The Role of Nonbonded Sulfur−Oxygen Interaction in the Dissociative Electron Transfer to Nitro-Substituted Arenesulfenyl Chlorides

The electrochemical reduction of p-nitrophenyl sulfenyl chloride, o-nitrophenyl sulfenyl chloride as well as bis(4-nitrophenyl) disulfide and bis(2-dinitrophenyl) disulfide was investigated in acetonitrile at an inert electrode. Reduction standard potentials as well standard heterogeneous electron-transfer rate constants have been determined using convolution analysis. An unexpected big difference in the thermodynamics and kinetics of the initial electron-transfer process as well as a striking change in the reductive cleavage mechanism of the S−Cl bond as a function of the nitro group position on the aryl ring of the aryl sulfenyl chloride is observed. A computational study at the B3LYP level shows that this difference in behavior is due to the through-space nonbonded S···O interaction in the o-nitrophenyl sulfenyl chloride

Radical/Ion Pair Formation in the Electrochemical Reduction of Arene Sulfenyl Chlorides

Important aspects of the electrochemical reduction of a series of substituted arene sulfenyl chlorides are investigated. A striking change is observed in the reductive cleavage mechanism as a function of the substituent on the aryl ring of the arene sulfenyl chloride. With p-substituted phenyl chlorides a “sticky” dissociative ET mechanism takes place where a concerted ET mechanism leads to the formation of a radical/anion cluster before decomposition. With o-nitropheyl sulfenyl substituted chlorides a stepwise mechanism is observed where through space S···O interactions play an important role stabilizing both the neutral molecules and their reduced forms. Disulfides are generated through a nucleophilic reaction of the two-electron reduction produced anion (arenethiolate) on the parent molecule. The dissociative electron transfer theory, as well as its extension to the case of strong in-cage interactions between the produced fragments, along with the gas phase chemical quantum calculations results helped rationalize both the observed change in the ET mechanism and the occurrence of the “sticky dissociative” ET mechanism. The radical/anion pair interactions have been determined both in solution as well as in gas phase. This study shows that despite the low magnitude of in-cage interactions in acetonitrile as compared to in the gas phase, their existence strongly affects the kinetics of the involved reactions. It also shows that, as expected, these interactions are reinforced by the existence of strong electron-withdrawing substituents

High Efficiency Nondispersive Reactor for Two-Phase Reactions

A novel continuous static reactor concept improves mass transfer in two-phase chemical reactions between 1 and 2 orders of magnitude. The current paradigm for chemical reactions between two liquids requires energy-intensive mixing to disperse droplets of one phase in the continuous phase. The new reactor contacts a continuous free phase with a continuous phase constrained to a multitude of fibers. Phases come out of the reactor cleanly separated. An etherification reaction, a dehydrochlorination reaction, a transesterification reaction, and a vegetable oil neutralization were evaluated in fiber reactors. High conversions of starting materials to products were observed in minutes. Benefits of the new reactor complement the benefits of phase transfer catalyzed reactions

Image_2_Activation of POMC neurons to adiponectin participating in EA-mediated improvement of high-fat diet IR mice.tif

BackgroundInsulin resistance (IR) is one of the common pathological manifestations of metabolic-related diseases, and the prevalence of relevant diseases is high. Acupuncture is beneficial to IR patients, but the central mechanism underlying this treatment remains unclear. This study provides mechanistic insights into how electroacupuncture (EA) improves IR through the response of Pro-opiomelanocortin (POMC) neurons to adiponectin (Adipo).MethodsGlucose tolerance tests (GTT), Insulin tolerance tests (ITT) and fasting blood glucose (FBG) were detected by glucometer. Serum insulin, Adipo and skeletal muscle adiponectin receptor 1 (AdipoR1) protein levels were examined by ELISA. Homeostasis model assessment estimated insulin resistance (HOMA-IR) was calculated using the following formula: HOMA-IR = fasting insulin (FINS) (mU/L) × FBG (mmol/L)/22.5. The expression levels of AdipoR1 and Adipo mRNA in skeletal muscle were detected by real-time PCR quantification. The co-marking of c-Fos/AdipoR1 and POMC neurons were investigated using immunofluorescence. Spontaneous excitatory postsynaptic currents (sEPSCs) of POMC neurons and the response of POMC neurons to Adipo were detected via electrophysiology.ResultsEA significantly ameliorated HFD-induced impairment of GTT, ITT, FBG, and HOMA-IR which was correlated with recovery of the expression level of AdipoR1 and Adipo in skeletal muscle. The improved response of POMC neurons to Adipo in the hypothalamus may be a key factor in correcting abnormal glucose tolerance and improving IR.ConclusionThis study demonstrates that EA can ameliorate HFD-induced impaired glucose tolerance through improved response of POMC neurons to Adipo in the hypothalamus, providing insight into the central mechanism of improving IR through EA.</p

Nitrogen-Doped Mesoporous Graphene as a Synergistic Electrocatalyst Matrix for High-Performance Oxygen Reduction Reaction

