Borohydride Compounds Catalyze the Selective 4e- Reduction of CO2 with 9-BBN.

The selective double hydroboration of CO2 into bis(boryl)acetal (BBA) is a challenging yet appealing reduction process since BBA can be used as a versatile C1 and Cn sources for the synthesis of value-added products. In the present study, we demonstrate that simple borohydride compounds are efficient and selective catalysts for the synthesis of BBA when using 9-borabicyclo(3.3.1)nonane (9-BBN) as a reductant. The experimental and theoretical investigations show that while the borohydride species catalyzes the first reduction step of CO2 into formoxyborane (2e- reduction intermediate), the observed 4e- reduction selectivity is mostly due to the ability of 9-BBN to reduce the formoxyborane into BBA without a catalyst. Notably, 0.2 mol % of LiH2BBN catalyzed the hydroboration of CO2 with 9-BBN as a reductant into the corresponding BBA in 77% yield with TON and TOF of 385 and 196 h-1, respectively. The simplicity of borohydride contrasts with the more elaborate catalytic systems used so far for the 4e- reduction of CO2.

Theoretical insights on boron reducing agent for the reduction of carbonyl compounds.

In this perspective, we present computational progress in the reduction of carbonyl compounds using boron reducing agents, such as L·BH3, HBcat, HBpin, and 9-BBN. For the catalytic reduction reactions, establishing a catalytic mechanism will provide an important theoretical basis for the improvement of a more efficient combination of reducing agents and catalysts. Current computational studies reveal that the mechanisms of reactions are different due to the various combinations of electrophilic boron reducing agents and catalysts (transition-metal catalyst, main group metal catalysts, and metal-free frustrated Lewis pair). We discuss the role of boron reducing agents on the efficiency of reactions and believe that possible Lewis acid-base interaction between Bδ+, Mδ+ and Oδ-, Hδ- existing in boron reducing agent, unsaturated substances, and catalyst should be considered fully. A tentative outlook on future opportunities of this research field is proposed.

A reversible conductivity modulation of azobenzene-based ionic liquids in aqueous solutions using UV/vis light.

Photo-induced conductivity modulation of stimuli-responsive materials is of great importance from the viewpoint of fundamental research and technology. In this work, 5 new kinds of azobenzene-based photo-responsive ionic liquids were synthesized and characterized, and UV/vis light modulation of their conductivity was investigated in an aqueous solution. The factors affecting the conductivity modulation of the photo-responsive fluids, such as photo-isomerization efficiency, photo-regulation aggregation, concentration and chemical structure of the ionic liquids, were examined systematically. It was found that the conductivity of the ionic liquids in water exhibited a significant increase upon UV light irradiation and the ionic liquids with a shorter alkyl spacer in the cation showed a more remarkable photo-induced conductivity enhancement with a maximum increase of 150%. In addition, the solution conductivity was restored (or very close) to the initial value upon an alternative irradiation with visible light. Thus, the solution conductivity can be modulated using alternative irradiation with UV and visible light. Although the reversible photo-isomerization of the azobenzene group under UV/vis irradiation is the origin of the conductivity modulation, the photo-regulated aggregation of the ionic liquid in water is indispensable for the maximum degree of conductivity modulation because UV irradiation can weaken, even break the aggregated cis-isomers of the ionic liquids in an aqueous solution.

Inhibition of DIXDC1 by microRNA-1271 suppresses the proliferation and invasion of prostate cancer cells.

Disheveled-Axin domain containing 1 (DIXDC1) is involved in the development and progression of multiple cancers. However, the function significance of DIXDC1 in prostate cancer remains unclear. In this study, we investigated the function of DIXDC1 in prostate cancer and the regulation of DIXDC1 by microRNAs (miRNAs). We found that DIXDC1 was highly expressed in prostate cancer cells. Knockdown of DIXDC1 by small interfering RNAs markedly suppressed proliferation, invasion and Wnt signaling in prostate cancer cells. DIXDC1 was identified as a target gene of miR-1271 by bioinformatics analysis, dual-luciferase reporter assay, real-time quantitative polymerase chain reaction and Western blot analysis. Furthermore, DIXDC1 expression was inversely correlated with miR-1271 expression in prostate cancer tissues. The overexpression of miR-1271 significantly inhibited proliferation, invasion and Wnt signaling in prostate cancer cells. However, the inhibition of miR-1271 exhibits the opposite effects. Moreover, the overexpression of DIXDC1 significantly reversed the inhibitory effects of miR-1271 overexpression. Taken together, our results suggest that DIXDC1 plays an important role in regulating prostate cancer cell proliferation and invasion. Targeting DIXDC1 by miR-1271 may be a promising therapeutic strategy for prostate cancer.

