Reactive stepping

Due to boron's metalloid properties, aromatic boron reagents are prevalent synthetic intermediates. The direct borylation of aryl C-H bonds for producing aromatic boron compounds offers an appealing, one-step solution. Despite significant advances in this field, achieving regioselective aryl C-H bond borylation using simple and readily available starting materials still remains a challenge. In this work, we attempted to enhance the reactivity of the electron-donor-acceptor (EDA) complex by selecting different bases to replace the organic base (NEt3 ) used in our previous research...

Glycolytic overload promotes accumulation of the highly reactive dicarbonyl compounds, resulting in harmful conditions called dicarbonyl stress. Methylglyoxal (MG) is a highly reactive dicarbonyl species and its accumulation plays a crucial pathophysiological role in diabetes and its vascular complications. MG cytotoxicity is mediated by reactive oxygen species (ROS) generation, a key event underlying the intracellular signaling pathways leading to inflammation and apoptosis. The identification of compounds able to inhibit ROS signaling pathways and counteract the MG-induced toxicity is a crucial step for developing new therapeutic strategies in the treatment of diabetic vascular complications...

BACKGROUND: L-Arginine (Arg) is an essential amino acid and a precursor for the synthesis of vascular nitric oxide, while L-Citrulline is a non-essential amino acid substrate for increasing L-arginine. Both L-arginine and L-Citrulline in translational studies may acutely lower the blood pressure. Current meta-analysis for L-arginine or L-Citrulline interventions in blood pressure have identified significant heterogeneity. Clinical trial evidence for L-arginine or L-Citrulline in chronic blood pressure reduction in the general population requires an examination of trial designs, as not all translational studies may have influenced vascular reactivity...

Reactive oxygen species (ROS) are implicated in various pathological conditions due to their ability to induce oxidative damage to cellular components. In this study, we investigated the antioxidant properties of a peptide isolated from the hydrolysate of Manila clam ( Ruditapes philippinarum ) muscle. Purification steps yielded RPTE2-2-4, exhibiting potent scavenging activities against DPPH•, HO•, and O2 •- , akin to Vitamin C. Structural analysis showed that the isolated peptide, LFKKNLLTL, exhibited characteristics associated with antioxidant activity, including a short peptide length and the presence of aromatic and hydrophobic amino acid residues...

In this study, we report the modification of flexible copper films via the spontaneous reduction of aryldiazonium gold salts [X-4-C6 H4 N≡N]AuCl4 (X═COOH, NO2 ). The electroless modification involves dipping of flexible copper films in the aryldiazonium gold solutions for a few seconds, under ambient conditions, followed by a washing step with deionized water to obtain a mechanically robust gold-aryl coating. The chemical composition, morphology, electronic structure, and optical properties of the gold-aryl layer and the flexibility of the modified copper films are supported by the results from X-ray photoelectron spectroscopy (XPS), electrochemistry, contact angle, scanning electron microscopy (SEM), and ultraviolet photoelectron spectroscopy (UPS)...

Metal sulfides in waste rocks and tailings are susceptible to serious soil and water contamination due to the generation of acid mine drainage (AMD) during stockpiling. The hydrometallurgical process is one of the most essential heavy metal remediation technologies through harmless disposal and resource utilization of the waste sulfides. However, atmospheric hydrometallurgy of sulfides still faces great challenges due to low leaching efficiency and high cost. In this work, we proposed a cooperative leaching system (Fe2 (SO4 )3 -O3 ) and investigated the oxidative dissolution process of sphalerite (ZnS)...

Klebsiella pneumoniae (Kp) is a Gram-negative bacterium, and a leading cause of neonatal sepsis in low- and middle-income countries, often associated with anti-microbial resistance. Two types of polysaccharides are expressed on the Kp cell surface and have been proposed as key antigens for vaccine design: capsular polysaccharides (known as K-antigens, K-Ags) and O-antigens (O-Ags). Historically, Kp has been classified using capsule serotyping and although 186 distinct genotypes have been predicted so far based on sequence analysis, many structures are still unknown...

The bimetallic species, [{SiNDipp }MgNa]2 [{SiNDipp } = {CH2 SiMe2 N(Dipp)}2 ; (Dipp = 2,6- i -Pr2 C6 H3 )], is shown to be a potent reducing agent, able to effect one- or two-electron reduction of either dioxygen, TEMPO, anthracene, benzophenone, or diphenylacetylene. In most cases, the bimetallic reaction products imply that the dissimilar alkaline metal centers react with a level of cooperativity. EPR analysis of the benzophenone-derived reaction and the concurrent isolation of [{SiNDipp }Mg(OCPh2 )2 ], however, illustrate that treatment with such reducible, but O -basic, species can also result in reactivity in which the metals provide independent reaction products...

Ammonia (NH3 ) is closely related to the fields of food and energy that humans depend on. The exploitation of advanced catalysts for NH3 synthesis has been a research hotspot for more than one hundred years. Previous studies have shown that the Ru B5 sites (step sites on the Ru (0001) surface uniquely arranged with five Ru atoms) and Fe C7 sites (iron atoms with seven nearest neighbors) over nanoparticle catalysts are highly reactive for N2 -to-NH3 conversion. In recent years, single-atom and cluster catalysts, where the B5 sites and C7 sites are absent, have emerged as promising catalysts for efficient NH3 synthesis...

Prehydrolysis liquid (PHL) from dissolving pulp and biorefinery industries is rich in saccharides and lignin, being considered as a potential source of value-added materials and platform molecules. This study proposed an environmentally friendly and simple method to prepare morphologically controllable hollow lignin nanoparticles (LNPs) and levulinic acid (LA) from PHL. In the first step, after hydrothermal treatment of PHL with p -toluenesulfonic acid ( p -TsOH), lignin with a uniform molecular weight was obtained to prepare LNPs...

