A structure determination protocol based on combined analysis of 3D-ED data,powder XRD data,solid-state NMR data and DFT-D calculations reveals the structure of a new polymorph of l-tyrosine

We report the crystal structure of a new polymorph of l-tyrosine (denoted the β polymorph), prepared by crystallization from the gas phase following vacuum sublimation. Structure determination was carried out by combined analysis of three-dimensional electron diffraction (3D-ED) data and powder X-ray diffraction (XRD) data. Specifically, 3D-ED data were required for reliable unit cell determination and space group assignment, with structure solution carried out independently from both 3D-ED data and powder XRD data, using the direct-space strategy for structure solution implemented using a genetic algorithm. Structure refinement was carried out both from powder XRD data, using the Rietveld profile refinement technique, and from 3D-ED data. The final refined structure was validated both by periodic DFT-D calculations, which confirm that the structure corresponds to an energy minimum on the energy landscape, and by the fact that the values of isotropic ¹³C NMR chemical shifts calculated for the crystal structure using DFT-D methodology are in good agreement with the experimental high-resolution solid-state ¹³C NMR spectrum. Based on DFT-D calculations using the PBE0-MBD method, the β polymorph is meta-stable with respect to the previously reported crystal structure of l-tyrosine (now denoted the α polymorph). Crystal structure prediction calculations using the AIRSS approach suggest that there are three other plausible crystalline polymorphs of l-tyrosine, with higher energy than the α and β polymorphs.

A new polymorph of l-tyrosine is reported, with the crystal structure determined by combined analysis of 3D-ED data and powder XRD data, augmented by information from periodic DFT-D calculations and solid-state ¹³C NMR data.     

Dioscin-Mediated Autophagy Alleviates MPP+-Induced Neuronal Degeneration: An In Vitro Parkinson’s Disease Model

Autophagy is a cellular homeostatic process by which cells degrade and recycle their malfunctioned contents, and impairment in this process could lead to Parkinson’s disease (PD) pathogenesis. Dioscin, a steroidal saponin, has induced autophagy in several cell lines and animal models. The role of dioscin-mediated autophagy in PD remains to be investigated. Therefore, this study aims to investigate the hypothesis that dioscin-regulated autophagy and autophagy-related (ATG) proteins could protect neuronal cells in PD via reducing apoptosis and enhancing neurogenesis. In this study, the 1-methyl-4-phenylpyridinium ion (MPP⁺) was used to induce neurotoxicity and impair autophagic flux in a human neuroblastoma cell line (SH-SY5Y). The result showed that dioscin pre-treatment counters MPP⁺-mediated autophagic flux impairment and alleviates MPP⁺-induced apoptosis by downregulating activated caspase-3 and BCL2 associated X, apoptosis regulator (Bax) expression while increasing B-cell lymphoma 2 (Bcl-2) expression. In addition, dioscin pre-treatment was found to increase neurotrophic factors and tyrosine hydroxylase expression, suggesting that dioscin could ameliorate MPP⁺-induced degeneration in dopaminergic neurons and benefit the PD model. To conclude, we showed dioscin’s neuroprotective activity in neuronal SH-SY5Y cells might be partly related to its autophagy induction and suppression of the mitochondrial apoptosis pathway.     

First observation of the P-wave spin-singlet bottomonium states hb(1P) and hb(2P)

We report the first observations of the spin-singlet bottomonium states h(b)(1P) and h(b)(2P). The states are produced in the reaction e(+)e(-)→h(b)(nP)π(+)π(-) using a 121.4 fb(-1) data sample collected at energies near the Υ(5S) resonance with the Belle detector at the KEKB asymmetric-energy e(+)e(-) collider. We determine M[h(b)(1P)]=(9898.2(-1.0-1.1)(+1.1+1.0)) MeV/c(2) and M[h(b)(2P)]=(10,259.8±0.6(-1.0)(+1.4)) MeV/c(2), which correspond to P-wave hyperfine splittings ΔM(HF)=(+1.7±1.5) and (+0.5(-1.2)(+1.6)) MeV/c(2), respectively. The significances of the h(b)(1P) and h(b)(2P) are 5.5σ and 11.2σ, respectively. We find that the production of the h(b)(1P) and h(b)(2P) is not suppressed relative to the production of the Υ(1S), Υ(2S), and Υ(3S).     

