Catalytic Intermolecular Deoxygenative Coupling of Carbonyl Compounds with Alkynes by a Cp*Mo(II)-Catalyst.

Carbonyl is highly accessible and acts as an essential functional group in chemical synthesis. However, the direct catalytic deoxygenative functionalization of carbonyl compounds via a putative metal carbene intermediate is a formidable challenge due to the requirement of a high activation energy for the cleavage of strong C═O double bonds. Here, we report a class of bench stable and readily available Cp*Mo(II)-complexes as efficient deoxygenation catalysts that could catalyze the direct intermolecular deoxygenative coupling of carbonyl compounds with alkynes. Enabled by this powerful Cp*Mo(II)-catalyst, various valuable heteroarenes (10 different classes) were obtained in generally good yields and remarkable chemo- and regioselectivities. Mechanistic studies suggested that this reaction might proceed via a sequence of C═O double bonds cleavage, carbene-alkyne metathesis, cyclization, and aromatization processes. This strategy not only provided a general catalytic platform for the rapid preparation of heteroarenes but also opened a new window for the applications of Cp*Mo(II)-catalysts in organic synthesis.

Adjacent Mn site boosts photocatalytic hydrogen evolution of MnXCd1-XS solid solution through a dual-metal-site design.

CdS has emerged as a possible candidate for photocatalytic hydrogen generation. However, further improvement in the performance of the Cd metal site is challenging due to limited optimization space. To solve this limitation, in this work, the Mn-Cd dual-metal photocatalyst was synthesized by a one-step solvothermal method, and the effects of different proportions of bimetals on hydrogen production activity were systematically studied. The ingenious design of the bimetallic sites enhances the carrier separation efficiency and the built-in electric field intensity, which leads to significant improvement in the photocatalytic hydrogen production performance of MCS0.19. Density functional theory (DFT) calculations confirm that the introduction of the Mn element can drive electrons through the Fermi level, resulting in enhanced conductivity of the catalyst. Meanwhile, electron channels are built between Mn and S, which speeds up the rate of electron transfer and is conducive to improving hydrogen production activity. This work provides a technical-methodological entrance to improve the photocatalytic hydrogen production performance of dual-metal S solid solutions and also promises to open a novel approach to creating high-efficiency solid solution photocatalysts.

Electronic and energy level structural engineering of graphitic carbon nitride nanotubes with B and S co-doping for photocatalytic hydrogen evolution.

The ideal photocatalyst used for photocatalytic water splitting requires strong light absorption, fast charge separation/transfer ability and abundant active sites. Heteroatom doping offers a promising and rational approach to optimize the photocatalytic activity. However, achieving high photocatalytic performance remains challenging if just relying on single-element doping. Herein, Boron (B) and sulfur (S) dopants are simultaneously introduced into graphitic carbon nitride (g-C3N4) nanotubes by supramolecular self-assembly strategy. The developed B and S co-doped g-C3N4 nanotubes (B,S-TCN) exhibited an outstanding photocatalytic performance in the conversion of H2O into H2 (9.321 mmol g-1h-1), and the corresponding external quantum efficiency (EQE) reached 5.3% under the irradiation of λ = 420 nm. It is well evidenced by the closely combined experimental and (density functional theory) DFT calculations: (1) the introduction of B dopants can facilitate H2O adsorption and drive interatomic electron transfer, leading to efficient water splitting reaction. (2) S dopants can stretch the VB position to promote the oxidation ability of g-C3N4, which can accelerate the consumption of holes and thus inhibit the recombination with electrons. (3) the simultaneous introduction of B and S can engineer the electronic and energy level structural of g-C3N4 for optimizing interior charge transfer. Finally, the purpose of maximizing photocatalytic performance is achieved.

Highly Efficient and Exceptionally Durable Photooxidation Properties on Co3O4/g-C3N4 Surfaces.

Water pollution is a significant social issue that endangers human health. The technology for the photocatalytic degradation of organic pollutants in water can directly utilize solar energy and has a promising future. A novel Co3O4/g-C3N4 type-II heterojunction material was prepared by hydrothermal and calcination strategies and used for the economical photocatalytic degradation of rhodamine B (RhB) in water. Benefitting the development of type-II heterojunction structure, the separation and transfer of photogenerated electrons and holes in 5% Co3O4/g-C3N4 photocatalyst was accelerated, leading to a degradation rate 5.8 times higher than that of pure g-C3N4. The radical capturing experiments and ESR spectra indicated that the main active species are •O2- and h+. This work will provide possible routes for exploring catalysts with potential for photocatalytic applications.

Genome-Wide Identification and Transcriptional Analysis of the MYB Gene Family in Pearl Millet (Pennisetum glaucum).

