Access to Diverse Organoborons by α-Deprotonation and Functionalization of Benzylboronates.

Described here is a simple and efficient method to prepare organoboron compounds through α-deprotonation and functionalization of benzylboronates. In addition to alkyl halides, chlorosilane, deuterium oxide, and trifluoromethyl alkene could also serve as electrophiles in this approach. Notably, the boryl group enables high diastereoselectivities when unsymmetrical secondary α-bromoesters are used. This methodology exhibits a broad substrate scope and high atomic efficiency and offers an alternative C-C bond disconnection for the synthesis of benzylboronates.

Nickel-Catalyzed Negishi Cross-Coupling of Alkyl Halides, Including Unactivated Tertiary Halides, with a Boron-Stabilized Organozinc Reagent.

Nickel-catalyzed cross-coupling of unactivated tertiary alkyl electrophiles with alkylmetal reagents is still a challenge. We report herein a nickel-catalyzed Negishi cross-coupling of alkyl halides, including unactivated tertiary halides, with boron-stabilized organozinc reagent BpinCH2ZnI, yielding versatile organoboron products with high functional-group tolerance. Importantly, the Bpin group was found to be indispensable for accessing the quaternary carbon center. The synthetic practicability of the prepared quaternary organoboronates was demonstrated by their conversion to other useful compounds.

Tuning Fluorination of Carbonates for Lithium-Ion Batteries: A Theoretical Study.

It is critical to design the solvents or additives to provide high oxidation stability of electrolyte and good solid-electrolyte interphase (SEI) in lithium secondary batteries. In this work, we used quantum chemical calculations to evaluate carbonates with various fluorinated patterns to satisfy the requirements of antioxidation, stabilize SEI films, and modify solvation structures. The thermodynamic cycle method was used to calculate the oxidation and reduction potentials of a series of fluorinated linear (dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate) and cyclic carbonates (ethylene carbonate, propylene carbonate, and 2,3-butanediol cyclic carbonate) vs Li+/Li. Both quantity and position of fluorine substitutions have a significant impact on the oxidation and reduction potentials according to correlation analyses. The instinctive causes for the potential change were the influence of the fluorinated position on the frontier orbital. We further studied lithium-ion coordinated fluorinated carbonates and found that the binding energy is mostly determined by electrostatic interaction according to the energy decomposition analysis. Fluorination will weaken the coordination ability of carbonates, which is demonstrated by their electrostatic potential distributions. Furthermore, it was found that the linear carbonate fluorinated at the α-position under reduction reaction easily produces LiF in situ, which was beneficial to the construction of good SEI. Finally, we provide some suggestions for the development of fluorinated carbonates based on the theoretical studies in this work.

Testing network autocorrelation without replicates.

In this paper, we propose a portmanteau test for whether a graph-structured network dataset without replicates exhibits autocorrelation across units connected by edges. Specifically, the well known Ljung-Box test for serial autocorrelation of time series data is generalized to the network setting using a specially derived central limit theorem for a weakly stationary random field. The asymptotic distribution of the test statistic under the null hypothesis of no autocorrelation is shown to be chi-squared, yielding a simple and easy-to-implement procedure for testing graph-structured autocorrelation, including spatial and spatial-temporal autocorrelation as special cases. Numerical simulations are carried out to demonstrate and confirm the derived asymptotic results. Convergence is found to occur quickly depending on the number of lags included in the test statistic, and a significant increase in statistical power is also observed relative to some recently proposed permutation tests. An example application is presented by fitting spatial autoregressive models to the distribution of COVID-19 cases across counties in New York state.

Photodynamic Therapy and Multi-Modality Imaging of Up-Conversion Nanomaterial Doped with AuNPs.

Two key concerns exist in contemporary cancer chemotherapy in clinic: limited therapeutic efficiency and substantial side effects in patients. In recent years, researchers have been investigating a revolutionary cancer treatment technique, and photodynamic therapy (PDT) has been proposed by many scholars. A drug for photodynamic cancer treatment was synthesized using the hydrothermal method, which has a high efficiency to release reactive oxygen species (ROS). It may also be utilized as a clear multi-modality bioimaging platform for photoacoustic imaging (PAI) due to its photothermal effect, computed tomography (CT), and magnetic resonance imaging (MRI). When compared to single-modality imaging, multi-modality imaging delivers far more thorough and precise details for cancer diagnosis. Furthermore, Au-doped up-conversion nanoparticles (UCNPs) have an exceptionally high luminous intensity. The Au-doped UCNPs, in particular, are non-toxic to tissues without laser at an 808 nm wavelength, endowing the as-prepared medications with outstanding therapeutic efficacy but exceptionally low side effects. These findings may encourage fresh effective imaging-guided approaches to meet the goal of photodynamic cancer therapy to be created.

Photothermal Effect and Multi-Modality Imaging of Up-Conversion Nanomaterial Doped with Gold Nanoparticles.

