DNP enhanced frequency-selective TEDOR experiments in bacteriorhodopsin

We describe a new approach to multiple ¹³C–¹⁵N distance measurements in uniformly labeled solids, frequency-selective (FS) TEDOR. The method shares features with FS-REDOR and ZF- and BASE-TEDOR, which also provide quantitative ¹⁵N–¹³C spectral assignments and distance measurements in U-[¹³C,¹⁵N] samples. To demonstrate the validity of the FS-TEDOR sequence, we measured distances in [U-¹³C,¹⁵N]-asparagine which are in good agreement with other methods. In addition, we integrate high frequency dynamic nuclear polarization (DNP) into the experimental protocol and use FS-TEDOR to record a resolved correlation spectrum of the Arg-¹³C_γ–¹⁵N_ε region in [U-¹³C,¹⁵N]-bacteriorhodopsin. We resolve six of the seven cross-peaks expected based on the primary sequence of this membrane protein.     

Synthesis of composite gold/tin-oxide nanoparticles by nano-soldering

Composite Au–SnO₂ nanoparticles (NPs) are synthesized by nano-soldering of pure Au and SnO₂ NPs. The multi-step process involves synthesis of pure Au and SnO₂ NPs separately by nanosecond pulse laser ablation of pure gold and pure tin targets in deionized water and post-ablation laser heating of mixed solution of Au colloidal and SnO₂ colloidal to form nanocomposite. Transmission Electron Microscopy (TEM) and High-Resolution Transmission Electron Microscopy (HRTEM) were used to study the effect of laser irradiation time on morphology of the composite Au–SnO₂ NPs. The spherical particles of 4 nm mean size were obtained for 5 min of post-laser heating. Increased mean size and elongated particles were observed on further laser heating. UV–vis spectra of Au–SnO₂ nanocomposites show red shift in the plasmon resonance absorption peak and line shape broadening with respect to pure Au NPs. The negative binding energy shift of Au 4f_7/2 peak observed in X-ray Photoelectron Spectra (XPS) indicates charge transfer in the nano-soldered Au–SnO₂ between gold and tin oxide and formation of soldered nanocomposite.     

Spectroscopic characterization of porous nanohydroxyapatite synthesized by a novel amino acid soft solution freezing method

In this paper, we have reported a novel method to synthesize nanoporous hydroxyapatite (HAP) powders by freezing organic–inorganic soft solutions. The formation of porous and crystalline HAP nanopowder was achieved via calcining the samples at 600 °C followed by sintering at temperatures ranging from 900 °C to 1100 °C. The samples were analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopic (SEM) techniques. The results showed the formation of a carbon free nanoporous hydroxyapatite powders due to the decomposition of organic template enclosing the precipitated HAP. It was also observed that the rapid grain growth with retainment of pores while the crystallinity of the HAP nanopowder increased with the increase in sintering temperature which is substantiated from the XRD and SEM results. Such organized porous materials can act as a better biomaterial for bone tissue engineering.     

Synthesis of modular building blocks using glycosyl phosphate donors for the construction of asymmetric N-glycans

Glycosyl phosphates are known as versatile donors for the synthesis of complex oligosaccharides both chemically and enzymatically. Herein, we report the stereoselective construction of modular building blocks for the synthesis of N-glycan using glycosyl phosphates as donors. We have synthesized four trisaccharide building blocks with orthogonal protecting groups, namely, Manβ2GlcNAc(OAc)₃β6GlcNAc (9), Manβ2GlcNAc-β6GlcNAc(OAc)₃ (15), Manβ2GlcNAc(OAc)₃β4GlcNAc (18) and Manβ2GlcNAcβ4GlcNAc(OAc) (22) for further selective elongation using glycosyltransferases. The glycosylation reaction using glycosyl phosphate was found to be high yielding with shorter reaction time. Initially, The phthalimide protected glucosamine donor was exploited to ensure the formation of β-glycosidic linkage and later converted to the N-acetyl group before the enzymatic synthesis. The selective deprotection of O-benzyl group was performed prior to enzymatic synthesis to avoid its negative interference.     

Enantioselective O-acetylcyanation/cyanoformylation of aldehydes using catalysts with built-in crown ether-like motif in chiral macrocyclic V(V) salen complexes

Chiral macrocyclic V(V) salen complexes 1a-f derived from macrocyclic ligands obtained by the reaction of 1R,2R-(−) diaminocyclohexane/(1R,2R)-(+)-1,2-diphenylethylenediamine with bis-aldehydes 2 and 3 were synthesized and used as efficient catalysts in asymmetric cyanation reactions. The V(V) catalysts demonstrated excellent performance (product yields and ees up to 99%) with potassium cyanide (KCN) and sodium cyanide (NaCN). The catalytic system also performed very well with a safer source of cyanide-ethyl cyanoformate to give cyanohydrin carbonates in excellent yield and ee (up to 97%). The V(V) macrocyclic salen complex 1b retained its performance at multi-gram level and was conveniently recycled for a number of times.     

