Dichloromethane as C1 Synthon for the Photoredox Catalytic Cyclopropanation of Aromatic Olefins.

Dichloromethane, as a readily available and inexpensive C1 synthon is proposed as a powerful building block for cyclopropanation of alkenes under mild conditions. Herein, we report a highly efficient and versatile dual photoredox system, involving a nickel aminopyridine coordination complex and a photocatalyst, for the cyclopropanation of aromatic olefins using dichloromethane, under visible-light irradiation. The cyclopropanation protocol has been successfully applied at gram scale. Mechanistic studies suggest a Ni(II) pyridyl radical complex as the key intermediate for the homolytic cleavage of the Csp3-Cl bond, generating a chloromethyl radical that is captured by the olefin coupling partner. Our findings also highlight the versatility of this methodology. By directing the radical/polar crossover process, we were able to selectively drive the reaction towards either the formation of cyclopropyl derivatives or the corresponding non-cyclic alkyl chloride products. The methodology also successfully apply to geminal dichloroalkanes, including the formation of spiro[2,2] compounds. Moreover, our methodology extends to the synthesis of deuterium-labelled cyclopropanes, demonstrating its utility in isotopic labelling and broadening its applicability in chemical synthesis and drug development.

Perturbation of clopyralid on bio-denitrification and nitrite accumulation: Long-term performance and biological mechanism.

The contaminant of herbicide clopyralid (3,6-dichloro-2- pyridine-carboxylic acid, CLP) poses a potential threat to the ecological system. However, there is a general lack of research devoted to the perturbation of CLP to the bio-denitrification process, and its biological response mechanism remains unclear. Herein, long-term exposure to CLP was systematically investigated to explore its influences on denitrification performance and dynamic microbial responses. Results showed that low-concentration of CLP (<15 mg/L) caused severe nitrite accumulation initially, while higher concentrations (35-60 mg/L) of CLP had no further effect after long-term acclimation. The mechanistic study demonstrated that CLP reduced nitrite reductase (NIR) activity and inhibited metabolic activity (carbon metabolism and nitrogen metabolism) by causing oxidative stress and membrane damage, resulting in nitrite accumulation. However, after more than 80 days of acclimation, almost no nitrite accumulation was found at 60 mg/L CLP. It was proposed that the secretion of extracellular polymeric substances (EPS) increased from 75.03 mg/g VSS at 15 mg/L CLP to 109.97 mg/g VSS at 60 mg/L CLP, which strengthened the protection of microbial cells and improved NIR activity and metabolic activities. Additionally, the biodiversity and richness of the microbial community experienced a U-shaped process. The relative abundance of denitrification- and carbon metabolism-associated microorganisms decreased initially and then recovered with the enrichment of microorganisms related to the secretion of EPS and N-acyl-homoserine lactones (AHLs). These microorganisms protected microbe from toxic substances and regulated their interactions among inter- and intra-species. This study revealed the biological response mechanism of denitrification after successive exposure to CLP and provided proper guidance for analyzing and treating herbicide-containing wastewater.

Photoredox Activation of Inert Alkyl Chlorides for the Reductive Cross-Coupling with Aromatic Alkenes.

The inertness of chloroalkanes has precluded them as coupling partners for cross-coupling reactions. Herein we disclose a general strategy for the activation of inert alkyl chlorides through photoredox catalysis and their use as coupling partners with alkenes. The catalytic system is formed by [Ni(OTf)(Py2 Ts tacn)](OTf) (1Ni ), which is responsible for the Csp3 -Cl bond activation, and [Ir(NMe2 bpy)(ppy)2 ]PF6, (PCIr NMe2 ), which is the photoredox catalyst. Combined experimental and theoretical studies show an in situ photogenerated NiI intermediate ([Ni(Py2 Ts tacn)]+ ) which is catalytically competent for the Csp3 -Cl bond cleavage via a SN 2 mechanism for primary alkyl chlorides, forming carbon-centered free radicals, which react with the olefin leading to the formation of the Csp3 -Csp3 bond. These results suggest inert alkyl chlorides can be electrophiles for developing new intermolecular strategies in which low-valent aminopyridine nickel complexes act as key catalytic species.

Effect of Whole-Course Continuous Nursing Intervention Combined with a Nursing Practice Teaching Method on Quality of Life of Children with Functional Dyspepsia and Parents' Satisfaction Based on Smart Health.

With the development of information technology, it has become a part of people's lives. WeChat is not only a popular chatting tool in daily life but can also be used in the medical field. Functional dyspepsia is a common pediatric disease, with complex pathogenic factors, which are usually attributed to abnormal gastric acid secretion and gastrointestinal dysfunction. In our research, we aim to investigate the effects of whole-course continuous nursing intervention combined with a nursing practice teaching method on the quality of life (QOL) of children with functional dyspepsia and parents' satisfaction. One hundred and twenty children with functional dyspepsia admitted to our hospital (February 2019-February 2020) were retrospectively analyzed and equally divided into the experimental group (EG) and the control group (CG) according to the order of admission. The CG received whole-course continuous nursing intervention, and the EG received whole-course continuous nursing intervention combined with the nursing practice teaching method. Children's psychological states and QOL and parents' satisfaction of both groups were compared. After discharge, compared with the CG, the negative emotion scores in the EG were remarkably lower (P < 0.001). After discharge, compared with the CG, the QOL scores (P < 0.001), the proportion of children with good and excellent QOL (P < 0.05), and parents' satisfaction (P < 0.001) in the EG were remarkably higher. For children with functional dyspepsia, whole-course continuous nursing intervention combined with the nursing practice teaching method can improve their negative emotions, QOL, and parents' satisfaction, which should be popularized in practice.

