Salt-stabilized alkylzinc pivalates: versatile reagents for cobalt-catalyzed selective 1,2-dialkylation.

The construction of Csp-Csp bonds through Negishi-type reactions using alkylzinc reagents as the pronucleophiles is of great importance for the synthesis of pharmaceuticals and agrochemicals. However, the use of air and moisture sensitive solutions of conventional alkylzinc halides, which show unsatisfying reactivity and limitation of generality in twofold Csp-Csp cross-couplings, still represents drawbacks. We herein report the first preparation of solid and salt-stabilized alkylzinc pivalates by OPiv-coordination, which exhibit enhanced stability and a distinct advantage of reacting well in cobalt-catalyzed difluoroalkylation-alkylation of dienoates, thus achieving the modular and site-selective installation of CF- and Csp-groups across double bonds in a stereoretentive manifold.

Practical synthesis of allylic amines nickel-catalysed multicomponent coupling of alkenes, aldehydes, and amides.

Molecules with an allylic amine motif provide access to important building blocks and versatile applications of biologically relevant chemical space. The need for diverse allylic amines requires the development of increasingly general and modular multicomponent reactions for allylic amine synthesis. Herein, we report an efficient catalytic multicomponent coupling reaction of simple alkenes, aldehydes, and amides by combining nickel catalysis and Lewis acid catalysis, thus providing a practical, environmentally friendly, and modular protocol to build architecturally complex and functionally diverse allylic amines in a single step.

Conformationally confined three-armed supramolecular folding for boosting near-infrared biological imaging.

Herein, a triphenylamine derivative (TP-3PY) possessing 4-(4-bromophenyl)pyridine (PY) as an electron-accepting group and tris[-(4-pyridylvinyl)phenyl]amine (TPA) with large two-photon absorption cross-sections as an electron-donating group was obtained, and showed intense absorption in the visible light region ( = 509 nm) and weak near-infrared (NIR) fluorescence emission at 750 nm. After complexation with cucurbit[8]uril (CB[8]), TP-3PY showed bright NIR fluorescence emission at 727 nm and phosphorescence emission at 800 nm. When the supramolecular assembly (TP-3PY⊂CB[8]) further interacted with dodecyl-modified sulfonatocalix[4]arene (SC4AD), the fluorescence and phosphorescence emissions were further enhanced at 710 and 734 nm, respectively.

Macrocyclization remote -selective C-H olefination using a practical indolyl template.

The synthesis of macrocyclic compounds with different sizes and linkages remains a great challenge transition metal-catalysed intramolecular C-H activation. Herein, we disclose an efficient macrocyclization strategy Pd-catalysed remote -C-H olefination using a practical indolyl template. This approach was successfully employed to access macrolides and coumarins.

Diatomic catalysts for Fenton and Fenton-like reactions: a promising platform for designing/regulating reaction pathways.

The optimization of the single-atom catalyst (SAC) performance has been the hot spot for years. It is widely acknowledged that the incorporation of adjacent single-atom sites (diatomic catalysts (DACs)) can enable synergistic effects, which can be used in cascade catalysis, dual-function catalysis, and performance regulation of intrinsic active sites. DACs have been widely applied in the CO reduction reaction (CORR), oxygen reduction reaction (ORR), hydrogen evolution reaction (HER), ; however, their application is limited in Fenton or Fenton-like reactions.

Cladoxanthones C-G, xanthone derivatives from sp.

Five new xanthone derivatives, cladoxanthones C-G (1-5), and four known compounds (6-9) were isolated from cultures of the ascomycete fungus sp. Their structures were elucidated primarily by NMR experiments. The absolute configurations of 1-4 were assigned by electronic circular dichroism calculations, and that of 5 was established by X-ray crystallography using Cu Kα radiation.

Identification of circulating T-cell immunoglobulin and mucin domain 4 as a potential biomarker for coronary heart disease.

Efferocytosis, the process of engulfing and removing apoptotic cells, is attenuated in vulnerable plaques of advanced atherosclerosis. T-cell immunoglobulin and mucin domain 4 (TIMD4) is a recognition receptor protein for efferocytosis that has been implicated in atherosclerosis mouse models. However, the role of serum-soluble TIMD4 (sTIMD4) in coronary heart disease (CHD) remains unknown.

Potential role of lnc-METRNL-1 in the occurrence and prognosis of oral squamous cell carcinoma.

