Regulating the reduction reaction pathways via manipulating the solvation shell and donor number of the solvent in Li-CO2 chemistry.

Transforming CO2 into valuable chemicals is an inevitable trend in our current society. Among the viable end-uses of CO2, fixing CO2 as carbon or carbonates via Li-CO2 chemistry could be an efficient approach, and promising achievements have been obtained in catalyst design in the past. Even so, the critical role of anions/solvents in the formation of a robust solid electrolyte interphase (SEI) layer on cathodes and the solvation structure have never been investigated. Herein, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in two common solvents with various donor numbers (DN) have been introduced as ideal examples. The results indicate that the cells in dimethyl sulfoxide (DMSO)-based electrolytes with high DN possess a low proportion of solvent-separated ion pairs and contact ion pairs in electrolyte configuration, which are responsible for fast ion diffusion, high ionic conductivity, and small polarization. The 3 M DMSO cell delivered the lowest polarization of 1.3 V compared to all the tetraethylene glycol dimethyl ether (TEGDME)-based cells (about 1.7 V). In addition, the coordination of the O in the TFSI- anion to the central solvated Li+ ion was located at around 2 Å in the concentrated DMSO-based electrolytes, indicating that TFSI- anions could access the primary solvation sheath to form an LiF-rich SEI layer. This deeper understanding of the electrolyte solvent property for SEI formation and buried interface side reactions provides beneficial clues for future Li-CO2 battery development and electrolyte design.

Three-dimensional digital PCR through light-sheet imaging of optically cleared emulsion.

The realization of the vast potential of digital PCR (dPCR) to provide extremely accurate and sensitive measurements in the clinical setting has thus far been hindered by challenges such as assay robustness and high costs. Here we introduce a lossless and contamination-free dPCR technology, termed CLEAR-dPCR, which addresses these challenges by completing the dPCR sample preparation, PCR, and readout all in one tube. Optical clearing of the droplet dPCR emulsion was combined with emerging light-sheet fluorescence microscopy, to acquire a three-dimensional (3D) image of a half million droplets sealed in a tube in seconds. CLEAR-dPCR provides ultrahigh-throughput readout results in situ and fundamentally eliminates the possibility of either sample loss or contamination. This approach exhibits improved accuracy over existing dPCR platforms and enables a greatly increased dynamic range to be comparable to that of real-time quantitative PCR.

Stabilizing Cobalt-free Li-rich Layered Oxide Cathodes through Oxygen Lattice Regulation by Two-phase Ru Doping.

The application of Li-rich layered oxides is hindered by their dramatic capacity and voltage decay on cycling. This work comprehensively studies the mechanistic behaviour of cobalt-free Li1.2 Ni0.2 Mn0.6 O2 and demonstrates the positive impact of two-phase Ru doping. A mechanistic transition from the monoclinic to the hexagonal behaviour is found for the structural evolution of Li1.2 Ni0.2 Mn0.6 O2, and the improvement mechanism of Ru doping is understood using the combination of in operando and post-mortem synchrotron analyses. The two-phase Ru doping improves the structural reversibility in the first cycle and restrains structural degradation during cycling by stabilizing oxygen (O2- ) redox and reducing Mn reduction, thus enabling high structural stability, an extraordinarily stable voltage (decay rate <0.45 mV per cycle), and a high capacity-retention rate during long-term cycling. The understanding of the structure-function relationship of Li1.2 Ni0.2 Mn0.6 O2 sheds light on the selective doping strategy and rational materials design for better-performance Li-rich layered oxides.

Analysis of differences in physicochemical properties of different sorghum varieties and their influence on the selection of raw materials for winemaking.

