[Evaluation of efficacy of Dihuang Baoyuan Granules for diabetes mellitus and composition and in vivo distribution analysis based on UHPLC-LTQ-Orbitrap MS].

Dihuang Baoyuan Granules is a prescription endorsed by HU Tianbao, a renowned and elderly Chinese medicine practitioner from Beijing, and has demonstrated definite clinical efficacy. The composition of this prescription is intricate as it includes 7 distinct herbal medicines. This study aims to analyze the chemical composition of Dihuang Baoyuan Granules, evaluate its efficacy in the treatment of diabetes and analyze the distribution of the drug components in the plasma, liver, and kidney after administration. The findings will serve as a reference for future research on pharmacodynamic substances of this prescription. UHPLC-LTQ-Orbitrap MS was employed to analyze the main chemical components of Dihuang Baoyuan Granules. A Waters ACQUITY Premier HSS T3 column(2.1 mm×100 mm, 1.8 µm) was used for chromatographic separation with 0.1% formic acid(A)-acetonitrile(B) as the mobile phases in a gradient elution at a flow rate of 0.3 mL·min~(-1). Electrospray ionization(ESI) source was used to acquire data in positive and negative ion modes. Furthermore, a rat model of diabetes mellitus was established by feeding with a high-sugar high-fat diet, and injection with streptozocin at a dose of 35 mg·kg~(-1), and the modeled rats were then administrated with Dihuang Baoyuan Granules. The fasting blood glucose, hemoglobin A1c, and other relevant indicators were measured, and the substances present in the plasma, liver, and kidney were identified. By reference to quasi-molecular ions, MS/MS fragment ions, MS spectra of reference substances, and compound information in available reports, 191 components were identified in Dihuang Baoyuan Granules, including 29 alkaloids, 24 flavonoids, 22 organic acids, 16 amino acids, 12 terpenes, 11 steroid saponins, 9 sugars, 8 phenylethanoid glycosides, 8 nucleosides, 2 phenylpropanoids, and 49 others compounds. Eighty-three chemical components were identified in rat plasma, 109 in the liver, and 98 in the kidney. Component identification and characterization of Dihuang Baoyuan Granules in vitro and in vivo provide efficacy information and guidance for the basic research on the pharmacodynamic substances and further clinical application of this prescription.

Enantioconvergent construction of stereogenic silicon via Lewis base-catalyzed dynamic kinetic silyletherification of racemic chlorosilanes.

Organosilanes possessing an enantioenriched stereogenic silicon center are important in many branches of chemistry, yet they remain challenging to synthesize in a practical and scalable way. Here we report a dynamic kinetic silyletherification process of racemic chlorosilanes with (S)-lactates using 4-aminopyridine as a Lewis base catalyst. This enantioconvergent approach asymmetrically constructs the stereogenic silicon center in a different manner from traditional resolution or desymmetrization. A range of silylethers have been prepared with high diastereoselectivity on up to 10 g-scale, allowing the practical synthesis of diverse enantioenriched organosilane analogs.

A Composite-Type MEMS Pirani Gauge for Wide Range and High Accuracy.

To achieve a wide range and high accuracy detection of the vacuum level, for example, in an encapsulated vacuum microcavity, a composite-type MEMS Pirani gauge has been designed and fabricated. The Pirani gauge consists of two gauges of different sizes connected in series, with one gauge having a larger heat-sensitive area and a larger air gap for extending the lower measurable limit of pressure (i.e., the high vacuum end) and the other gauge having a smaller heat-sensitive area and a smaller air gap for extending the upper measurable limit. The high-resistivity titanium metal was chosen as the thermistor; SiNx was chosen as the dielectric layer, considering the factors relevant to simulation and manufacturing. By simulation using COMSOL Multiphysics and NI Multisim, a range of measurement of 2 × 10-2 to 2 × 105 Pa and a sensitivity of 52.4 mV/lgPa were obtained in an N2 environment. The performance of the fabricated Pirani gauge was evaluated by using an in-house made vacuum test system. In the test, the actual points of measurement range from 6.6 × 10-2 to 1.12 × 105 Pa, and the highest sensitivity is up to 457.6 mV/lgPa. The experimental results are better in the range of measurement, sensitivity, and accuracy than the simulation results. The Pirani gauge proposed in this study is simple in structure, easy to manufacture, and suitable for integration with other MEMS devices in a microcavity to monitor the vacuum level therein.