Insight into the electrocatalytic performance of in-situ fabricated electroactive biofilm-Pd: The role of biofilm thickness, initial Pd(II) concentration and the exposure time to Pd precursor.

Biogenic palladium (bio-Pd) nanoparticles have been considered as promising biocatalyst for energy generation and contaminants remediation in water and sediment. Recently, an electroactive biofilm-Pd (EAB-Pd) network, which can be used directly as electrocatalyst and show enhanced electrocatalytic performance, has exhibited tremendous application potential. However, the information regarding to the controllable biosynthetic process and corresponding catalytic properties is scarce. This study demonstrated that the catalytic performance of EAB-Pd could be influenced by Pd loading on bacteria cells (Pd/cells), which was crucial to determine the final distribution characteristic of Pd nanocrystal on EAB skeleton. For instance, the high Pd/cells (over 0.18 pg cell-1) exhibited almost 6-fold and 1.5-fold enhancement over EAB-Pds with Pd/cells below 0.03 in catalytic current toward hydrogen evolution reaction and nitrobenzene reduction, respectively. In addition, the Pd/cells was found to be affected by the synthesis factors, such as the ratio of biomass to initial Pd(II) concentration (cells/PdII) and the exposure time of EAB to Pd(II) precursor solution. The Pd/cells increased significantly as the cell/PdII ratio decreased from ~5.5 × 107 to ~1.3 × 107 cells L mg-1 or the prolongation of exposure time from 3 h to 24 h. The findings developed in this work extensively expand our knowledge for the in-situ designing biogenic electrocatalyst and provide important information for the development of its catalytic property.

Shewanella oneidensis MR-1 self-assembled Pd-cells-rGO conductive composite for enhancing electrocatalysis.

Biosynthesized noble metal nanoparticles (NPs) as promising green catalysts for electrochemical application has invited a lot of attention. However, effective electron transfer between biosynthesized NPs and electrode remains a challenge due to the uncontrollable and poor conductive property of cell substrates. In this study, graphene oxide (GO) was introduced into a bio-Pd synthesis process governed by Shewanella oneidensis MR-1, which was demonstrated to be simultaneously reduced with Pd(II) and transformed to reduced GO (rGO), resulting in the formation of a Pd-cells-rGO composite. Compared to the control without rGO (Pd-cells), the electrochemical conductivity of Pd-cells-rGO composite increased from almost zero to 196 µS cm-1, indicating the rGO facilities the electron transport across the composite. Electrochemical characterizations revealed the electrochemical active surface area (ECSA) of Pd in Pd-cells-rGO was enlarged by increasing the amount of rGO in the composite, clearly indicating that the conductive network created by rGO enable the Pd NPs receive electrons from electrode and become electrochemical active. A considerable enhancement of electrocatalytic activity was further confirmed for Pd-cells-rGO as indicated by 36.7- and 17.2-fold increase (Pd-cells-rGO with Pd/GO ratio of 5/1 vs Pd-cells) of steady state current density toward hydrogen evolution and nitrobenzene reduction at -0.7 V and -0.55 V vs Ag/AgCl, respectively. We also compared the electrocatalytic performance with MWCNTs hybrids Pd-cells-CNTs. It was found that the association of Pd, cells and rGO creates an interactive and synergistic environment to allow higher conductivity and catalytic activity under the same amount of carbon nanomaterial. The strategy developed in this work activates a highly reactive NPs and proposed a designable protocol for enhancing electrocatalytic activity of biocatalysts.

Facile Access to Bridged Ring Systems via Point-to-Planar Chirality Transfer: Unified Synthesis of Ten Cyclocitrinols.

Bridged ring systems are found in a wide variety of biologically active molecules including pharmaceuticals and natural products. However, the development of practical methods to access such systems with precise control of the planar chirality presents considerable challenges to synthetic chemists. In the context of our work on the synthesis of cyclocitrinols, a family of steroidal natural products, we herein report the development of a point-to-planar chirality transfer strategy for preparing bridged ring systems from readily accessible fused ring systems. Inspired by the proposed pathway for biosynthesis of cyclocitrinols from ergosterol, our strategy involves a bioinspired cascade rearrangement, which enabled the gram-scale synthesis of a common intermediate in nine steps and subsequent unified synthesis of 10 cyclocitrinols in an additional one to three steps. Our work provides experimental support for the proposed biosynthetic pathway and for the possible interrelationships between members of the cyclocitrinol family. In addition to being a convenient route to 5(10→19) abeo-steroids, our strategy also offers a generalized approach to bridged ring systems via point-to-planar chirality transfer. Mechanistic investigations suggest that the key cascade rearrangement involves a regioselective ring scission of a cyclopropylcarbinyl cation rather than a direct Wagner-Meerwein rearrangement.

