Comparison and Characterization of Compounds with Antioxidant Activity in Lycium barbarum Using High‐Performance Thin Layer Chromatography Coupled with DPPH Bioautography and Tandem Mass Spectrometry

Methanol extracts from 50 batches of Lycium barbarum (L. barbarum, wolfberry) in China were compared and characterized using high‐performance thin‐layer chromatography coupled with 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) bioautography (HPTLC‐DPPH) and electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry (ESI‐Q‐TOF‐MS/MS), respectively. Results showed that similar components occupying the major antioxidant activity existed in L. barbarum collected from different origins. However, the average antioxidant capacities of methanol extracts of L. barbarum collected in Ningxia were significantly higher than those of Qinghai, Xinjiang, Inner Mongolia, and Gansu, which may contribute to rational use of L. barbarum in China. Furthermore, the chemical structure of compound with the highest antioxidant capacity was tentatively identified as 2‐O‐β‐d ‐glucopyranosyl‐l ‐ascorbic acid using ESI‐Q‐TOF‐MS/MS analysis, which possessed high potentials to be used as an antioxidant biomarker for the quality control of L. barbarum. Results are helpful for the bioactivity‐based quality control of L. barbarum, and beneficial for the improvement of their performance in functional/health foods area, suggesting that HPTLC‐DPPH bioautography with ESI‐Q‐TOF‐MS/MS could be used as a routine approach for quality control of antioxidant components in L. barbarum.     

Rapid Identification and Comparison of Compounds with Antioxidant Activity in Coreopsis tinctoria Herbal Tea by High‐Performance Thin‐Layer Chromatography Coupled with DPPH Bioautography and Densitometry

A simple and efficient method based on high‐performance thin‐layer chromatography coupled with 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) bioautography (HPTLC‐DPPH) was established for the screening and comparison of antioxidants in different parts of Coreopsis tinctoria herbal tea from different origins and other related herbal tea materials, which used Chrysanthemum morifolium cv. “Gongju” and “Hangju” in this study. Scanning densitometry after DPPH derivatization was applied for the determination of antioxidant capacities of isolated compounds in each sample. It is considered that ethanol extracts of C. tinctoria had stronger antioxidant activity and more characteristic bands than those of 2 compared samples, C. morifolium cv. “Gongju” and “Hangju.” Chemometric analysis results showed that the combination of hierarchical clustering analysis and principal component analysis based on determined antioxidant capacities could be used for the discrimination of different parts of C. tinctoria and C. morifolium. Results showed that 7 compounds made up the major contributions of antioxidant activity in C. tinctoria, including okanin, isookanin, marein, flavanomarein, 5,7,3′,5′‐tetrahydroxyflavanone‐7‐O‐glucoside, 3,5‐dicaffeoylquinic acid, and chlorogenic acid. Therefore, 7 compounds were identified as major antioxidant biomarkers for quality control of C. tinctoria. Results demonstrated that the established method could be applied for the identification of C. tinctoria, and were beneficial for the bioactivity‐based quality control of C. tinctoria.     

Low‐level PGAS computing on many‐core processors with TSHMEM

Diminishing returns from increased clock frequencies and instruction‐level parallelism have forced computer architects to adopt architectures that exploit wider parallelism through multiple processor cores. While emerging many‐core architectures have progressed at a remarkable rate, concerns arise regarding the performance and productivity of numerous parallel‐programming tools for application development. Development of parallel applications on many‐core processors often requires developers to familiarize themselves with unique characteristics of a target platform while attempting to maximize performance and maintain correctness of their applications. The family of partitioned global address space (PGAS) programming models comprises the current state of the art in balancing performance and programmability. One such PGAS approach is SHMEM, a lightweight, shared‐memory programming library that has demonstrated high performance and productivity potential for parallel‐computing systems with distributed‐memory architectures. In the paper, we present research, design, and analysis of a new SHMEM infrastructure specifically crafted for low‐level PGAS on modern and emerging many‐core processors featuring dozens of cores and more. Our approach (with a new library known as TSHMEM) is investigated and evaluated atop two generations of Tilera architectures, which are among the most sophisticated and scalable many‐core processors to date, and is intended to enable similar libraries atop other architectures now emerging. In developing TSHMEM, we explore design decisions and their impact on parallel performance for the Tilera TILE‐Gx and TILEPro many‐core architectures, and then evaluate the designs and algorithms within TSHMEM through microbenchmarking and applications studies with other communication libraries. Our results with barrier primitives provided by the Tilera libraries show dissimilar performance between the TILE‐Gx and TILEPro; therefore, TSHMEM's barrier design takes an alternative approach and leverages the on‐chip mesh network to provide consistent low‐latency performance. In addition, our experiments with TSHMEM show that naive collective algorithms consistently outperformed linear distributed collective algorithms when executed in an SMP‐centric environment. In leveraging these insights for the design of TSHMEM, our approach outperforms the OpenSHMEM reference implementation, achieves similar to positive performance over OpenMP and OSHMPI atop MPICH, and supports similar libraries in delivering high‐performance parallel computing to emerging many‐core systems. Copyright © 2015 John Wiley & Sons, Ltd.     

Cobalt-Containing Hyperbranched Poly(silylenearylene)s

A group of hyperbranched poly(silylenearylene)s are synthesized by homopolycyclotrimerizations of A₂-type silylenediynes. The polymers can be readily metallized by complexations of their periphery triple bonds with cobalt octacarbonyls Co₂(CO)₈. Pyrolysis of these organometallic polymers gives magnetic ceramics in good yields. Analyses by SEM, TEM, XPS, EDX, and XRD demonstrate that the ceramics comprise ferromagnetic Co and paramagnetic Co₂Si nanocrystallites wrapped by carboneous shell. The ceramics show high magnetic susceptibilities (M _s up to ~50 emu/g) and near-zero coercivity (H _c down to ~0.14 kOe), suggesting that they are good soft magnetic materials with low hysteresis loss. This article was to be included in the March issue of Volume 19, which was dedicated to Professor Takakazu Yamamoto. The journal editors sincerely apologize for the omission and delay in publication for which the authors and the guest editor bare no responsibility. M. Zeldin and A. S. Abd-El-Aziz, Editors.     

