UPLC–ESI–Q-TOF–MS/MS analysis of anticancer fractions from Ophiocordyceps xuefengensis and Ophiocordyceps sinensis

Ophiocordyceps xuefengensis (O. xuefengensis), a new species of caterpillar fungus, has been identified as the sister taxon of Ophiocordyceps sinensis (O. sinensis). The aims of the present study are to evaluate the anticancer activity and to qualitatively analyze the potential bioactive chemical constituents of O. xuefengensis and O. sinensis, comparatively. An MTT assay was used to evaluate the in vitro anticancer activities of different fractions from O. xuefengensis and O. sinensis. The results show that ethyl acetate fractions of O. xuefengensis and O. sinensis have significant in vitro anticancer activity. These two bioactive fractions were analyzed by ultra-performance liquid chromatography–electrospray ionization with quadrupole–time of flight tandem mass spectrometry technology. A total of 82 compounds and 101 compounds were identified or tentatively characterized in the bioactive fractions of O. xuefengensis and O. sinensis, respectively. Among these compounds, 68 existed in both O. xuefengensis and O. sinensis. A total of 67 compounds were reported in O. xuefengensis and 8 compounds were reported in caterpillar fungus for the first time. This is the first detailed comparative analysis of the in vitro anticancer activity and chemical ingredients between O. xuefengensis and O. sinensis. The application of this work will provide reliable fundamental pharmacological substances for the use of O. xuefengensis by Yao people.     

Decorating Mn3O4 nanoparticle on NiO nanoflake arrays for high-performance electrochemical biosensors

Journal of Solid State Electrochemistry - Substrate materials play a significant role in the improvement of electrochemical biosensors. In the present work, NiO nanoflake arrays were fully and...     

An ab initio-based global potential energy surface for the SH3 system and full-dimensional state-to-state quantum dynamics study for the H2 + HS → H2S + H reaction

An accurate potential energy surface for the ground electronic state of SH₃ system has been constructed with 41,882 high level ab initio energy points and the neural network fitting method. The time-dependent wave packet method has been used to calculate the first state-to-state differential cross sections for the title reaction up to 1.2 eV in full dimensions, based on the reactant–product decoupling scheme. It is found that the majority of H₂S are produced in the ground vibrational state, with a large fraction of available energy for the reaction ending up as product translational motion. The differential cross sections at the threshold energy are dominated by a very narrow peak in the backward direction. With the increase of collision energy, the width of the angular distribution increases considerably, which is a typical feature of a direct reaction via abstract mechanism, similar to the H₂ + OH → H₂O + H reaction. © 2018 Wiley Periodicals, Inc.     

Nanoporous Gold Embedded ZIF Composite for Enhanced Electrochemical Nitrogen Fixation

The electrochemical nitrogen reduction reaction (NRR) offers an energy‐saving and environmentally friendly approach to produce ammonia under ambient conditions. However, traditional catalysts have extremely poor NRR performances because of their low activity and the competitive hydrogen evolution reaction. The high catalytic activity of nanoporous gold (NPG) and the hydrophobicity and molecular concentrating effect of the zeolitic imidazolate framework‐8 (ZIF‐8) were incorporated in the NPG@ZIF‐8 nanocomposite so that the ZIF‐8 shell could weaken hydrogen evolution and retard reactant diffusion. A highest Faradaic efficiency of 44 % and an excellent rate of ammonia production of (28.7±0.9) μg h^?1 cm^?2 were achieved, which are superior to traditional gold nanoparticles and NPG. Moreover, the composite catalyst shows high electrochemical stability and selectivity (98 %). The superior NRR performance makes NPG@ZIF‐8 one of the most promising water‐based NRR electrocatalysts for ammonia production.     

Scaled‐Up Synthesis of Amorphous NiFeMo Oxides and Their Rapid Surface Reconstruction for Superior Oxygen Evolution Catalysis

The anode oxygen evolution reaction (OER) is known to largely limit the efficiency of electrolyzers owing to its sluggish kinetics. While crystalline metal oxides are promising as OER catalysts, their amorphous phases also show high activities. Efforts to produce amorphous metal oxides have progressed slowly, and how an amorphous structure benefits the catalytic performances remains elusive. Now the first scalable synthesis of amorphous NiFeMo oxide (up to 515 g in one batch) is presented with homogeneous elemental distribution via a facile supersaturated co‐precipitation method. In contrast to its crystalline counterpart, amorphous NiFeMo oxide undergoes a faster surface self‐reconstruction process during OER, forming a metal oxy(hydroxide) active layer with rich oxygen vacancies, leading to superior OER activity (280 mV overpotential at 10 mA cm^?2 in 0.1 m KOH). This opens up the potential of fast, facile, and scale‐up production of amorphous metal oxides for high‐performance OER catalysts.     