Density functional theory (DFT) calculations have been conducted to elucidate the detailed mechanisms of yttrium-catalyzed C-H polyaddition of 1,4-dimethoxybenzene (DMB) to 1,4-divinylbenzene (DVB). It was computationally determined that DMB not only serves as a substrate but also performs a crucial role as a ligand, stabilizing the catalytically active species and promoting alkene insertion. Side pathways involving Cβ -H activation and C═C continuous insertion were excluded due to steric and electronic factors, respectively, explaining why the reaction occurred efficiently and selectively to give perfectly alternating DMB-DVB polymers...

Aryldiazonium salts remain a staple in organic synthesis and are still prepared largely in accord with the protocol developed in the 19th century. Because of the favorable reactivity that often cannot be achieved with other aryl(pseudo)halides, diazonium chemistry continues to grow. Facile extrusion of dinitrogen contributes to the desired reactivity but is also reason for safety concerns. Explosions have occurred since the discovery of these reagents and still result in accidents. In this study, we report a diazonium chemistry paradigm shift based on nitrate reduction using thiosulfate or dihalocuprates as electron donors that avoids diazonium accumulation...

Synergistic therapy has shown greater advantages compared with monotherapy. However, the complex multiple-administration plan and potential side effects limit its clinical application. A transformable specific-responsive peptide (TSRP) is utilized to one-step achieve synergistic therapy integrating anti-tumor, anti-angiogenesis and immune response. The TSRP is composed of: i) Recognition unit could specifically target and inhibit the biological function of FGFR-1; ii) Transformable unit could self-assembly and trigger nanofibers formation; iii) Reactive unit could specifically cleaved by MMP-2/9 in tumor micro-environment; iv) Immune unit, stimulate the release of immune cells when LTX-315 (Immune-associated oncolytic peptide) exposed...

We investigate the chemical interaction of carbon monoxide (CO) and oxygen (O2 ) with kink atoms on steps of platinum crystal surfaces using a specially designed Pt curved sample. We aim at describing the fundamental stages of the CO oxidation reaction, i.e., CO-covered/poisoned stage and O-covered/active stage, at the poorly known kinked Pt facets by probing CO uptake/saturation and O2 saturation, respectively. Based on the systematic analysis that the curved surface allows, and using high-resolution X-ray photoemission, a diversity of terrace and step/kink species are straightforwardly identified and accurately quantified, defining a smooth structural and chemical variation across different crystal planes...

Reactive metals hydrolysis offers significant advantages for hydrogen storage and production. However, the regeneration of common reactive metals (e.g., Mg, Al, etc.) is energy-intensive and produces unwanted byproducts such as CO2 and Cl2. Herein, we employ Zn as a reactive mediator that can be easily regenerated by electrolysis of ZnO in an alkaline solution with a Faradaic efficiency of > 99.9%. H2 is produced in the same electrolyte by constructing a Zn-H2O hydrolysis battery consisting of a Zn anode and a Raney-Ni cathode to unlock the Zn-H2O reaction...

In recent years, noninnocent pyridine diimine (PDI) complexes featuring first-row transition metals have emerged as prominent catalysts, demonstrating efficacy in a diverse range of vital organometallic transformations. However, the inherent complexity of the fundamental reactivity paradigm in these systems arises from the presence of a noninnocent ligand and the multispin feasibility of 3d metals. While density functional theory (DFT) has been widely used to unravel mechanistic insights, its limitations as a single-reference method can potentially misrepresent spin-state energetics, compromising our understanding of these intricate systems...

INTRODUCTION: An effective reactive step response to an unexpected balance loss is an important factor that determines if a fall will happen. We investigated reactive step strategies and kinematics of unsuccessful balance recovery responses that ended with falls in older adults. METHODS: We compared the strategies and kinematics of reactive stepping after a lateral loss of balance, i.e., perturbations, between 49 older female adults who were able to successfully recover from perturbations (perturbation-related non-fallers, PNFs) and 10 female older adults who failed to recover (perturbation-related fallers, PFs)...

A novel class of (P^N^C) pincer ligands capable of stabilizing elusive gold(III) species is reported here. Straightforward access to (P^N^C)gold(III) hydroxo, formate, and hydride complexes has been streamlined by first incorporating a cycloauration step devoid of toxic metals or harsh conditions. The resulting gold complexes exhibit remarkable stability in solution as well as in the solid state under ambient conditions, which enabled their characterization by X-ray diffraction analyses. Interestingly, the influence of the ligand allowed the preparation of gold(III)-hydrides using mild hydride donors such as H-Bpin, which contrasts with sensitive super hydrides or strong acids and cryogenic conditions employed in previous protocols...

T helper 17 (TH 17) cells are implicated in autoimmune diseases, and several metabolic processes are shown to be important for their development and function. In this study, we report an essential role for sphingolipids synthesized through the de novo pathway in TH 17 cell development. Deficiency of SPTLC1, a major subunit of serine palmitoyl transferase enzyme complex that catalyzes the first and rate-limiting step of de novo sphingolipid synthesis, impaired glycolysis in differentiating TH 17 cells by increasing intracellular reactive oxygen species (ROS) through enhancement of nicotinamide adenine dinucleotide phosphate oxidase 2 activity...

The development and characterization of materials for solid oxide fuel cells (SOFC) is an important step towards sustainable energy technologies. This present study models cubic CeO2 , Gd2 O3 , and gadolinium-doped ceria (GDC) using newly constructed interaction potentials based on a partial atom charge framework. The interaction model was validated by comparing the structural properties with experimental reference data, which were found to be in good agreement. Validation of the potential model was conducted considering the surface stability of CeO2 and Gd2 O3 ...