The MYB gene family widely exists in the plant kingdom and participates in the regulation of plant development and stress response. Pearl millet (Pennisetum glaucum (L.) R. Br.), as one of the most important cereals, is not only considered a good source of protein and nutrients but also has excellent tolerances to various abiotic stresses (e.g., salinity, water deficit, etc.). Although the genome sequence of pearl millet was recently published, bioinformatics and expression pattern analysis of the MYB gene family are limited. Here, we identified 208 PgMYB genes in the pearl millet genome and employed 193 high-confidence candidates for downstream analysis. Phylogenetic and structural analysis classified these PgMYBs into four subgroups. Eighteen pairs of segmental duplications of the PgMYB gene were found using synteny analysis. Collinear analysis revealed pearl millet had the closest evolutionary relationship with foxtail millet. Nucleotide substitution analysis (Ka/Ks) revealed PgMYB genes were under purifying positive selection pressure. Reverse transcription-quantitative PCR analysis of eleven R2R3-type PgMYB genes revealed they were preferentially expressed in shoots and seeds and actively responded to various environment stimuli. Current results provide insightful information regarding the molecular features of the MYB family in pearl millet to support further functional characterizations.

Parameters Affecting the Mechanical Properties of Three-Dimensional (3D) Printed Carbon Fiber-Reinforced Polylactide Composites.

Three-dimensional (3D) printing is a manufacturing technology which creates three-dimensional objects layer-by-layer or drop-by-drop with minimal material waste. Despite the fact that 3D printing is a versatile and adaptable process and has advantages in establishing complex and net-shaped structures over conventional manufacturing methods, the challenge remains in identifying the optimal parameters for the 3D printing process. This study investigated the influence of processing parameters on the mechanical properties of Fused Deposition Modelling (FDM)-printed carbon fiber-filled polylactide (CFR-PLA) composites by employing an orthogonal array model. After printing, the tensile and impact strengths of the printed composites were measured, and the effects of different parameters on these strengths were examined. The experimental results indicate that 3D-printed CFR-PLA showed a rougher surface morphology than virgin PLA. For the variables selected in this analysis, bed temperature was identified as the most influential parameter on the tensile strength of CFR-PLA-printed parts, while bed temperature and print orientation were the key parameters affecting the impact strengths of printed composites. The 45° orientation printed parts also showed superior mechanical strengths than the 90° printed parts.

YSA-conjugated mesoporous silica nanoparticles effectively target EphA2-overexpressing breast cancer cells.

PURPOSE: Neoadjuvant chemotherapy is commonly used to treat patients with locally advanced breast cancer and a common option for primary operable disease. However, systemic toxicity including cardiotoxicity and inefficient delivery are significant challenges form any chemotherapeutics. The development of targeted treatments that lower the risk of toxicity has, therefore, become an active area of research in the field of novel cancer therapeutics. Mesoporous silica nanoparticles (MSNs) have attracted significant attention as efficient drug delivery carriers, due to their high surface area and tailorable mesoporous structures. Eph receptors are the largest receptor tyrosine kinase family, which are divided into the A- and the B-type. Eph receptors play critical roles in embryonic development and human diseases including cancer. EphA2 is expressed in breast cancer cells and has roles in carcinogenesis, progression and prognosis of breast cancer. METHODS: A homing peptide with the sequence YSAYPDSVPMMSK (YSA) that binds specifically to EphA2 was used to functionalize MSN. We focus on a novel EphA2-targeted delivery MSN system for breast cancer cells. RESULTS: We show that the EphA2 receptor is differentially expressed in breast cancer cells and highly expressed in the HER2-negative breast cancer cell line MCF7. Our results suggest that EphA2-targeted MSN for doxorubicin delivery (MSN-YSA-DOX) are more effective than MSN-DOX in treating breast cancer cell lines in vitro. CONCLUSIONS: Our preliminary observations suggest that the EphA2-targeted MSN delivery system may provide a strategy for enhancing delivery of therapeutic agents to breast cancer cells expressing EphA2, and potentially reduce toxicity while enhancing therapeutic efficacy.

[Clinical study of the characteristics of lymph node metastasis in thoracic esophageal cancer].

OBJECTIVE: To explore the characteristics of lymph node metastasis in thoracic esophageal cancer in order to provide evidence for the extent of lymph node dissection and the operation access. METHODS: A retrospective study was performed on the specimens of 72 patients who underwent radical operation of right transthoracic approach and the features of lymph node metastasis were explored. RESULTS: Lymph node metastases were found in 48 of 72 patients (66.7%). In 1495 lymph nodes dissected, metastases was identified in 181 lymph nodes (12.1%). The rate of lymph node metastasis in the right and left recurrent laryngeal nerve was 30.6% and 12.5% respectively. Lymph node metastasis was associated with tumor size and tumor invasion depth (both P<0.05), while tumor location and differentiation of tumor cells were not significant (both P>0.05). CONCLUSIONS: The lymph node metastasis in thoracic esophageal carcinoma can be easily found in the right recurrent laryngeal nerve. The best surgical approach of thoracic esophageal carcinoma is the right transthoracic approach.