Two key concerns exist in contemporary cancer chemotherapy in clinics: limited therapeutic efficiency and substantial side effects in patients. In recent years, researchers have been investigating revolutionary cancer treatment techniques and photo-thermal therapy (PTT) has been proposed by many scholars. A drug for photothermal cancer treatment was synthesized using the hydrothermal method, which has a high light-to-heat conversion efficiency. It may also be utilized as a clear multi-modality bioimaging platform for photoacoustic imaging (PAI), computed tomography (CT), and magnetic resonance imaging (MRI). When compared to single-modality imaging, multi-modality imaging delivers far more thorough and precise details for cancer diagnosis. Furthermore, gold-doped upconverting nanoparticles (UCNPs) have an exceptionally high target recognition for tumor cells. The gold-doped UCNPs, in particular, are non-toxic to normal tissues, endowing the as-prepared medications with outstanding therapeutic efficacy but exceptionally low side effects. These findings may encourage the creation of fresh effective imaging-guided approaches to meet the goal of photothermal cancer therapy.

SiO2 Coated Up-Conversion Nanomaterial Doped with Ag Nanoparticles for Micro-CT Imaging.

In this study, a new method for synthesizing Ag-NaYF4:Yb3+/Er3+ @ SiO2 nanocomposites was introduced. Using a hydrothermal method, the synthesized Yb3+- and Er3+-codoped NaYF4 up-conversion luminescent materials and Ag nanoparticles were doped into up-conversion nanomaterials and coated with SiO2 up-conversion nanomaterials. This material is known as Ag-UCNPs@SiO2, it improves both the luminous intensity because of the doped Ag nanoparticles and has low cytotoxicity because of the SiO2 coating. The morphology of UCNPs was observed using scanning electron microscopy (SEM), and the mapping confirmed the successful doping of Ag nanoparticles. Successful coating of SiO2 was confirmed using transmission electron microscopy (TEM). Fluorescence spectra were used to compare changes in luminescence intensity before and after doping Ag nanoparticles. The reason for the increase in luminescence intensity after doping with Ag nanoparticles was simulated using first-principles calculations. The cytotoxicity of Ag-UCNPs@SiO2 was tested via the cell counting kit-8 (CCK-8) method, and its imaging ability was characterized using the micro-CT method.

[Establishment and evaluation of multiplex PCR for detection of main pathogenic bacteria of endometritis in Tibetan sheep].

A multiplex PCR method was developed to detect the main pathogens of Qinghai Tibetan sheep endometritis. First, the genomes of five standard bacterial strains were extracted and specific primers were selected; the multiplex PCR method was established by using the genome of the standard strain as a template. The samples were collected by sterile cotton swab from Tibetan sheep uterus, and then placed in LB medium and numbered. After 48 h, the genomes of cultured bacteria were extracted and detected by single PCR method, then the positive samples were recorded. The positive samples detected by single PCR were selected for multiplex PCR detection and recorded again. The coincidence rate between these two methods was calculated to measure the accuracy of multiplex PCR. In order to identify the species of the pathogen, 30 positive samples verified by single and multiplex PCR were randomly selected for bacterial isolation and identification. In the 600 samples, the infected ratio of Streptococcus agalactiae (GBS) was 47.33%, Escherichia coli 34.83%, Staphylococcus aureus 6.5%, Salmonella and Trueperella pyogenes were negatively detected. Among the positive samples detected by multiplex PCR, the positive ratio of GBS was 45.50%, E. coli 33.50%, S. aureus 6.5%. Comparison of two detection results, Multiplex PCR detection coincidence rate is more than 95%. The isolated pathogens were identified as E. coli, GBS and S. aureus, which was consistent with the results of two methods. The multiplex PCR method was successfully established and the main pathogens of endometritis in Qinghai Tibetan sheep were GBS, E. coli and S. aureus.

Anti-inflammatory Effect of Astragalin and Chlorogenic Acid on Escherichia coli-Induced Inflammation of Sheep Endometrial Epithelium Cells.

Endometritis is one of the main diseases which harm sheep husbandry. Astragalin and chlorogenic acid (CGA) are common active ingredients of traditional Chinese medicine (TCM) with immunoprotective, antioxidant, and anti-inflammatory properties. In the present study, sheep endometrial epithelium cells (SEECs) were successfully purified and identified, and the in vitro inflammation model of SEECs induced by Escherichia coli (E. coli) was successfully established. To explore the effect of astragalin and CGA on the inflammation induced by E. coli and its potential mechanism, six groups were set up, namely, group C, M, astragalin, CGA, BAY, and STR. Cells in group C were incubated with DMEM/F12 for 6 h, while cells in group M, astragalin, CGA, BAY, and STR were incubated with DMEM/F12, astragalin, CGA, BAY, and STR for 3 h, respectively, followed by E. coli infection at a multiplicity of infection (MOI) of 1 E. coli per cell for 3 h. Subsequently, the cells and the supernatant were collected to detect the expression of genes in the toll-like receptor 4 (TLR4)/nuclear factor-kappa B (NF-κB) pathway by ELISA, qPCR, and western blot. The results showed that E. coli could induce inflammation of SEECs in vitro, while astragalin and CGA could alleviate the inflammatory response induced by E. coli via inhibiting the activation of the TLR4/NF-κB signaling pathway, which provides a theoretical and experimental foundation for preventing sheep endometritis clinically.