Structure transition and photoluminescence of CdS/Si nanoheterostructure array on thermal annealing

CdS/Si heterojunctions have been prepared through growing CdS nanocrystallites (nc-CdS) on the silicon nanoporous pillar array (Si-NPA) by the chemical bath deposition method. Cadmium nanocrystallites (nc-Cd) have been observed and ascribed to the reducibility of Si-NPA. The reason for the appearance of CdO is indistinct and the related work will be done in the future. The blue, green and red emissions are ascribed to the silicon oxide layer, band gap of nc-CdS and the sulphur vacancies, respectively. Redshift and blueshift with the annealing temperature about green emissions are contributed to quantum size effect and the structure transition from nc-Cd to CdO. It is beneficial for investigating the structures and defects to the application of CdS/Si in the optoelectronic field.     

Disulfide‐Unit Conjugation Enables Ultrafast Cytosolic Internalization of Antisense DNA and siRNA

Development of intracellular delivery methods for antisense DNA and siRNA is important. Previously reported methods using liposomes or receptor‐ligands take several hours or more to deliver oligonucleotides to the cytoplasm due to their retention in endosomes. Oligonucleotides modified with low molecular weight disulfide units at a terminus reach the cytoplasm 10 minutes after administration to cultured cells. This rapid cytoplasmic internalization of disulfide‐modified oligonucleotides suggests the existence of an uptake pathway other than endocytosis. Mechanistic analysis revealed that the modified oligonucleotides are efficiently internalized into the cytoplasm through disulfide exchange reactions with the thiol groups on the cellular surface. This approach solves several critical problems with the currently available methods for enhancing cellular uptake of oligonucleotides and may be an effective approach in the medicinal application of antisense DNA and siRNA.     

Crossed Beam Study on the F+D2→DF+D Reaction at Hyperthermal Collision Energy of 23.84 kJ/mol

We presented an experimental apparatus combining the H-atom Rydberg tagging time-of-flight technique and the laser detonation source for studying crossed beam reactions athyperthermal collision energies. The preliminary study of the F+D₂→DF+D reaction at hyperthermal collision energy of 23.84 kJ/mol was performed. Two beam sources were used in this study: one is the hyperthermal F beam source produced by a laser detonation process, and the other is D₂ beam source generated by liquid-N₂ cooled pulsed valve. Vibrational state-resolved di erential cross sections (DCSs) of product for the title reaction were determined. From the product vibrational state-resolved DCS, it can be concluded that products DF(v'=0, 1, 2, 3) are predominantly distributed in the sideway and backward scattering directions at this collision energy. However, the highest vibrational excited product DF(v'=4), is clearly peaked in the forward direction. The probable dynamical origins for these forward scattering products were analyzed and discussed.     

General π‐Electron‐Assisted Strategy for Ir,Pt, Ru,Pd, Fe,Ni Single‐Atom Electrocatalysts with Bifunctional Active Sites for Highly Efficient Water Splitting

Both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) are crucial to water splitting, but require alternative active sites. Now, a general π‐electron‐assisted strategy to anchor single‐atom sites (M=Ir, Pt, Ru, Pd, Fe, Ni) on a heterogeneous support is reported. The M atoms can simultaneously anchor on two distinct domains of the hybrid support, four‐fold N/C atoms (M@NC), and centers of Co octahedra (M@Co), which are expected to serve as bifunctional electrocatalysts towards the HER and the OER. The Ir catalyst exhibits the best water‐splitting performance, showing a low applied potential of 1.603 V to achieve 10 mA cm^?2 in 1.0 m KOH solution with cycling over 5 h. DFT calculations indicate that the Ir@Co (Ir) sites can accelerate the OER, while the Ir@NC₃ sites are responsible for the enhanced HER, clarifying the unprecedented performance of this bifunctional catalyst towards full water splitting.     

Comparative analysis of the main active components and hypoglycemic effects after the compatibility of Scutellariae Radix and Coptidis Rhizoma

In this study, a rapid and highly sensitive ultra high performance liquid chromatography with triple quadrupole mass spectrometry method with the mobile phase of acetonitrile and 0.1% aqueous formic acid was established and successfully applied to comparatively analyze main active components after their compatibility. Besides, the effects of Scutellariae Radix, Coptidis Rhizoma and combined extracts on type 2 diabetic rats induced by high‐fat diet along with low dose of streptozocin were investigated. Under the optimized chromatographic conditions, good separation of seven target components was achieved within 12 min. All calibration curves exhibited good linearity (R² ≥ 0.999). The relative standard deviation of precision, repeatability and stability varied from 0.69 to 2.23, 0.98 to 2.56, and 0.92 to 2.57%, respectively. The recovery ranged from 91.11 to 105.35%. The contents of seven active components were notably reduced after compatibility; however, the hypoglycemic effect of combined extracts was stronger than single drug by decreasing the activities of fructose‐1,6‐bisphosphatase, glucose 6‐phosphatase, phosphoenolpyruvate carboxykinase and increasing the activities of glucokinase, phosphofructokinase, pyruvate kinase. Accordingly, the established analytical method was accurate and sensitive enough for quantitative evaluation of seven investigated compounds. Moreover, the combined extract had definite effects on type 2 diabetes through multiple components against multiple targets.