Tunable electrochemical diverse sulfurization of sulfoxonium ylides with disulfides.

An electrochemical protocol for the synthesis of sulfursulfoxonium ylides and 1,3-dithioketals by reacting sulfoxonium ylides with disulfides has been developed under simple and mild conditions. By changing the solubility of the raw materials and the dielectric parameters of the electrolyte, sulfurization enabled a selective dehydrogenation of C-S and the construction of 1,3-dithioketals. The transformation is an ideal approach to prepare organosulfur reagents with a broad functional group tolerance as well as high selectivity, which leads to vicinal difunctionalized organosulfur compounds.

Electrochemical synthesis of peptide aldehydes via C‒N bond cleavage of cyclic amines.

Peptide aldehydes are crucial biomolecules essential to various biological systems, driving a continuous demand for efficient synthesis methods. Herein, we develop a metal-free, facile, and biocompatible strategy for direct electrochemical synthesis of unnatural peptide aldehydes. This electro-oxidative approach enabled a step- and atom-economical ring-opening via C‒N bond cleavage, allowing for homoproline-specific peptide diversification and expansion of substrate scope to include amides, esters, and cyclic amines of various sizes. The remarkable efficacy of the electro-synthetic protocol set the stage for the efficient modification and assembly of linear and macrocyclic peptides using a concise synthetic sequence with racemization-free conditions. Moreover, the combination of experiments and density functional theory (DFT) calculations indicates that different N-acyl groups play a decisive role in the reaction activity.

Adsorption of uranium(VI) by natural vermiculite: Isotherms, kinetic, thermodynamic and mechanism studies.

Human activities such as mining uranium resources, hydrometallurgy, and nuclear fuel preparation inevitably produce wastewater sludge containing radionuclides, posing a severe threat to the environment around the production site. Natural clay minerals have been widely used in groundwater pollution remediation because of their high cation exchange capacity. Through static batch experiments, the optimal pH range of vermiculite for U(VI) adsorption was 6-8,the maximum adsorption capacity was 1.62 × 10-5 mol g-1. The kinetic adsorption results indicated that the adsorption mode was mainly multilayer non-homogeneous chemisorption. In addition, the adsorption of vermiculite on U(VI) was found to be a heat absorption process according to the thermodynamic model fitting, and the spontaneous reactivity of U(VI) adsorption on vermiculite surface was positively correlated with temperature and negatively correlated with the initial concentration of U(VI). Combined with SEM-EDS and FT-IR results, the adsorption process of vermiculite on U(VI) is mainly an ion exchange and complexation reaction, and U(VI) is removed in the form of ≡ SUOU22+ or ≡ SOUO2OH, etc., by XPS means. The results of this study not only investigated the adsorption behavior and mechanism of natural vermiculite in groundwater contaminated with simulated uranium but also provided theoretical support for its feasibility in remediating uranium-polluted groundwater.

The electrochemically enabled α-C(sp3)-H azolation of ketones.

C-H/N-H cross-coupling has become a key technology for the selective conjugation of azole drug molecules. However, the development of new synthetic models and green chemical methods is imperative to enhance the construction of multi-functional compounds and compounds with unique functional groups. We herein reported an electrochemical synthesis of α-tetrazolyl ketones with excellent yields and broad substrate scope, encompassing electron-donating and electron-withdrawing groups of aryl ketones, heterocycles, and alkyl and various ketone drugs. It was further proved that α-iodoketone was involved in this transformation of the reaction as a critical intermediate.

Electrochemical Selenylation of Sulfoxonium Ylides for the Synthesis of gem-Diselenides as Antimicrobials against Fungi.

Organoselenium compounds are important scaffolds in pharmaceutical molecules. Herein, we report metal-free, electrochemical, highly chemo- and regioselective synthesis of gem-diselenides through the coupling of α-keto sulfoxonium ylides with diselenides. The versatility of the electrochemical manifold enabled the selenylation with ample scope and broad functional group tolerance, as well as setting the stage for modification of complex bioactive molecules. Detailed mechanistic studies revealed that the key C-Se bond was constructed using n-Bu4NI as an electrolyte and catalyst through the electrosynthetic protocol. Finally, the desired α-keto gem-diselenides showed excellent antimicrobial activity against Candida albicans, which can be identified as the lead compounds for further exploration.

Effect of La Doping on Kinetic and Thermodynamic Performances of Ti1.2CrMn Alloy upon De/Hydrogenation.