Oil-Triggered and Template-Confined Dewetting for Facile and Low-Loss Sample Digitization.

This paper proposes a simple and robust method for spontaneously digitizing aqueous samples into a high-density microwell array. The method is based on an oil-triggered template-confined dewetting phenomenon. To realize the dewetting-induced sample digitization, an aqueous sample is first infused into a networked microwell array (NMA) through a pre-degassing-based self-pumping mechanism, and an immiscible oil phase is then applied over the surface of NMA chip to induce the templated dewetting. Due to periodic interfacial tension heterogeneity, such dewetting ruptures the sample at the thinnest parts (i.e., connection channels) and spontaneously splits the sample into droplets in individual microwells. Without requiring any complex pumping or valving systems, this method can discretize a sample into tens of thousands of addressable droplets in a matter of minutes with nearly 98% usage. To demonstrate the utility and universality of this self-digitization method, we exploited it to discretize samples into 40 233 wells for a digital PCR assay, the digital quantification of bacteria, the self-assembly of spherical colloidal photonic crystals, and the spherical crystallization of drugs. We believe this facile technique will provide a substantial benefit to many compartmentalized assays or syntheses where it is necessary to partition samples into a large number of small individual volumes.

A facile and rapid route to self-digitization of samples into a high density microwell array for digital bioassays.

Digital bioassays are powerful methods to detect rare analytes from complex mixtures and study the temporal processes of individual entities within biological systems. In digital bioassays, a crucial first step is the discretization of samples into a large number of identical independent partitions. Here, we developed a rapid and facile sample partitioning method for versatile digital bioassays. This method is based on a detachable self-digitization (DSD) chip which couples a reversible assembly configuration and a predegassing-based self-pumping mechanism to achieve an easy, fast, and large-scale sample partitioning. The DSD chip consists of a channel layer used for loading the sample and a microwell layer used for holding the sample partitions. Benefitting from its detachability, the chip avoids a lengthy oil flushing process used to remove the excess sample in loading channels and can compartmentalize a sample into more than 100,000 wells of picoliter volume with densities up to 14,000 wells/cm2 in less than 30 s. We also demonstrated the utility of the proposed method by applying it to digital PCR and digital microbial assays.

Electrical tension-triggered conversion of anaerobic to aerobic respiration of Shewanella putrefaciens CN32 cells while promoting biofilm growth in microbial fuel cells.

A global gene expression analysis of Shewanella putrefaciens CN32 cells nearby a nanostructured microbial anode reveals an electrical tension-triggered conversion of anaerobic respiration to aerobic respiration with increased excretion of flavin electron shuttles and cytochrome C proteins, which sheds light on the role of electric tension in cell organisms.

One-Pot Twofold Unsymmetrical C-Si Bond 2,6-Bifunctionalization of Arenes via Sequential [1,4]-Csp2 to O-Silyl Migration.

Twofold unsymmetrical C-Si bond bifunctionalization of 2,6-di(trimethylsilyl) benzyl alcohols has been achieved in one pot via sequential [1,4]-Csp2 to O-silyl migration. The hydroxyl group functions as an "on-off-on" switch to control two successive silyl migrations, and 4,7-dimethyl-o-phenanthroline ligand favors cleavage of the endocyclic C-Si bond. Diverse Csp3/Csp3 or Csp2/Csp3 electrophiles can be installed at the 2- and 6-positions. This approach was used to chemoselectively functionalize the three C-Si bonds of 2,4,6-tri(trimethylsilyl) benzyl alcohol, transforming it into isochroman derivatives. The approach even works as a five-component reaction to construct complex symmetric structures.

Rhodium-Catalyzed Reaction of Silacyclobutanes with Unactivated Alkynes to Afford Silacyclohexenes.

A Rh-catalyzed reaction of silacyclobutanes (SCBs) with unactivated alkynes has been developed to form silacyclohexenes with high chemoselectivity. Good enantioselectivity at the stereogenic silicon center was achieved using a chiral phosphoramidite ligand. The resulting silacyclohexenes are useful scaffolds for synthesizing structurally attractive silacyclic compounds.