conducting ZnS:Al films

Al-doped ZnS films were deposited using close-spaced evaporation of the powders synthesized by chemical precipitation method. The films were prepared for different Al concentrations in the range 0–10 at.% on glass substrates kept at 300 °C. The effect of Al-doping on ZnS composition, microstructure and optoelectronic properties of as-grown ZnS layers was determined using appropriate techniques. The films were polycrystalline and showed (111) preferred orientation for all the doping concentrations in spite of an additional phase of Al₂S₃ observed at higher dopant levels. The surface morphological studies indicated that the Al incorporation had a considerable effect on the surface roughness of the films. The optical measurements indicated that the optical energy band gap decreased slightly with the increase of dopant concentration without affecting the optical transmittance characteristics significantly. The electrical analysis indicated that the resistivity of the layers changed significantly with the doping concentration in the layers. The change of photoluminescence behaviour of the as-grown ZnS:Al films with dopant concentration was also studied.     

Selective lighting up of segments around Gly,Ala and Ser/Thr in proteins

Direct detection of ¹³C nucleus can be used as a valuable alternative where ¹H detection poses a challenge due to relaxation effects, chemical exchange and poor chemical shift dispersion. In this context, we have designed a suite of 2D ¹³C^α‐detected hNCA experiments that provide sequential correlations of ¹³C^α with ¹⁵N on one hand and efficient spectroscopic labeling of certain groups of residues, namely, Gly, Ala, Ser and Thr, on the other. These residues act as checkpoints in the sequential walk, which in turn offer new possibilities of backbone assignment of small proteins from a set of 2D experiments, thereby providing great economy in terms of spectrometer time. The direct identification of peptide segments around Gly, Ala, Ser and Thr residues along a protein chain will be highly valuable for deriving important information on sites of ligand binding, phosphorylation, inhibitor/substrate binding, understanding protein folding pathways, comprehending local conformational dynamics etc. without having to obtain complete sequence‐specific assignments, which can be time consuming and at times formidable, especially in large proteins. We have illustratively demonstrated the multifaceted applications of these variants of 2D experiments on ubiquitin and M‐crystallin. We foresee that these 2D hNCA experiments will provide economic and efficient strategies for studying the structure and function of proteins. Copyright © 2012 John Wiley & Sons, Ltd.     

Palladium complexes of bis(acyclic diaminocarbene) ligands with chiral N-substituents and 8-membered chelate rings

Reaction of cis-dichloridobis(p-trifluoromethylphenylisocyanide)palladium(II) with N,N′-bis[(R)-1-phenylethyl]-1,3-diaminopropane afforded an enantiomerically pure, C₁-symmetric bis(acyclic diaminocarbene)PdCl₂ complex in 41% yield. The X-ray crystal structure of the complex revealed that three of the four carbene nitrogens are twisted out of conjugation with the carbene units, apparently as a result of steric interactions between one phenyl group and the propylene backbone of the chelate. A similar reaction with N,N′-bis[(R)-1-(1-naphthyl)ethyl]-1,3-diaminopropane did not lead to an isolable bis(carbene) complex, instead forming significant amounts of bis(ammonium) salt as a decomposition product. However, reaction of the same palladium isocyanide precursor with a mixture of all diastereomers of N,N′-bis[1-(1-naphthyl)ethyl]-1,3-diaminopropane provided an achiral, C_s-symmetric palladium bis(acyclic diaminocarbene) complex derived exclusively from the (R,S) diamine in 20% yield. An X-ray structure showed that the (R,S) stereochemistry allows the bulky naphthyl groups to adopt an orientation that avoids steric interactions with the backbone that likely lead to the instability of the homochiral analogue. The two palladium carbene complexes catalyzed the aza-Claisen rearrangement of an allylic imidate to an allylic amide in 24–34% yield, with an enantiomeric excess of 8% ee for the [(R)-1-phenylethyl]-substituted complex.     

Stereoselective synthesis of N-benzyl conduramine F-1, N-benzyl ent-conduramine E-1, dihydroconduramine F-1 and ent-dihydroconduramine E-1

A short and stereoselective synthesis of conduramine F-1 and ent-conduramine E-1 derivatives have been achieved starting from d-mannitol using nucleophilic vinylation on imine. A concise sequence of vinylation at both ends of d-mannitol and followed by RCM allowed us to prepare target compound.     

Oxidative decarboxylation of arylacetic acids in water: One-pot transition-metal-free synthesis of aldehydes and ketones

One-pot transition-metal-free synthesis of aromatic aldehydes and ketones via oxidative decarboxylation of arylacetic acids in water is developed. Protocol relies on the direct decarboxylation of sp³-hybridized carbon in water without any over oxidation into carboxylic acids with minimal waste. Reaction mechanism is investigated and application of this protocol is demonstrated on a gram scale.     

Ultrasound assisted,VOSO4 catalyzed synthesis of 4-thiazolidinones: Antimicrobial evaluation of indazole-4-thiazolidinone derivatives

A simple and expedient multicomponent protocol was developed to synthesize 4-thiazolidinones by employing VOSO₄ as a catalyst under ultrasonic irradiation. The significant features of this protocol includes shorter reaction time, high yields, low catalyst loading, and also the catalyst can be recovered and reused up to next four cycles without significant loss in catalytic activity. All the synthesized novel indazole compounds were evaluated for their antibacterial and anti-biofilm activities. Compounds 9n, 9o and 9q showed promising activity (MIC value of 3.9?µg/mL) against K. planticola (MTCC 530). They also exhibited significant bactericidal activity against K. planticola (MTCC 530) (MBC value of 15.6?µg/mL). Additionally, 9n, 9o and 9q inhibited biofilm formation (IC₅₀ values ranging between 20.28–20.79?μg/mL) in this organism.