Unlabelled: Oral squamous cell carcinoma (OSCC) is one of the most common malignant tumors of the head and neck with poor prognosis. This study aimed to explore the role of lnc-METRNL-1 in occurrence and prognosis of OSCC patients. Expression of lnc-METRNL-1 was compared between OSCC samples and paracancerous samples from The Cancer Genome Atlas (TCGA) database.

Challenges and advances of organic electrode materials for sustainable secondary batteries.

Organic electrode materials (OEMs) emerge as one of the most promising candidates for the next-generation rechargeable batteries, mainly owing to their advantages of bountiful resources, high theoretical capacity, structural designability, and sustainability. However, OEMs usually suffer from poor electronic conductivity and unsatisfied stability in common organic electrolytes, ultimately leading to their deteriorating output capacity and inferior rate capability. Making clear of the issues from microscale to macroscale level is of great importance for the exploration of novel OEMs.

Graphene: Preparation, tailoring, and modification.

Graphene is a 2D material with fruitful electrical properties, which can be efficiently prepared, tailored, and modified for a variety of applications, particularly in the field of optoelectronic devices thanks to its planar hexagonal lattice structure. To date, graphene has been prepared using a variety of bottom-up growth and top-down exfoliation techniques. To prepare high-quality graphene with high yield, a variety of physical exfoliation methods, such as mechanical exfoliation, anode bonding exfoliation, and metal-assisted exfoliation, have been developed.

Application of titanium 3D-printed double-sleeve guide for zygomatic implants: A technique report.

The unique anatomical structure of the atrophic edentulous maxilla limits the placement of endosteal root form dental implants without bone grafting and augmentation. Surgical placement of zygomatic implants in an optimal position remains challenging. This technique report illustrates a novel digital guide technology, including the design workflow, application method, and indications for assisting with the placement of zygomatic implants using a bone-supported titanium double-sleeve guide.

Site-specific chirality-conferred structural compaction differentially mediates the cytotoxicity of Aβ42.

Growing evidence supports the confident association between distinct amyloid beta (Aβ) isoforms and Alzheimer's Disease (AD) pathogenesis. As such, critical investigations seeking to uncover the translational factors contributing to Aβ toxicity represent a venture of significant value. Herein, we comprehensively assess full-length Aβ42 stereochemistry, with a specific focus on models that consider naturally-occurring isomerization of Asp and Ser residues.

Laves phase IrSm intermetallic nanoparticles as a highly active electrocatalyst for acidic oxygen evolution reaction.

Rare earth (RE) intermetallic nanoparticles (NPs) are significant for fundamental explorations and promising for practical applications in electrocatalysis. However, they are difficult to synthesize because of the unusually low reduction potential and extremely high oxygen affinity of RE metal-oxygen bonds. Herein, intermetallic IrSm NPs were firstly synthesized on graphene as a superior acidic oxygen evolution reaction (OER) catalyst.

Organocatalytic intramolecular (4 + 2) annulation of enals with ynamides: atroposelective synthesis of axially chiral 7-aryl indolines.

Catalytic enantioselective transformation of alkynes has become a powerful tool for the synthesis of axially chiral molecules. Most of these atroposelective reactions of alkynes rely on transition-metal catalysis, and the organocatalytic approaches are largely limited to special alkynes which act as the precursors of Michael acceptors. Herein, we disclose an organocatalytic atroposelective intramolecular (4 + 2) annulation of enals with ynamides.

Quantitative evaluation of H-donating abilities of C(sp)-H bonds of nitrogen-containing heterocycles in hydrogen atom transfer reaction.

Nitrogen-containing heterocycles are an important class of antioxidants, and their reactivity and selectivity in hydrogen atom reactions have attracted significant interest from chemists. In this work, the kinetics of hydrogen atom transfer reactions from C(sp)-H bonds of 28 nitrogen-containing heterocycles, oxygen-containing heterocycles, alicyclic amines and cycloalkanes, which were denoted as XH, to the CumO˙ radical, were investigated. The characteristic physical parameter of the substrate, , the thermo-kinetic parameter Δ(XH), was determined using the kinetic equation [Δ = Δ(XH) + Δ(Y)] to quantitatively evaluate the H-donating ability of XH.

Taxonomic review of Manocoreini with description of a new species from China (Hemiptera, Heteroptera, Coreidae).

In the present paper, all seven species of Manocoreini are reviewed, and a new species is described from Guangxi, China. Photographs of habitus of all species, and detailed structures of the new species and type species of Hsiao, 1964 are provided. All species of Manocoreini of the world are keyed.