Sorghum is one of the oldest crops in the world, an important grain crop in northern China, and a major raw material in the liquor-brewing industry. The physicochemical properties, cooking characteristics, and starch quality of sorghum seeds considerably affect the liquor-brewing process.To select suitable sorghums for liquor brewing and to determine the cooking characteristics and starch physicochemical properties of different sorghum varieties, 30 types of sorghum were used in this study, and their compositions were compared; six types of sorghum were further studied for their cooking quality and starch physicochemical and pasting characteristics. Gas chromatography time of flight mass spectrometry was used to analyse the cooking aroma of sorghum seeds. Additionally, scanning electron microscopy, a rapid visco analyser, and a differential calorimetric scanner were used to analyse the microstructure of sorghum starch, starch pasting characteristics, and thermodynamic properties, respectively. The results revealed that the water absorption and saccharification forces of glutinous sorghum were higher than those of japonica sorghum and that the aroma substances were significantly different. Glutinous sorghum starch had high crystallinity, freeze-thaw stability, and enthalpy, thus indicating its structural stability. This study provides a theoretical basis for the selection of wine raw materials in the future.

Catalytic role of in-situ formed C-N species for enhanced Li2CO3 decomposition.

Sluggish kinetics of the CO2 reduction/evolution reactions lead to the accumulation of Li2CO3 residuals and thus possible catalyst deactivation, which hinders the long-term cycling stability of Li-CO2 batteries. Apart from catalyst design, constructing a fluorinated solid-electrolyte interphase is a conventional strategy to minimize parasitic reactions and prolong cycle life. However, the catalytic effects of solid-electrolyte interphase components have been overlooked and remain unclear. Herein, we systematically regulate the compositions of solid-electrolyte interphase via tuning electrolyte solvation structures, anion coordination, and binding free energy between Li ion and anion. The cells exhibit distinct improvement in cycling performance with increasing content of C-N species in solid-electrolyte interphase layers. The enhancement originates from a catalytic effect towards accelerating the Li2CO3 formation/decomposition kinetics. Theoretical analysis reveals that C-N species provide strong adsorption sites and promote charge transfer from interface to *CO22- during discharge, and from Li2CO3 to C-N species during charge, thereby building a bidirectional fast-reacting bridge for CO2 reduction/evolution reactions. This finding enables us to design a C-N rich solid-electrolyte interphase via dual-salt electrolytes, improving cycle life of Li-CO2 batteries to twice that using traditional electrolytes. Our work provides an insight into interfacial design by tuning of catalytic properties towards CO2 reduction/evolution reactions.

General approach for preparing epidithiodioxopiperazines from trioxopiperazine precursors: enantioselective total syntheses of (+)- and (-)-gliocladine C, (+)-leptosin D, (+)-T988C, (+)-bionectin A, and (+)-gliocladin A.

A common strategy for preparing tryptophan-derived epidithiodioxopiperazine (ETP) natural products containing a hydroxyl substituent adjacent to a quaternary carbon stereocenter is reported. This strategy is exemplified by enantioselective total syntheses of four heptacyclic ETP natural products--gliocladine C (6), leptosin D (7), T988C (8), and bionectin A (9)--starting with the di-(tert-butoxycarbonyl) derivative 17 of the trioxopiperazine natural product gliocladin C, which is readily available by enantioselective chemical synthesis. In addition, total syntheses of the enantiomer of gliocladine C (ent-6) and gliocladin A (11), the di(methylthio) congener of bionectin A, are reported. These syntheses illustrate a synthetic strategy wherein diversity in the dioxopiperazine unit of ETP natural products is introduced at a late stage in a synthetic sequence. In vitro cytotoxicity of compounds in this series against invasive human prostrate (DU145) and melanoma (A2058) cancer cell lines is described and compared to that of chaetocin A (4).

Determination of decabrominated diphenyl ether in soils by Soxhlet extraction and high performance liquid chromatography.

This study described the development of a method based on Soxhlet extraction combining high performance liquid chromatography (Soxhlet-HPLC) for the accurate detection of BDE-209 in soils. The solvent effect of working standard solutions in HPLC was discussed. Results showed that 1:1 of methanol and acetone was the optimal condition which could totally dissolve the BDE-209 in environmental samples and avoid the decrease of the peak area and the peak deformation difference of BDE-209 in HPLC. The preliminary experiment was conducted on the configured grassland (1 µ g/g) to validate the method feasibility. The method produced reliable reproducibility, simulated soils (n = 4) RSD 1.0%, and was further verified by the analysis e-waste contaminated soils, RSD range 5.9-11.4%. The contamination level of BDE-209 in burning site was consistent with the previous study of Longtang town but lower than Guiyu town, and higher concentration of BDE-209 in paddy field mainly resulted from the long-standing disassembling area nearby. This accurate and fast method was successfully developed to extract and analyze BDE-209 in soil samples, showing its potential use for replacing GC to determinate BDE-209 in soil samples.

