PHRONESIS: A One-Shot Approach for Sequential Assignment of Protein Resonances by Ultrafast MAS Solid-State NMR Spectroscopy

Solid-state NMR (ssNMR) spectroscopy has emerged as the method of choice to analyze the structural dynamics of fibrillar, membrane-bound, and crystalline proteins that are recalcitrant to other structural techniques. Recently, ¹H detection under fast magic angle spinning and multiple acquisition ssNMR techniques have propelled the structural analysis of complex biomacromolecules. However, data acquisition and resonance-specific assignments remain a bottleneck for this technique. Here, we present a comprehensive multi-acquisition experiment (PHRONESIS) that simultaneously generates up to ten 3D ¹H-detected ssNMR spectra. PHRONESIS utilizes broadband transfer and selective pulses to drive multiple independent polarization pathways. High selectivity excitation and de-excitation of specific resonances were achieved by high-fidelity selective pulses that were designed using a combination of an evolutionary algorithm and artificial intelligence. We demonstrated the power of this approach with microcrystalline U-¹³C,¹⁵N GB1 protein, reaching 100 % of the resonance assignments using one data set of ten 3D experiments. The strategy outlined in this work opens up new avenues for implementing novel ¹H-detected multi-acquisition ssNMR experiments to speed up and expand the application to larger biomolecular systems.     

A confocal laser scanning microscopic study on thermoresponsive binary microgel dispersions incorporated with CdTe quantum dots

Monodisperse poly(N-isopropylacrylamide) (PNIPAM) particles loaded with cadmium telluride (CdTe) quantum dots (QDs) of two different sizes (4.7 nm and 5.6 nm) were synthesized in aqueous medium by bonding the capping agent on the quantum dots to the amide groups of PNIPAM and incubating the samples at 45°C. A huge increase in the photoluminescence (PL) intensity (green and red regions) is observed for the PNIPAM-CdTe QDs composites compared to the parent CdTe QDs. We report here for the first time the imaging of binary dispersion of green and red luminescent PNIPAM-CdTe QDs composites using a fluorescence confocal laser scanning microscope. These composites have potential applications both in material science and biology.     

Gas-solid coexistence in highly charged colloidal suspensions

Aqueous suspensions of highly charged polystyrene particles with different volume fractions have been investigated for structural ordering and phase behavior using static light scattering (SLS) and confocal laser scanning microscope (CLSM). Under deionized conditions, suspensions of high-charge-density colloidal particles remained disordered whereas suspensions of relatively low charge density showed crystallization by exhibiting iridescence for the visible light. Though for the unaided eye crystallized suspensions appeared homogeneous, SLS measurements and CLSM observations have revealed their inhomogeneous nature in the form of the coexistence of voids with dense ordered regions. CLSM investigations on disordered suspensions showed their inhomogeneous nature in the form coexistence of voids with dense disordered (amorphous) regions. Our studies on highly charged colloids confirm the occurrence of gas-solid transition and are in accordance with predictions of Monte Carlo simulations using a pair-potential having a long-range attractive term [Mohanty, P. S.; Tata, B. V. R. J. Colloid Interface Sci. 2003, 264, 101]. On the basis of our experimental and simulation results, we argue that the reported reentrant disordered state [Yamanaka et al. Phys. Rev. Lett. 1998, 80, 5806 and Toyotama et al. Langmuir 2003, 19, 3236] in charged colloids observed at high charge densities is a gas-solid coexistence state.     

Ruthenium(VI) in the oxidation of 2-propanol and 1-propanol: A kinetic study

Transition Metal Chemistry - Sodium ruthenate catalyses the oxidation of 2-propanol by hexacyanoferrate(III) ([Fe(CN)6]3?), diperiodato-cuprate(III) (DPC), periodate $ (IO_{4}^{-}) $ and...     

Gas-liquid transition in a two-dimensional system of millimeter-sized like-charged metal balls

Metal balls with a diameter of 1.59 mm, gently rubbed against a dielectric surface using a shaker, are seen to spontaneously exhibit a two-dimensional liquidlike order with macroscopic dimensions, viz., interball distances of several millimeters. This liquidlike order transforms to a gaslike order through coexistence upon decreasing the area fraction of the balls. The measured pair interaction of like-charged balls surprisingly exhibits a long-range attractive term analogous to that in charged colloids.     

On outstanding values in a sequence of random variables

Summary A sequence {X _n} of independent and identically distributed (i.i.d.) random variables is considered. Outstanding values in the sequence are those that strictly exceed values preceding them. Let L _n be the index of the n-th outstanding value. Limit theorems are given for the sequences and {L _n} and { _n} where _n=L_n–L_n–1. A characterization of the exponential distribution in terms of the sequence is also given.     

New Synthesis of α′‐Hydroxydienones

Herein, attempted oxidation of selected allenols with PCC affording α′‐hydroxydienones rather than simple oxidation products is described. The formation of the products observed is rationalized via a series of sigmatropic shifts, followed by hydrolysis.     

Photochemistry of 4-Pyrones in water. Formation of dihydroxycyclopentenones and furan derivatives

Irradiation of aqueous solutions of aikyl substituted 4-pyrones leads to the formation of dihydroxycyclopentenones. These primary products are also photolabile and in certain cases are photochemically converted to furan derivatives.     

Recent advances in heterogeneous TiO2 photocatalysis

Current progress in the area of photocatalysis is presented, particularly regarding technological applications. Highly efficient TiO₂ films on different substrates such as tile and glass have been developed for indoor environmental clean-up. TiO₂ films coated on SiO₂-precoated soda lime glass showed about 80% transparency and high photocatalytic activity towards the decomposition of thin oil films. A novel phenomenon, superhydrophilicity, has been observed on these transparent TiO₂ coatings. In addition, we have made use of a microelectrode system to monitor oxidation and reduction products separately. The mechanistic and kinetic aspects of TiO₂ photocatalysis are discussed.