Systemic immune-inflammation index is associated with high risk for prostate cancer among the U.S. elderly: Evidence from NHANES 2001-2010.

Purpose: The Systemic Immuno-Inflammation Index (SII) is a crucial clinical measure of inflammation, and there is currently no solid evidence linking SII to an increased risk of prostate cancer (PCa). Through the analysis of serum total prostate-specific antigen (tPSA), free prostate-specific antigen (fPSA), and the tPSA/fPSA (fPSA%) ratio, this study sought to investigate the relationship between SII and PCa risk among the U.S.

Nonlinear association between non-high-density lipoprotein cholesterol to high-density lipoprotein cholesterol ratio and hyperuricemia in cancer patients: evidence from NHANES 2007-2018.

Background: Evidence shows that cancer patients are more likely to have hyperuricemia (HUA) compared to the general population, with lipid metabolism playing a significant role. However, it is still unclear whether there is a non-linear relationship between the non-high-density lipoprotein cholesterol to high-density lipoprotein cholesterol ratio (NHHR) and HUA in these patients. This study aims to explore the association between NHHR and HUA in cancer patients.

Electrochemical Cyanation of Alcohols Enabled by an Iodide-Mediated Phosphine P(V/III) Redox Couple.

We report herein a mild electrochemical method to transform alcohols into their corresponding nitriles by using commercially available reagents. This protocol accepts substrates with various functional groups including those that are susceptible to oxidative decomposition. Mechanistic studies revealed a critical iodide-mediated phosphine electrochemical oxidation pathway leading to the alkoxyphosphonium intermediate, followed by nucleophilic substitution by a cyanide nucleophile.

Association between non-high-density lipoprotein cholesterol to high-density lipoprotein cholesterol ratio and sarcopenia in individuals with cancer: a cross-sectional study.

Background: Cancer and sarcopenia are both closely related to lipid metabolism, but the relationship between lipid metabolism and patients with cancer and sarcopenia has not been thoroughly studied. The non-high-density lipoprotein cholesterol to high-density lipoprotein cholesterol ratio (NHHR) is a reliable measure of lipid metabolism. The purpose of this study was to determine the possible relationship between the NHHR and sarcopenia in individuals with cancer.

Threonine Aldolase-Catalyzed Enantioselective α-Alkylation of Amino Acids through Unconventional Photoinduced Radical Initiation.

Visible light-driven pyridoxal radical biocatalysis has emerged as a promising strategy for the stereoselective synthesis of valuable noncanonical amino acids (ncAAs). Previously, the use of well-tailored photoredox catalysts represented the key to enable efficient pyridoxal phosphate (PLP) enzyme-catalyzed radical reactions. Here, we report a PLP-dependent threonine aldolase-catalyzed asymmetric α-C-H alkylation of abundant amino acids using Katritzky pyridinium salts as alkylating agents.

Disulfide radical anion as a super-reductant in biology and photoredox chemistry.

Disulfides are involved in a broad range of radical-based synthetic organic and biochemical transformations. In particular, the reduction of a disulfide to the corresponding radical anion, followed by S-S bond cleavage to yield a thiyl radical and a thiolate anion plays critical roles in radical-based photoredox transformations and the disulfide radical anion in conjunction with a proton donor, mediates the enzymatic synthesis of deoxynucleotides from nucleotides within the active site of the enzyme, ribonucleotide reductase (RNR). To gain fundamental thermodynamic insight into these reactions, we have performed experimental measurements to furnish the transfer coefficient from which the standard (RSSR/RSSR˙) reduction potential has been determined for a homologous series of disulfides.

Taming the Chlorine Radical: Enforcing Steric Control over Chlorine-Radical-Mediated C-H Activation.

Chlorine radicals readily activate C-H bonds, but the high reactivity of these intermediates precludes their use in regioselective C-H functionalization reactions. We demonstrate that the secondary coordination sphere of a metal complex can confine photoeliminated chlorine radicals and afford steric control over their reactivity. Specifically, a series of iron(III) chloride pyridinediimine complexes exhibit activity for photochemical C(sp)-H chlorination and bromination with selectivity for primary and secondary C-H bonds, overriding thermodynamic preference for weaker tertiary C-H bonds.

Mechanistic Investigation and Optimization of Photoredox Anti-Markovnikov Hydroamination.

The reaction mechanism and the origin of the selectivity for the photocatalytic intermolecular anti-Markovnikov hydroamination of unactivated alkenes with primary amines to furnish secondary amines have been revealed by time-resolved laser kinetics measurements of the key reaction intermediates. We show that back-electron transfer (BET) between the photogenerated aminium radical cation (ARC) and reduced photocatalyst complex (Ir(II)) is nearly absent due to rapid deprotonation of the ARC on the sub-100 ns time scale. The selectivity for primary amine alkylation is derived from the faster addition of the primary ARCs (as compared to secondary ARCs) to alkenes.

Photocatalytic Hydromethylation and Hydroalkylation of Olefins Enabled by Titanium Dioxide Mediated Decarboxylation.

A versatile method for the hydromethylation and hydroalkylation of alkenes at room temperature is achieved by using the photooxidative redox capacity of the valence band of anatase titanium dioxide (TiO). Mechanistic studies support a radical-based mechanism involving the photoexcitation of TiO with 390 nm light in the presence of acetic acid and other carboxylic acids to generate methyl and alkyl radicals, respectively, without the need for stoichiometric base. This protocol is accepting of a broad scope of alkene and carboxylic acids, including challenging ones that produce highly reactive primary alkyl radicals and those containing functional groups that are susceptible to nucleophilic substitution such as alkyl halides.