[Extracting municipal solid waste dumps based on high resolution images].

The dramatically increasing informal MSW dumps are endangering the urban environment. Remote sensing (RS) technologies are more efficient to monitor and manage municipal solid wastes (MSW) than traditional survey-based methods. In high spatial resolution remotely sensed images, these irregularly distributed dumps have complex compositions and strong heterogeneities, thus it is still hard to extract them automatically no matter the pixel-or object-based image analysis method is used. Therefore, based on the analysis of MSW characteristics, the present study develops a multiresolution strategy to extract MSW dumps by combining image features at both high resolution and resampled low heterogeneity images, while the high resolution images can provide detailed information and the low resolution images can suppress the strong heterogeneities of informal MSW dumps. Taking the QuickBird image covering part of Beijing as an example, this multi-resolution strategy produced a high accuracy (75%), indicating that this multi-resolution strategy is quite effective for extracting the open-air informal MSW dumps.

Revisiting the Role of Discharge Products in Li-CO2 Batteries.

Rechargeable lithium-carbon dioxide (Li-CO2 ) batteries are promising devices for CO2 recycling and energy storage. However, thermodynamically stable and electrically insulating discharge products (DPs) (e.g., Li2 CO3 ) deposited at cathodes require rigorous conditions for completed decomposition, resulting in large recharge polarization and poor battery reversibility. Although progress has been achieved in cathode design and electrolyte optimization, the significance of DPs is generally underestimated. Therefore, it is necessary to revisit the role of DPs in Li-CO2 batteries to boost overall battery performance. Here, a critical and systematic review of DPs in Li-CO2 batteries is reported for the first time. Fundamentals of reactions for formation and decomposition of DPs are appraised; impacts on battery performance including overpotential, capacity, and stability are demonstrated; and the necessity of discharge product management is highlighted. Practical in situ/operando technologies are assessed to characterize reaction intermediates and the corresponding DPs for mechanism investigation. Additionally, achievable control measures to boost the decomposition of DPs are evidenced to provide battery design principles and improve the battery performance. Findings from this work will deepen the understanding of electrochemistry of Li-CO2 batteries and promote practical applications.

Treatment of Aniline Wastewater by Membrane Distillation and Crystallization.

Aniline is a highly toxic organic pollutant with "carcinogenic, teratogenic and mutagenesis" characteristics. In the present paper, a membrane distillation and crystallization (MDCr) process was proposed to achieve zero liquid discharge (ZLD) of aniline wastewater. Hydrophobic polyvinylidene fluoride (PVDF) membranes were used in the membrane distillation (MD) process. The effects of the feed solution temperature and flow rate on the MD performance were investigated. The results showed that the flux of the MD process was up to 20 L·m-2·h-1 and the salt rejection was above 99% under the feeding condition of 60 °C and 500 mL/min. The effect of Fenton oxidation pretreatment on the removal rate of aniline in aniline wastewater was also investigated, and the possibility of realizing the ZLD of aniline wastewater in the MDCr process was verified.

The history, stereochemistry, ethnopharmacology and quality assessment of borneol.