Highly Efficient NiS/Ni(OH)x Heterogeneous Structure Electrocatalyst with Regenerative Oxygen Vacancies for Oxygen Evolution Reaction.

Developing low-cost and highly efficient electrocatalysts toward oxygen evolution reaction (OER) is of vital significance for electrochemical water splitting. Herein, we fabricate a heterostructure NiS/Ni(OH)x electrocatalyst (Ni-S-n) with regenerative oxygen vacancies via electro-deposition on nickel foam (NF) followed by a facile NaBH4 reduction. The resulting Ni-S-5 catalyst with appropriate amount of oxygen vacancies (Ovs) exhibits extraordinary activity for alkaline OER with overpotential of 142 mV and 248 mV to reach the current density of 10 mA cm-2 and 100 mA cm-2, respectively. This catalyst also shows remarkable durability with 40 h. After the stability test, the excellent OER performance is well recovered by regenerating the surface oxygen vacancies (Ovs) significantly with additional NaBH4 reduction. The Ni-S-5 catalyst still displays good activity even after repeating it three times (180 h). The surface oxygen vacancies act as vital active sites for OER. A mechanism of Ovs species transformation and regeneration based on the Ni-S-5 catalyst is proposed, which provides a new direction for exploring ultrastable and efficient OER electrocatalysts with renewable active species.

Computational study on the mechanism of hydroboration of CO2 catalysed by POCOP pincer nickel thiolate complexes: concerted catalysis and hydride transfer by a shuttle.

Hydroboration of carbon dioxide (CO2) catalysed by bis(phosphinite) (POCOP) pincer nickel complexes is among the most efficient homogeneous processes for the reduction of CO2 to the methanol level. Although both POCOP pincer nickel hydride and thiolate complexes are effective catalysts, the latter is far more effective under the same conditions. The mechanism for nickel hydride complexes catalysed reactions is well-established. However, that for nickel thiolate complex catalysed reactions remains elusive. In this work, the mechanism for the reduction of CO2 catalysed by POCOP pincer nickel thiolate complexes was investigated using density functional theory. The calculated results indicated that the reaction occurs via a concerted catalytic process involving two active species and the hydride is transferred by a shuttle species. Specifically, the reaction proceeds through four cycles: formation of two active species (cycle I) followed by further reaction of these two species to form a hydride transfer shuttle which is responsible for hydride transfers CO2→HCOOBcat (cycle II), HCOOBcat→CH2O (cycle III) and CH2O→catBOCH3 (cycle IV). The calculated mechanism is in good agreement with the experimental observation that the reaction is exothermic with simultaneous HBcat degradation.

Synthesis of a Stable Solid Acid Catalyst from Chloromethyl Polystyrene through a Simple Sulfonation for Pretreatment of Lignocellulose in Aqueous Solution.

A stable solid acid catalyst, SCPR140-1, was synthesized from chloromethyl polystyrene resin (CPR) and used for catalytic pretreatment of corncob in aqueous solution. Under the optimized pretreatment condition, 73.07 % of xylose was directly obtained, and the enzymatic digestibility of treated residue reached up to 94.65 %, indicating that the SCPR140-1 had high selectivity for xylose production and effectively deconstructed the structure of corncob. The -CH2 Cl group of CPR was substituted by -SO3 H through the sulfonation, and the -SO3 H was stably bound on the catalyst during the pretreatment process. Compared with other similar reports, the SCPR140-1 was not only synthesized through a simpler process but also had a more stable catalytic activity during multiple recycling runs.

Torrefaction of herbal medicine wastes: Characterization of the physicochemical properties and combustion behaviors.

To explore the feasibility of using herbal medicine waste (HMW) as solid fuel, HMW was torrefied under different temperatures and atmospheres. The physicochemical properties and combustion behaviors of the torrefied HMW were investigated. Temperature was found to be the most influential factor affecting the torrefaction. Torrefaction improved the hydrophobicity of HMW and decreased the equilibrated moisture uptake from 24.48(0.083) % to 15.22(0.054) %. The HMW samples torrefied under different conditions are easy to ignite. The comprehensive combustibility index (S) of the torrefied HMW increased by 3-5 folds compared to that of the raw sample. In general, the HMW torrefied under lower temperatures and under CO2 and O2 have better flammability. The present results revealed that the torrefied HMW exhibited good combustion characteristics and can thus be used for solid fuel production, such as fuels for co-combustion or raw materials for pelletization.

Effects of vitamin D combined with pioglitazone hydrochloride on bone mineral density and bone metabolism in Type 2 diabetic nephropathy.