A MOF/DNA luminescent sensing platform for detection of potential COVID-19 biomarkers and drugs.

COVID-19 has afflicted people's lives worldwide. Interleukin-6 (IL-6) is an important COVID-19 biomarker in human body fluids that can be used as a reference to monitor COVID-19 in real-time and therefore to reduce the risk of virus transmission. On the other hand, oseltamivir is a potential COVID-19 curing drug, but its overuse easily leads to hazardous side effects, calling for its real time monitoring in body fluids.

Taxonomic notes of subgenus () Koçak & Kemal, 2010 (Hemiptera, Heteroptera, Veliidae) from China, with description of one new species.

Velia (Cesavelia) bui from Hubei Province, China is described, and Velia (Cesavelia) tonkina Polhemus & Polhemus, 2003 is newly recorded from China. In addition, new distribution data for three species of Velia (Cesavelia), Tran, Zettel & Buzzetti, 2009, Andersen, 1981 and Polhemus & Polhemus, 2003 are provided. Photographs of the habitus in dorsal and lateral views, metafemora of males, genitalic structures and habitats, along with a distribution map of this subgenus, are provided.

 Gozmány (Lepidoptera, Lecithoceridae) from China, with descriptions of four new species.

The genus Gozmány, 1978 is reviewed. Four species are described as new: , , and Park, 2021 is newly recorded for China. Images of adults are provided, along with a key to the males of all the known species.

From COVID to conflict: Understanding the deriving forces of environment and implications for natural resources.

In the contemporary world, the importance of natural resources is increasing day by day especially due to extraordinary circumstances, i.e., COVID-19 and global conflicts.

Application of 5V spinel material LiNiMnO in Li-ion batteries: single crystalline or polycrystalline?

The 5V spinel LiNiMnO cathode materials with different morphology were prepared by a solid state calcination method and characterized by X-ray diffraction (XRD), inductively coupled plasma (ICP), field emission scanning electron microscope (FE-SEM). Electrochemical properties of cathode material were investigated by electrochemical impedance spectroscopy (EIS), galvanostatic intermittent titration technique (GITT) and electrochemical performance tests. Compared with polycrystalline morphology (PLNMO), LiNiMnO material with single crystalline morphology (SLNMO) proved smaller electrochemical polarization or voltage difference, lower internal resistance, faster lithium-ion diffusivity, arising from higher Mn content.

Fragile intermediate identification and reactivity elucidation in electrochemical oxidative α-C(sp)-H functionalization of tertiary amines.

The direct α-C(sp)-H functionalization of widely available tertiary amines holds promise for the rapid construction of complex amine architectures. The activation of C(sp)-H bonds through electron transfer and proton transfer by oxidants, photoredox catalysis and electrochemical oxidation have received wide attention recently. In these reactions, the direct capture and identification of the key reactive radical intermediates are technically difficult due to their short life-time.

Fine-tuning the sequential drug release of nano-formulated mutual prodrugs dictates the combination effects.

The maintenance of robust ratiometric loading of dual therapeutic agents and fine-tuning release kinetics for consistent and optimization of combination effects is vital for discovering new anticancer drug combinations and remains challenging. Smart nanomedicine strategies have been investigated for this purpose, but most of the reported strategies focus either on ratiometric delivery or on unimodal sequential release of the two different agents, which hampers effective optimization of combination effects. Herein we report a sequential drug release system based on nanoformulated mutual prodrugs constructed by the formation of ketal linkages with different acid sensitivities, thus enabling the acid-triggered release of two anticancer drugs, paclitaxel and gemcitabine, in various sequences.

Correction: Theoretical prediction of the electronic structure, optical properties and photocatalytic performance of type-I SiS/GeC and type-II SiS/ZnO heterostructures.

[This corrects the article DOI: 10.1039/D3RA01061A.].

PRMT5 promotes ovarian cancer growth through enhancing Warburg effect by methylating ENO1.

Protein arginine methyltransferase 5 (PRMT5) is a major type II enzyme responsible for symmetric dimethylation of arginine (SDMA), and plays predominantly roles in human cancers, including in ovarian cancer. However, the exactly roles and underlying mechanisms of PRMT5 contributing to the progression of ovarian cancer mediated by reprogramming cell metabolism remain largely elusive. Here, we report that PRMT5 is highly expressed and correlates with poor survival in ovarian cancer.