Development of efficient hydrogen storage materials is one of the great challenges in the area of hydrogen energy and fuel cells. Herein, a La-doped Ti1.2CrMn alloy with high hydriding capacity (2.1 wt % H) and dehydriding capacity (1.8 wt % H) was successfully developed. The crystallographic characteristics, microstructural evolution, and hydrogen storage mechanisms of the alloy were investigated systematically. It was found that the introduction of La increased the cell volume of alloy and thus improved the hydrogenation kinetic, practical hydrogenation capacity, and cyclic property. The hydrogenation kinetic results of the La-doped alloy indicate that it exhibited a higher hydrogenation rate than that of the La-free alloy. It is ascribed to the formation of LaH3, which provides a fast diffusion channel for hydrogen atoms to enter the alloy matrix. The dehydrogenation enthalpy (ΔH) of the La-doped alloy was calculated by the van't Hoff equation and PCT curves to be ∼18.2 kJ/mol. The cycle test proves that the La-doped Ti1.2CrMn alloy, due to La addition, reduces the lattice expansion and lattice stress and exhibits excellent durability.

Cyclocarboamination of Alkynes with N-Aminopyridiniums by Photoredox Catalysis.

A visible-light photoredox-catalyzed reaction to access structurally diverse pyridoimidazoles has been developed. This transformation features intermolecular carboamination of N-sulfonylaminopyridiniums with a broad scope of alkynes.

Selenium-Electrocatalytic Cyclization of 2-Vinylanilides towards Indoles of Peptide Labeling.

A novel selenium-electrocatalytic intramolecular cyclization of 2-vinylanilides for synthesis of functionalized indoles and azaindoles has been developed. In contrast to the previous synthetic methods, this sustainable protocol enabled unparalleled broad substrates scope for viable indoles with highly functional and sensitive groups by employing recyclable selenium catalyst, under mild, metal- and external-oxidant-free conditions. The approach can be used to the late-stage modification of complex bioactive molecular system, thereby setting the stage for versatile syntheses of decorated indoles with peptide labeling. A plausible catalytic pathway was proposed.

Development of a Colloidal Gold Immunochromatographic Strip for Rapid Detection of Cyfra 21-1 in Lymph Node Metastasis of Thyroid Cancer.

Thyroid cancer is the most common endocrine tumor, and the rate of early lymph node metastasis may be as high as 60%. Currently, detection of lymph node metastasis of thyroid cancer during surgery is limited and time-consuming. Elevated levels of Cyfra 21-1, the proteolytic portion of cytokeratin, are associated with the metastasis and progression of thyroid cancer and are an effective biomarker for the prognosis and diagnosis of thyroid cancer. In this study, an immunochromatographic strip test based on colloidal gold nanoparticles was developed to semi-quantitatively detect the levels of Cyfra 21-1 in lymph nodes within 15 min. The standard (calibration) curve equation was Y = 0.003708 × X + 0.1101, and the detection limit was 0.55-1.14 ng mL-1. The strip did not detect other protein markers of epithelial cells at a concentration of 500 ng mL-1, including cytokeratin 8, cytokeratin 18, epithelial membrane antigen, and epidermal surface antigen. The ability of the strip to differentiate positive from negative metastasis in 40 lymph node specimens was 100% concordant with that of immunohistochemical staining for Cyfra 21-1. In an assessment of 20 lymph node specimens that had been determined by postoperative histopathology to be positive for lymph node metastasis and 20 specimens that were negative, the sensitivity and specificity of the strip were 100% and 95%, respectively. The sensitivity of the strip remained stable when stored at room temperature for 6 months. Together, these results indicated that although further testing using a larger sample size will be required, this immunochromatographic strip test may be useful for rapid intraoperative detection of thyroid cancer metastasis to lymph nodes.

Bimetal Cooperatively Catalyzed Arylalkynylation of Alkynylsilanes.

An unprecedented Pd/Rh cooperatively catalyzed arylalkynylation of alkynylsilanes was developed to merge an alkynylidene moiety with benzosilacycle. These silaarenes possess a particular aggregation-induced emission behavior. Mechanistic investigations demonstrate that the relay trimetallic transmetalation plays a pivotal role in governing this transformation.

Rh(III)-Catalyzed Csp2-Csp3 σ-Bond Enolation of α-Indolyl Alcohols.

A Rh(III)-catalyzed Csp2-Csp3 σ-bond carbenoid functionalization of α-(2-indolyl)alcohols with acceptor/acceptor diazo compounds has been developed. This transformation provides an efficient strategy to assemble stable C2-enolated indole skeletons via Csp2-Csp3 σ-bond cleavage.

Rhodium(i)-catalyzed vinylation/[2 + 1] carbocyclization of 1,6-enynes with α-diazocarbonyl compounds.

A sequential Rh(i)-catalyzed vinylation/[2 + 1]carbocyclization between enynes and diazo compounds has been developed. This transformation features a wide range of enynes and acceptor/acceptor diazo compounds, providing easy access to versatile vinyl-substituted azabicyclo[3.1.0]hexanes having a broad tolerance to functional groups.

Zn(OAc)2-Catalyzed C3-Carbonylacetylation of Indoles with α-Diazoketones Involving Wolff Rearrangement.