ETHNOPHARMACOLOGICAL RELEVANCE: Borneol (BO) represents a global trade-driven spreading of ethnic medicine traceable to the classical age, and won its name specific to its original habitat "Borneo". BO shows broad spectral pharmacological effects, such as anti-inflammatory, analgesic, antipyretic, inducing resuscitation, and widely applied in the protection and treatment of cardiovascular and cerebrovascular diseases, used singly or mostly in compound formulae. AIM OF THE STUDY: Three stereoscopic configuration forms of BO, l-borneol (LB), d-borneol (DB), and dl-borneol (synthetic, SB), are formulated in broad spectral application, yet their diverse pharmacodynamic and pharmacokinetic properties caused by configurations, and accurate assay and quality assessment are often overlooked. A systematic review and analysis of lumped studies and applications is necessary to clarify the relationship between configuration and its original plant, analysis method, activity and side effect BO in order to guarantee the efficacy and safety during their application. MATERIALS AND METHODS: The public databases including PubMed, Web of Science, Google Scholar, China National Knowledge Infrastructure were referenced to summarize a comprehensive research and application data of BO published up to date. RESULTS: This review includes following sections: History and current status, Stereochemistry, Ethnopharmacology, and Quality assessment. In the section of history, the changes of the plant origins of the two isomeric forms of natural BO were described respectively, and the methods for synthetic racemate SB were also included. The section of stereochemistry deals with the stereoscopic structures, physical/chemical property, optical rotation of the three forms of BO, as well as the main related substances like isoborneol, obtained in SB via chemical transformation of camphor and turpentine oil. In the section of Ethnopharmacology, pharmacological activities and pharmacokinetics of different forms of BO were discussed. BO is usually used as an "adjuvant", by enhancing the permeability of the blood-brain barrier and intervene the ADME/T pathways of the other ingredients in the same formulation. In the section of quality assessment, the analytical methods, including chromatography, especially GC, and spectroscopy were addressed on the chiral separation of the coexisting enantiomers. CONCLUSIONS: This overview systematically summarized three forms of BO in terms of history, stereochemistry, ethnopharmacology, and quality assessment, which, hopefully, can provide valuable information and strategy for more reasonable application and development of the globally reputed ethnic medicine borneol with characteristics in stereochemistry.

Recent Progress and Future Advances on Aqueous Monovalent-Ion Batteries towards Safe and High-Power Energy Storage.

Aqueous monovalent-ion batteries have been rapidly developed recently as promising energy storage devices in large-scale energy storage systems owing to their fast charging capability and high power densities. In recent years, Prussian blue analogues, polyanion-type compounds, and layered oxides have been widely developed as cathodes for aqueous monovalent-ion batteries because of their low cost and high theoretical capacity. Furthermore, many design strategies have been proposed to expand their electrochemical stability window by reducing the amount of free water molecules and introducing an electrolyte addictive. This review highlights the advantages and drawbacks of cathode and anode materials, and summarizes the correlations between the various strategies and the electrochemical performance in terms of structural engineering, morphology control, elemental compositions, and interfacial design. Finally, this review can offer rational principles and potential future directions in the design of aqueous monovalent-ion batteries.

Enantioselective total synthesis of (+)-gliocladine C: convergent construction of cyclotryptamine-fused polyoxopiperazines and a general approach for preparing epidithiodioxopiperazines from trioxopiperazine precursors.

A concise second-generation total synthesis of the fungal-derived alkaloid (+)-gliocladin C (11) in 10 steps and 11% overall yield from isatin is reported. In addition, the epipolythiodioxopiperazine (ETP) natural product (+)-gliocladine C (6) has been prepared in six steps and 29% yield from the di-(tert-butoxycarbonyl) precursor of 11. The total synthesis of 6 constitutes the first total synthesis of an ETP natural product containing a hydroxyl substituent adjacent to a quaternary carbon stereocenter in the pyrrolidine ring.

Surfactant and oil formulations for monodisperse droplet emulsion PCR.

Emulsion PCR has become a popular and widely applied method in biological research and clinical diagnostics to provide evenly amplified products and perform highly quantitative counting of target sequences. However, there is still a lack of information to support further development of appropriate water-in-oil emulsion formulations, which need to be both thermally and mechanically stable for digital amplification reactions. Here, we present a systematic survey of the oil and surfactant components of stable monodisperse w/o emulsions suitable for use with our previously developed micro-capillary array (MiCA)-based centrifugal emulsion generation method. Our findings show that a binary formula consisting of isopropyl palmitate and a silicone copolymer demonstrated the best performance, and provided a general guideline for the development of emulsion systems for digital PCR and emulsion amplification applications.

High-throughput single-cell whole-genome amplification through centrifugal emulsification and eMDA.