Flexible organic crystals. Understanding the tractable co-existence of elastic and plastic bending

As an emerging class of flexible materials, mechanically bendable molecular crystals are broadly classified as elastic or plastic. Nevertheless, flexible organic crystals with mutually exclusive elastic and plastic traits, with contrasting structural requirements, co-existing under different stress settings are exceptional; hence, it is imperative to establish the concurring factors that beget this rare occurrence. We report a series of halogen-substituted benzil crystals showing elastic bending (within ∼2.45% strain), followed by elastoplastic deformation under ambient conditions. Under higher stress settings, they display exceptional plastic flexibility that one could bend, twist, or even coil around a capillary tube. X-ray diffraction, microscopy, and computational data reveal the microscopic and macroscopic basis for the exciting co-existence of elastic, elastoplastic, and plastic properties in the crystals. The layered molecular arrangement and the weak dispersive interactions sustaining the interlayer region provide considerable tolerance towards breaking and making upon engaging or releasing the external stress; it enables restoring the original state within the elastic strain. Comparative studies with oxalate compounds, wherein the twisted diketo moiety in benzil was replaced with a rigid and coplanar central oxalate moiety, enabled us to understand the effect of the anisotropy factor on the crystal packing induced by the C O⋯C tetral interactions. The enhanced anisotropy depreciated the elastic domain, making the oxalate crystals more prone to plastic deformation. Three-point bending experiments and the determined Young''s moduli further corroborate the co-existence of the elastic and plastic realm and highlight the critical role of the underlying structural elements that determine the elastic to plastic transformation. The work highlights the possible co-existence of orthogonal mechanical characteristics in molecular crystals and further construed the concurrent role of microscopic and macroscopic elements in attaining this exceptional mechanical trait.

Structural and mechanical studies of benzil and oxalate crystals highlight the microscopic and macroscopic basis for the co-existence of orthogonal mechanical traits and the elastic to plastic transformation under different stress settings.     

Ultra‐Low‐Field NMR Relaxation and Diffusion Measurements Using an Optical Magnetometer

Nuclear magnetic resonance (NMR) relaxometry and diffusometry are important tools for the characterization of heterogeneous materials and porous media, with applications including medical imaging, food characterization and oil‐well logging. These methods can be extremely effective in applications where high‐resolution NMR is either unnecessary, impractical, or both, as is the case in the emerging field of portable chemical characterization. Here, we present a proof‐of‐concept experiment demonstrating the use of high‐sensitivity optical magnetometers as detectors for ultra‐low‐field NMR relaxation and diffusion measurements.     

Enhanced photocatalytic degradation of nitrobenzene using MWCNT/β-ZnMoO4 composites under UV light emitting diodes (LEDs)

The β-ZnMoO₄/MWCNT nanocrystal composites were synthesized using hydrothermal method. The physicochemical properties such as structure, morphology and bandgap of synthesized photocatalysts were characterized using PXRD, UV-vis DRS, FTIR, FT-Raman, SEM and TEM analytical methods. PXRD pattern shows the peak shift in the case of synthesized ZnMoO₄/MWCNT which confirms the formation of nanocomposites. Moreover, the strong absorbance in UV region which was evidenced in UV-vis DRS spectra for all the case of synthesized ZnMoO₄ and ZnMoO₄/MWCNT composites. From the SEM and TEM images, the MWCNT was found to have adhered over the ZnMoO₄ nanocrystals. Compared to bare β-ZnMoO₄, β-ZnMoO₄/MWCNT nanocrystal composites exhibited significant higher photocatalytic activity under ultraviolet light emitting diodes (UVLEDs) irradiation for the degradation of nitrobenzene (NB; 2.606 × 10^?4 M). This may be due to the effective charge transfer in the composite and optimized electron hole pair recombination. The photocatalytic activity of the synthesized photocatalysts was also studied under visible LEDs and it is observed that the photocatalytic degradation of NB was 97%, 77%, 65% and 52% under the irradiation of UV, blue, green, and red LEDs respectively.     

Energy levels of hydrogenic impurity states in GaAs-Ga1−xAlxAs quantum well structures

Binding energies of the ground state and of four excited states of a hydrogenic impurity in quantum well structures consisting of a single slab of GaAs sandwiched between two semi-infinite slabs of Ga_1?xAl_xAs are calculated using a variational approach. The ground-state binding energy is calculated as a function of the barrier potential for a given size of the GaAs quantum well and is found to be linearly dependent on the inverse of the square root of the barrier potential except for very small potentials. The variation of the binding energies of all five states as a function of the size of the GaAs quantum well are also calculated and their behavior is discussed.