Attenuated associations between increasing BMI and unfavorable lipid profiles in Chinese Buddhist vegetarians.

UNLABELLED: Obesity is related to hyperlipidemia and risk of cardiovascular disease. Health benefits of vegetarian diets have well-documented in the Western countries where both obesity and hyperlipidemia were prevalent. We studied the association between BMI and various lipid/lipoprotein measures, as well as between BMI and predicted coronary heart disease probability in lean, low risk populations in Southern China. The study included 170 Buddhist monks (vegetarians) and 126 omnivore men. Interaction between BMI and vegetarian status was tested in the multivariable regression analysis adjusting for age, education, smoking, alcohol drinking, and physical activity. Compared with omnivores, vegetarians had significantly lower mean BMI, blood pressures, total cholesterol, low density lipoprotein cholesterol, high density lipoprotein cholesterol, total cholesterol to high density lipoprotein ratio, triglycerides, apolipoprotein B and A-I, as well as lower predicted probability of coronary heart disease. Higher BMI was associated with unfavorable lipid/lipoprotein profile and predicted probability of coronary heart disease in both vegetarians and omnivores. However, the associations were significantly diminished in Buddhist vegetarians. CONCLUSIONS: Vegetarian diets not only lower BMI, but also attenuate the BMI-related increases of atherogenic lipid/ lipoprotein and the probability of coronary heart disease.

Relationship of carotid intima-media thickness and duration of vegetarian diet in Chinese male vegetarians.

OBJECTIVE: Many studies have shown that vegetarian diet has beneficial effects on the prevention of cardiovascular diseases. However, the effect of vegetarian diet on carotid intima-media thickness (IMT), as well as the association between IMT and duration of vegetarian diet, are still unclear. The present study aims to investigate the influence of duration of vegetarian diet on cardiovascular risk factors, and more importantly on IMT among Chinese vegetarians. METHODS: One hundred and seventy-one Chinese male vegetarians were screened for metabolic profile, cardiovascular risk and carotid IMT. They were compared with 129 age-matched omnivores recruited from a community-based health project. The effects of confounding factors were adjusted by stepwise logistic regression analysis. RESULTS: Compared to the omnivores, the vegetarians had lower BMI, weight, systolic blood pressure and diastolic blood pressure. Also, the levels of triglyceride, total cholesterol, HDL-Cholesterol, LDL-Cholesterol, ApoA1, ApoB, uric acid, albumin and γ-glutamyltransferase were significantly reduced in vegetarians. Omnivores had significantly higher fasting blood glucose than that of vegetarians. However, there were no differences in fasting insulin, C-reactive protein and HOMA-IR between the two groups. IMT was thinner in the vegetarian group than in the omnivore group (0.59 ± 0.16 vs. 0.63 ± 0.10 cm, P < 0.05). The vegetarians were divided according to duration of vegetarian diet (< 6 years, 6 to ≤ 11 years, > 11 years), those in tertile 1 (< 6 years) and tertile 2 (6 to ≤ 11 years) had shown thinner IMT as compared to the omnivores, and tertile 3 had shown no reduction. CONCLUSION: A decrease in multiple cardiovascular risk factors such as BMI, blood pressure and lipid profile was associated with vegetarian diet. Moreover, taking a low-calorie, low-protein, or vegetarian diet might have great beneficial effects on IMT through improved lipid profile, and the beneficial effects appeared to be correlated with the duration of vegetarian diet.

Puerarin improves insulin resistance and modulates adipokine expression in rats fed a high-fat diet.

The link between obesity and insulin resistance largely accounts for the pathogenesis of metabolic syndrome and diabetes mellitus, in which adipokine expression plays a key role. Puerarin, a major active isoflavone extracted from the traditional Chinese medicine Radix Puerariae, has been studied for its comprehensive biological actions. However, its effect on high-fat diet (HFD)-induced insulin resistance and adipokine expression in rat has not been well investigated. In the present study, male Sprague-Dawley rats were fed on a normal control diet (NCD) or HFD for 6 weeks, followed by administration of puerarin (100 and 200 mg/kg) for up to 8 weeks. Compared to NCD, HFD feeding for 6 weeks led to increased body weight gain and impaired glucose/insulin tolerance manifested by oral glucose/intraperitoneal insulin tolerance tests in rats. These exacerbations prolonged through HFD feeding, but were effectively reversed by puerarin administration. Enzyme-linked immunosorbent assay demonstrated that, serum levels of leptin and resistin, but not that of adiponectin, were markedly augmented by HFD and retarded by puerarin treatment. Real-time reverse transcription polymerase chain reaction results showed that, in agreement with the circulating levels, mRNA expression of leptin and resistin in epididymal white adipose tissue was modified by HFD and improved by puerarin in the same pattern. Collectively, we revealed that puerarin could improve body weight gain, glucose/insulin intolerance and adipokine expression in HFD-induced insulin resistant rats, indicating its potential value for treatment of metabolic syndrome.