The work function of hydrothermally synthesized UO2 and the implications for semiconductor device fabrication

The photoelectric work function of nearly stoichiometric (111) and (100) hydrothermally grown UO₂ was measured to be 6.28 ± 0.36 eV and 5.80 ± 0.36 eV, respectively. Candidate metals for electrical contacts are identified for both rectifying and non‐rectifying contacts based on work function, lattice compatibility, and electrical conductivity.     

Radiation exposure to operator and patients during cardiac electrophysiology study,radiofrequency catheter ablation and cardiac device implantation procedures

The purpose of this study was to measure the radiation exposure to operator and patient during cardiac electrophysiology study, radiofrequency catheter ablation and cardiac device implantation procedures and to calculate the allowable number of cases per year. We carried out 9 electrophysiology studies, 40 radiofrequency catheter ablation and 11 cardiac device implantation procedures. To measure occupational radiation dose and dose–area product (DAP), 13 photoluminescence glass dosimeters were placed at eyes (inside and outside lead glass), thyroids (inside and outside thyroid collar), chest (inside and outside lead apron), wrists, genital of the operator (inside lead apron), and 6 of photoluminescence glass dosimeters were placed at eyes, thyroids, chest and genital of the patient. Exposure time and DAP values were 11.7?±?11.8?min and 23.2?±?26.2?Gy?cm² for electrophysiology study; 36.5?±?42.1?min and 822.4?±?125.5?Gy?cm² for radiofrequency catheter ablation; 16.2?±?9.3?min and 27.8?±?16.5?Gy?cm² for cardiac device implantation procedure, prospectively. 4591 electrophysiology studies can be conducted within the occupational exposure limit for the eyes (150?mSv), and 658-electrophysiology studies with radiofrequency catheter ablation can be carried out within the occupational exposure limit for the hands (500?mSv). 1654 cardiac device implantation procedure can be conducted within the occupational exposure limit for the eyes (150?mSv). The amounts of the operator and patient's radiation exposure were comparatively small. So, electrophysiology study, radio frequency catheter ablation and cardiac device implantation procedures are safe when performed with modern equipment and optimized protective radiation protect equipment.     

Clicked (AB)2C‐type miktoarm terpolymers: Synthesis,thermal and self‐assembly properties,and preparation of nanoporous materials

A well‐defined (PEO‐PS)₂‐PLA miktoarm terpolymer ( 1 ) was synthesized by stepwise click reactions of individually prepared poly(ethylene oxide) (PEO), polystyrene (PS, polymerized by atom transfer radical polymerization), and polylactide (PLA, polymerized by ring‐opening polymerization) blocks. As characterized by differential scanning calorimetry and small‐angle X‐ray scattering techniques, the terpolymer self‐assembled into a hexagonal columnar structure consisting of PLA/PEO cylindrical cores surrounded by PS chains. In contrast, the ion‐doped sample ( 1‐Li⁺ ) with lithium concentration per ethylene oxide = 0.2 exhibited a three‐phase lamellar structure, which was attributed to the microphase separation between PEO and PLA blocks and to the conformational stabilization of the longest PLA chain. The two‐phase columnar morphology before the ion doping was used to prepare a nanoporous material. PLA chains in the cylindrical core region were hydrolyzed by sodium hydroxide, producing nanopores with a pore diameter of about 14 nm. The resulted nanoporous material sank to the bottom in water, because of water‐compatible PEO chains on the walls. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Palladium‐catalyzed carbonylative cyclization of β‐bromo‐α,β‐unsaturated carboxylic acids with primary amines leading to N‐alkylmaleimides

Cyclic β‐bromo‐α,β‐unsaturated carboxylic acids are carbonylatively cyclized with primary amines under carbon monoxide pressure in MeCN in the presence of a catalytic amount of PdCl₂(PPh₃)₂ to give N‐alkylmaleimides. Copyright © 2012 John Wiley & Sons, Ltd.