PCET-Enabled Olefin Hydroamidation Reactions with -Alkyl Amides.

Olefin aminations are important synthetic technologies for the construction of aliphatic C-N bonds. Here we report a catalytic protocol for olefin hydroamidation that proceeds through transient amidyl radical intermediates that are formed via proton-coupled electron transfer (PCET) activation of the strong N-H bonds in -alkyl amides by an excited-state iridium photocatalyst and a dialkyl phosphate base. This method exhibits a broad substrate scope, high functional group tolerance, and amenability to use in cascade polycyclization reactions.

C-H Alkylation via Multisite-Proton-Coupled Electron Transfer of an Aliphatic C-H Bond.

The direct, site-selective alkylation of unactivated C(sp)-H bonds in organic substrates is a long-standing goal in synthetic chemistry. General approaches to the activation of strong C-H bonds include radical-mediated processes involving highly reactive intermediates, such as heteroatom-centered radicals. Herein, we describe a catalytic, intermolecular C-H alkylation that circumvents such reactive species via a new elementary step for C-H cleavage involving multisite-proton-coupled electron transfer (multisite-PCET).

Intermolecular Anti-Markovnikov Hydroamination of Unactivated Alkenes with Sulfonamides Enabled by Proton-Coupled Electron Transfer.

Here we report a catalytic method for the intermolecular anti-Markovnikov hydroamination of unactivated alkenes using primary and secondary sulfonamides. These reactions occur at room temperature under visible light irradiation and are jointly catalyzed by an iridium(III) photocatalyst, a dialkyl phosphate base, and a thiol hydrogen atom donor. Reaction outcomes are consistent with the intermediacy of an N-centered sulfonamidyl radical generated via proton-coupled electron transfer activation of the sulfonamide N-H bond.

Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer.

Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process-a subset of the classical Hofmann-Löffler-Freytag reaction-amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds.

Catalytic Carbocation Generation Enabled by the Mesolytic Cleavage of Alkoxyamine Radical Cations.

A new catalytic method is described to access carbocation intermediates via the mesolytic cleavage of alkoxyamine radical cations. In this process, electron transfer between an excited state oxidant and a TEMPO-derived alkoxyamine substrate gives rise to a radical cation with a remarkably weak C-O bond. Spontaneous scission results in the formation of the stable nitroxyl radical TEMPO(.

The rescuable function and mechanism of resveratrol on As₂O₃-induced hERG K⁺ channel deficiency.

Arsenic trioxide (As2O3) is used to treat acute promyelocytic leukemia. However, the cardiotoxicity of long QT syndrome restricts its clinical application. Previous studies showed that As2O3 can damage the human ether-a-go-go-related gene (hERG) current via disturbing its trafficking to cellular membrane.

Ginkgo biloba extract and ginkgolide antiarrhythmic potential by targeting hERG and ICa-L channel.

We investigated the effects of Ginkgo biloba extract (GBE) and ginkgolide (GLD) on human ether-a-go-go-related gene (hERG)-encoded K(+) channels and its underlying mechanisms in the hERG-HEK293 cell line by determining GBE- and GLD-induced changes in action potential duration (APD), L-type calcium currents (ICa-L), and the intracellular calcium concentration ([Ca(2+)]i) in guinea-pig ventricular myocytes. hERG currents, APD and ICa-L were recorded using the whole-cell patch clamp technique, the [Ca(2+)]i was examined by an immunofluorescence experiment. In the present study, we found that a low concentration of GBE (0.

Controllable Mono-/Dialkenylation of Benzyl Thioethers through Rh-Catalyzed Aryl C-H Activation.

Under solvent control: Benzyl thioethers were alkenylated in excellent yields with broad substrate scope and the selectivity (mono- vs. disubstituted product) was controlled by the solvent and ratio of reactants. Sequential alkenylation with two different alkenes was also carried out in a one-pot process.

Direct lactonization of 2-arylacetic acids through Pd(II)-catalyzed C-H activation/C-O formation.

Palladium-catalyzed direct lactonization of 2-arylacetic acids through a reaction sequence that includes C-H activation/C-O formation is reported. This method provides a concise and efficient pathway to synthesize fully functionalized benzofuranone derivatives, which are highly relevant to bioactive natural and synthetic products.

Olefinic C-H bond addition to aryl aldehyde and its N-sulfonylimine via Rh catalysis.

The first example of olefinic C-H addition to N-sulfonylaldimines and aryl aldehydes is reported. This strategy offered a concise and high atom-economic approach to vinyl amines and vinyl alcohols.

Rhodium/copper-catalyzed annulation of benzimides with internal alkynes: indenone synthesis through sequential C-H and C-N cleavage.

Doubled up: a rhodium(III)/copper(II) system co-catalyzes the annulation of benzimides with internal alkynes for the synthesis of indenones (see scheme; Cp*=C(5) Me(5)). The reaction involves an uncommon nucleophilic addition of a transition-metal-carbon bond to an imide moiety. This novel reaction provides a facile route to synthesize indenones from readily available benzimides and internal alkynes.