The study aims to investigate the effect of vitamin D (VD) combined with pioglitazone hydrochloride (PIO) on bone mineral density (BMD) and bone metabolism in patients with Type 2 diabetic nephropathy (T2DN). T2DN patients were selected and assigned into mild, moderate, and severe groups. In each group, three therapy regimens (VD, PIO, and VD plus PIO) were administered. X-ray absorptiometry was used to measure BMD. Intact parathyroid hormone (iPTH) and 25-hydroxyvitamin D3 (25-OH-VD3) were measured by chemiluminescence meter. ELISA was applied to detect levels of osteoprotegerin (OPG), bone gla protein (BGP), C-terminal telopeptides of type I collagen (ß-CTX), procollagen type I N-propeptide (PINP), pyridinoline (Pyr), and deoxypyridinoline (D-Pyr). Compared with the mild group, T2DN patients in the moderate and severe groups had longer course of disease and higher levels of total cholesterol (TC), triglyceride (TG), serum phosphorus, fasting plasma glucose (FPG), glycosylated hemoglobin (HbAlc) and creatine (Cr), and lower blood calcium. The BMD in different parts increased among the mild, moderate, and severe groups, and the highest BMD was found after VD plus PIO treatment. OPG, iPTH, BGP, ß-CTX, Pyr/Cr, and D-Pyr/Cr levels were reduced, while 25-OH-VD3 and PINP levels were elevated among three groups after different treatments, and the most obvious change was observed after VD plus PIO treatment. Our findings indicate that VD combined with PIO may be more effective in improving BMD and bone metabolism than VD or PIO alone in the treatment of T2DN patients, especially for T2DN patients with mild disease.

Suppression of forkhead box Q1 by microRNA-506 represses the proliferation and epithelial-mesenchymal transition of cervical cancer cells.

MicroRNAs (miRNAs) play a pivotal role in cancer progression and development, representing novel therapeutic tools for cancer therapy. Forkhead box Q1 (FOXQ1) functions as an oncogene in various cancer types. However, the functional significance of FOXQ1 in cervical cancer remains unknown. In this study, we investigated the biological function of FOXQ1 in cervical cancer and tested whether or not FOXQ1 can be targeted and regulated by specific miRNAs. We found that FOXQ1 was highly expressed in cervical cancer cell lines. Knockdown of FOXQ1 by small interfering RNA (siRNA) significantly suppressed the proliferation and epithelial-mesenchymal transition (EMT) of cervical cancer cells. FOXQ1 was predicted as a target gene of microRNA-506 (miR-506), and this prediction was validated by dual-luciferase reporter assay. Quantitative real-time PCR and western blot analyses demonstrated that mRNA and protein expression was negatively regulated by miR-506. The expression of miR-506 was downregulated in cervical cancer tissues, and miR-506 expression was inversely correlated with FOXQ1 expression in cervical cancer. The overexpression of miR-506 dramatically suppressed the proliferation and EMT of cervical cancer cells that mimicked the suppression of FOXO1 siRNA. Furthermore, the restoration of FOXQ1 expression significantly reversed the inhibitory effect of miR-506. Overall, our study demonstrated that miR-506 inhibited the proliferation and EMT of cervical cancer cells by targeting FOXQ1 and provided evidence that the miR-506/FOXQ1 axis plays an important role in the pathogenesis of cervical cancer, representing potential molecular targets for the development of anticancer agents for cervical cancer treatment.

Cellular response of chondrocytes to magnesium alloys for orthopedic applications.

In the present study, the effects of Mg-Nd-Zn-Zr (JDBM), brushite (CaHPO4·2H2O)-coated JDBM (C-JDBM), AZ31, WE43, pure magnesium (Mg) and Ti alloy (TC4) on rabbit chondrocytes were investigated in vitro. Adhesion experiments revealed the satisfactory morphology of chondrocytes on the surface of all samples. An indirect cytotoxicity test using MTT assay revealed that C­JDBM and TC4 exhibited results similar to those of the negative control, better than those obtained with JDBM, AZ31, WE43 and pure Mg (p<0.05). There were no statistically significant differences observed between the JDBM, AZ31, WE43 and pure Mg group (p>0.05). The results of indirect cell cytotoxicity and proliferation assays, as well as those of apoptosis assay, glycosaminoglycan (GAG) quantification, assessment of collagen Ⅱ (Col Ⅱ) levels and RT-qPCR revealed a similar a trend as was observed with MTT assay. These findings suggested that the JDBM alloy was highly biocompatible with chondrocytes in vitro, yielding results similar to those of AZ31, WE43 and pure Mg. Furthermore, CaHPO4·2H2O coating significantly improved the biocompatibility of this alloy.