Zn(OAc)2-catalyzed highly regioselective carbonylacetylation of indoles and pyrroles with α-diazoketones has been developed. This transformation involves a combination of Wolff rearrangement/cross-coupling relay and provides an efficient approach to versatile 3-carbonylacetylindoles and 2-carbonylacetylpyrroles with a broad range of functional group tolerance.

Rhodium(I)-Catalyzed Coupling-Cyclization of C═O Bonds with α-Diazoketones.

An unprecedented intermolecular nucleophilic attack of C═X bonds (X = O and S) on the rhodium(I)-carbenes has been developed. This transformation allows for the coupling-cyclization of aroylamides with α-diazoketones and provides concise access to 2,4,5-trisubstituted 1,3-oxazoles and 1,3-thiazoles with a broad tolerance of functional groups.

Rh(III)-Catalyzed Carboamination of Propargyl Cycloalkanols with Arylamines via Csp2-H/Csp3-Csp3 Activation.

A Rh(III)-catalyzed carboamination of alkynyl cycloalkanols with arylamines has been developed. This transformation involves a novel Csp2-H/Csp3-Csp3 activation relay and provides an efficient approach to versatile 1,2,3-trisubstituted indoles with a broad range of functional group tolerance.

An Ir(iii)-catalyzed aryl C-H bond carbenoid functionalization cascade: access to 1,3-dihydroindol-2-ones.

An Ir(iii)-catalyzed relay aryl C-H bond carbenoid insertion cascade of N-aryl-2-pyridinamines with diazo Meldrum's acid has been developed. This method provides an efficient approach to multifunctionalized 1,3-dihydroindol-2-ones with a broad range of functional group tolerance. Furthermore, this protocol could be applied for the concise synthesis of bioactive hematopoietic growth factor analogues.

A [4 + 1] Cyclative Capture Access to Indolizines via Cobalt(III)-Catalyzed Csp(2)-H Bond Functionalization.

A Co(III)-catalyzed [4 + 1] cycloaddition of 2-arylpyridines or 2-alkenylpyridines with aldehydes through Csp(2)-H bond activation has been developed. This protocol provides a facile approach to structurally diverse indolizines including benzoindolizines with a broad range of functional group tolerance.

Rh(III)-Catalyzed [4 + 2] Annulation of Indoles with Diazo Compounds: Access to Pyrimido[1,6-a]indole-1(2H)-ones.

The Rh(III)-catalyzed regioselective C2-H bond carbenoid insertion/cyclization of N-amidoindoles with α-acyl diazo compounds has been developed. This method provides a novel approach to 2H-pyrimido[1,6-a]indol-1-ones with a broad range of functional group tolerance. The synthetic utilities of the approach are demonstrated by versatile chemical transformations.

[Effects of rhBNP on left ventricular remodeling in rats with acute myocardial infarction].

OBJECTIVE: To assess the effects of rhBNP on left ventricular (LV) remodeling in rats with acute myocardial infarction (AMI). METHODS: AMI was induced by ligating coronary artery in male Sprague Dawley rats. Two days after surgery, AMI rats received intravenous infusion of rhBNP (15 microg/kg or 5 microg/kg once daily, n = 15 each) or saline (placebo control, n = 15) through Jugular Vein. Sham-operated rats (n = 15) served as normal control. Four weeks later, hemodynamic measurements were performed, left ventricular weight (LVW), ratio of left ventricular weight to body weight (LVW/BW), left ventricular diameter (LVD) and infarct size were determined. Plasma angiotensin II and myocardial angiotensin II levels were also measured. RESULTS: Compared with sham-operated rats, LVW, LVW/BW, LVD and myocardial angiotensin II level were significantly increased, while the LV systolic pressure (LVSP), +/- dp/dt were significantly reduced in saline treated AMI rats (all P < 0.05). LVW/BW, MI size, LVD and myocardial angiotensin II in rhBNP treated AMI rats were significantly lower [LVW: (492.6 +/- 34.0) mg, (498.8 +/- 47.8) mg, (570.0 +/- 24.2) mg, P < 0.01; LVW/BW: 2.0 +/- 0.2, 2.0 +/- 0.2, 2.3 +/- 0.1, P < 0.01; LVD: (25.3 +/- 2.9)%, (31.4 +/- 3.0)%, (46.4 +/- 3.0)%, P < 0.01; myocardial angiotensin II: (881.3 +/- 62.7) pg/L, (1186.0 +/- 94.5) pg/L, (2436.7 +/- 280.3) pg/L, P < 0.05], while LVSP and +/- dp/dt in rhBNP treatment groups were significantly increased than saline treated AMI rats (P < 0.05 or P < 0.01). CONCLUSION: RhBNP is effective in attenuating left ventricular remodeling after AMI in rats.