The characterization of thermoset cure behavior by differential scanning calorimetry. Part I: Isothermal and Dynamic Study

A study of the isothermal cure kinetics of an unsaturated polyester resin by differential scanning calorimetry is described. An autocatalyzed second order kinetic model is adopted to elucidate the cure reaction and also assess the kinetic parameters. The rate constant, the maximum cure rate, the extent of cure, and the degree of conversion at the maximum cure rate, all increase with increasing cure temperature, while the half-life and the time required to reach the maximum cure rate both decrease. Discrepancies between the experimental results and the predicted values of some of the kinetic parameters, especially at high degrees of conversion, are attributed to the highly different-controlled cure reaction following the gel point. The activation energy (E) and the pre-exponential factor (1n A) of the polyester cure reaction were estimated, using differential graphical techniques, to be 131 ± 4 kJ/mol and 39 ± 1 respectively. An ASTM method (E698) produces erroneously low values of the Arrhenius parameters, suggesting that the assumptions of the method may be overly simplified.     

The Tiny Companion Matters: The Important Role of Protons in Active Transports in Plants

In plants, the translocation of molecules, such as ions, metabolites, and hormones, between different subcellular compartments or different cells is achieved by transmembrane transporters, which play important roles in growth, development, and adaptation to the environment. To facilitate transport in a specific direction, active transporters that can translocate their substrates against the concentration gradient are needed. Examples of major active transporters in plants include ATP-binding cassette (ABC) transporters, multidrug and toxic compound extrusion (MATE) transporters, monosaccharide transporters (MSTs), sucrose transporters (SUTs), and amino acid transporters. Transport via ABC transporters is driven by ATP. The electrochemical gradient across the membrane energizes these secondary transporters. The pH in each cell and subcellular compartment is tightly regulated and yet highly dynamic, especially when under stress. Here, the effects of cellular and subcellular pH on the activities of ABC transporters, MATE transporters, MSTs, SUTs, and amino acid transporters will be discussed to enhance our understanding of their mechanics. The relation of the altered transporter activities to various biological processes of plants will also be addressed. Although most molecular transport research has focused on the substrate, the role of protons, the tiny counterparts of the substrate, should also not be ignored.     

Untersuchungen zur Thermischen Umsetzung von Phenylcyclopentan, -hexan, -heptan und -octan in der Gasphase

Studies on Thermal Conversion of Phenyleyclopentane, -hexane, -heptane, and -octane in the Gas Phase The title compounds were pyrolyzed from 700 to 780°C in a metallic laboratory tubular reactor in the presence of steam. The reaction products were analyzed by gas chromatography and by a combination of gas chromatography and mass spectrometry. From the phenylcyclanes tested, more than 65 hydrocarbons could be detected in the liquids, besides gaseous reaction products. In most cases unambiguous structures could be derived by using different analytical methods. As typical initial-step products phenylcyclenes, ω-phenyl-1-alkenes and 1-phenyl-1-alkenes are formed by dehydrogenation and isomerization of the title compounds. The detection of phenylalkenes corresponds well with the isomerization of unsubstituted cyclanes to the corresponding α-olefines described in former papers.     

Potassium ferrioxalate as a new inexpensive photochemical pyranometer for extensive field work

The feasibility of using a potassium ferioxalate actinometer as a photochemical pyranometer was studied. The preparation, exposure, and spectrophotometric analysis of the pyranometer cell are described. By calibrating it against a Yellot Mark IV solameter, linear correlations were obtained with respect to total insolation and time of exposure. The spectral response, the quantum yields at different wavelengths, the mechanism of photochemical reaction, and the conversion factor for converting the absorption reading into cal/cm²/min are discussed. The advantages of the new pyranometer are its low cost, simplicity of operation and calibration, high sensitivity, and high tolerance to field conditions. It is useful for mapping solar intensity distribution over a wide area.     

Expanding the Spectrum of Antibiotics Capable of Killing Multidrug-Resistant Staphylococcus aureus and Pseudomonas aeruginosa

Infections from antibiotic-resistant Staphylococcus aureus and Pseudomonas aeruginosa are a serious threat because reduced antibiotic efficacy complicates treatment decisions and prolongs the disease state in many patients. To expand the arsenal of treatments against antimicrobial-resistant (AMR) pathogens, 600-Da branched polyethylenimine (BPEI) can overcome antibiotic resistance mechanisms and potentiate β-lactam antibiotics against Gram-positive bacteria. BPEI binds cell-wall teichoic acids and disables resistance factors from penicillin binding proteins PBP2a and PBP4. This study describes a new mechanism of action for BPEI potentiation of antibiotics generally regarded as agents effective against Gram-positive pathogens but not Gram-negative bacteria. 600-Da BPEI is able to reduce the barriers to drug influx and facilitate the uptake of a non-β-lactam co-drug, erythromycin, which targets the intracellular machinery. Also, BPEI can suppress production of the cytokine interleukin IL-8 by human epithelial keratinocytes. This enables BPEI to function as a broad-spectrum antibiotic potentiator, and expands the opportunities to improve drug design, antibiotic development, and therapeutic approaches against pathogenic bacteria, especially for wound care.