Single-cell whole-genome sequencing (scWGS) is mainly used to probe intercellular genomic variations, focusing on the copy number variations or alterations and the single-nucleotide variations (SNVs) occurring within single cells. Single-cell whole-genome amplification (scWGA) needs to be applied before scWGS but is challenging due to the low copy number of DNA. Besides, many genomic variations are rare within a population of cells, so the throughput of currently available scWGA methods is far from satisfactory. Here, we integrate a one-step micro-capillary array (MiCA)-based centrifugal droplet generation technique with emulsion multiple displacement amplification (eMDA) and demonstrate a high-throughput scWGA method, MiCA-eMDA. MiCA-eMDA increases the single-run throughput of scWGA to a few dozen, and enables the assessment of copy number variations and alterations at 50-kb resolution. Downstream target enrichment further enables the detection of SNVs with 20% allele drop-out.

Centrifugal micro-channel array droplet generation for highly parallel digital PCR.

Stable water-in-oil emulsion is essential to digital PCR and many other bioanalytical reactions that employ droplets as microreactors. We developed a novel technology to produce monodisperse emulsion droplets with high efficiency and high throughput using a bench-top centrifuge. Upon centrifugal spinning, the continuous aqueous phase is dispersed into monodisperse droplet jets in air through a micro-channel array (MiCA) and then submerged into oil as a stable emulsion. We performed dPCR reactions with a high dynamic range through the MiCA approach, and demonstrated that this cost-effective method not only eliminates the usage of complex microfluidic devices and control systems, but also greatly suppresses the loss of materials and cross-contamination. MiCA-enabled highly parallel emulsion generation combines both easiness and robustness of picoliter droplet production, and breaks the technical challenges by using conventional lab equipment and supplies.

miR-200c enhances sensitivity of drug-resistant non-small cell lung cancer to gefitinib by suppression of PI3K/Akt signaling pathway and inhibites cell migration via targeting ZEB1.

Acquired resistance to epidermal growth factor receptor tyrosine kinase inhibitors (EGFR-TKIs) is a major obstacle in the treatment of non-small cell lung cancer (NSCLC) patients. We explored the role of miR-200c in modulating the sensitivity of gefitinib-resistant NSCLC cells and examined the underlying mechanism. The gefitinib-resistant cell line PC-9-ZD and its parental PC-9 cells were used. Growth inhibition was detected by MTT assay. The cell apoptosis was detected by Annexin V/PI assay. Cell migration was assessed by wound-healing assay. RT-PCR was used to detected levels of miR-200c and ZEB1. The PI3k, Bcl-2, Bax, caspase-3 and ZEB1 protein expression were detected using Western blot analysis, and TUNEL, Immunohistochemistry for xenograft model. PC-9-ZD cells had low level of miR-200c expression compared to its parental PC-9 cells. PC-9-ZD cells with miR-200c transfection were more sensitive to gefitinib treatment. Apoptosis induced by gefitinib was observed in PC-9-ZD cells with miR-200c transfection significantly. The levels of phosphorylated-Akt and Bcl-2 expression decreased and levels of Bax and Caspase-3 expression increased in PC-9-ZD cells with miR-200c transfection. Cell migration was inhibited and ZEB1 mRNA level and protein expression were significantly decreased in PC-9-ZD cells with miR-200c transfection. Further in gefitinib resistant xenograft model, miR-200c enhanced sensitivity of gefitinib and induced apoptosis significantly through PI3K/Akt signaling pathway and targeting ZEB1. These results provided insights into the functions of miR-200c and offered an alternate approach in treating gefitinib-resistance NSCLC.

Spinning micropipette liquid emulsion generator for single cell whole genome amplification.

Many on-chip approaches that use flow-focusing to pinch the continuous aqueous phase into droplets have become the most popular methods that provide monodisperse emulsion droplets. However, not every lab can easily adapt a microfluidic workflow into their familiar protocols. We develop an off-chip approach, spinning micro-pipette liquid emulsion (SiMPLE) generator, to produce highly stable monodisperse water-in-oil emulsions using a moving micropipette to disperse the aqueous phase in an oil-filled microcentrifuge tube. This method provides a simple way to produce picoliter-size droplets in situ with no dead volume during emulsification. With SiMPLE, single-cell emulsion whole genome amplification was performed to demonstrate that this novel method can seamlessly be integrated with experimental operations and supplies that most researchers are familiar with. The SiMPLE generator has effectively lowered the technical difficulties in applications relying on emulsion droplets.