To balance the anchoring sites and conductivity of the catalyst supports is a dilemma in electrocatalytic oxygen reduction reaction (ORR). Nitrogen-doped mesoporous graphene (N-MG) with large surface area, high porosity, and superior intrinsic conductivity has been developed to address this issue. Using N-MG as the backbone, a hybrid catalyst of Co₃O₄ nanocrystals embedded on N-MG (Co₃O₄/N-MG) was prepared for the electrocatalytic ORR in alkaline media. The Co₃O₄/N-MG showed high catalytic activity for the four-electron ORR, giving a more positive onset potential (0.93 V vs RHE) and a higher current density. The unique property of N-MG and the synergetic effect of Co₃O₄ and N-MG are prominent for ORR. With improved electrocatalytic activity and durability, the Co₃O₄/N-MG can be an efficient nonprecious metal catalyst and potentially used to substitute the platinum-based cathode catalysts in fuel cells and metal–air batteries

Image_1_Activation of POMC neurons to adiponectin participating in EA-mediated improvement of high-fat diet IR mice.tif

BackgroundInsulin resistance (IR) is one of the common pathological manifestations of metabolic-related diseases, and the prevalence of relevant diseases is high. Acupuncture is beneficial to IR patients, but the central mechanism underlying this treatment remains unclear. This study provides mechanistic insights into how electroacupuncture (EA) improves IR through the response of Pro-opiomelanocortin (POMC) neurons to adiponectin (Adipo).MethodsGlucose tolerance tests (GTT), Insulin tolerance tests (ITT) and fasting blood glucose (FBG) were detected by glucometer. Serum insulin, Adipo and skeletal muscle adiponectin receptor 1 (AdipoR1) protein levels were examined by ELISA. Homeostasis model assessment estimated insulin resistance (HOMA-IR) was calculated using the following formula: HOMA-IR = fasting insulin (FINS) (mU/L) × FBG (mmol/L)/22.5. The expression levels of AdipoR1 and Adipo mRNA in skeletal muscle were detected by real-time PCR quantification. The co-marking of c-Fos/AdipoR1 and POMC neurons were investigated using immunofluorescence. Spontaneous excitatory postsynaptic currents (sEPSCs) of POMC neurons and the response of POMC neurons to Adipo were detected via electrophysiology.ResultsEA significantly ameliorated HFD-induced impairment of GTT, ITT, FBG, and HOMA-IR which was correlated with recovery of the expression level of AdipoR1 and Adipo in skeletal muscle. The improved response of POMC neurons to Adipo in the hypothalamus may be a key factor in correcting abnormal glucose tolerance and improving IR.ConclusionThis study demonstrates that EA can ameliorate HFD-induced impaired glucose tolerance through improved response of POMC neurons to Adipo in the hypothalamus, providing insight into the central mechanism of improving IR through EA.</p

Flexible Cascaded Wire-in-Cavity-in-Bowl Structure for High-Performance and Polydirectional Sensing of Contaminants in Microdroplets

To improve the drawback of surface-enhanced Raman scattering (SERS) sensors that are sensitive to excitation angles and realize the monitoring of contaminants in complex environments, we have proposed and prepared a cascaded wire-in-cavity-in-bowl (WICIB) structure on flexible polydimethysiloxane, with feasibility for plasmonic coupling. We demonstrated that the WICIB structure can serve as a highly sensitive, homogeneous, and stable SERS substrate for conventional detection. The plasmonic coupling and distribution of the enhanced electromagnetic field were evidently proven by finite element simulations, and the strong electromagnetic field was regulated around the wire and inside the cavity, which is very beneficial for the polydirectional and in situ detection. By virtue of the triple synergistic enhancement effect and unique optical properties, we successfully achieved the in situ detection of the residual pollutant molecules, ziram and 2-naphthalenethiol, in microdroplets of apple juice and lake water. Accordingly, such a flexible SERS sensor exhibits great potential in on-site environmental monitoring

Supplementary document for MoS2-based multiple surface plasmonic coupling for enhanced surface-enhanced Raman scattering and photoelectrocatalytic platform utilizing the size effect - 5410675.pdf

This supplementary information is about some characteristic of SEM, XPS, XRD and other Raman spectra

The Origin of Mo₂C Films for Surface-Enhanced Raman Scattering Analysis: Electromagnetic or Chemical Enhancement?

The relatively weak Raman enhanced factors of semiconductor-based substrate limit its further application in surface-enhanced Raman scattering (SERS). Here, a kind of two-dimensional (2D) semimetal material, molybdenum carbide (Mo2C) film, is prepared via a chemical vapor deposition (CVD) method, and the origin of SERS is investigated for the first time. The detection limits of the prepared Mo2C films for crystal violet (CV) and rhodamine 6G (R6G) molecules are low at 10–6 M and 10–8 M, respectively. Our detailed theoretical analysis, based on density functional theory and the finite element method, demonstrates that the enhancement of the 2D Mo2C film is indeed CM in nature rather than the EM effects. Besides, the basic doping strategies are proposed to further optimize the SERS sensitivity of Mo2C for Fermi level regulation. We believe this work will provide a helpful guide for developing a highly sensitive semimetal SERS substrate

Three-Dimensional MXene–AgNP Hollow Spheres for In Situ Surface-Enhanced Raman Scattering Detection of Catalysis Reactions

MXenes are attractive candidates in the fields of surface-enhanced Raman scattering (SERS) and catalysis. However, most of the current studies on MXenes are based on blocks and nanosheets, limiting their SERS and catalytic properties. Herein, we have prepared 3D MXene hollow spheres wrapped with silver nanoparticles (Ti3C2–AgNP HSs) using a sacrificial template method, which exhibits excellent sensitivity with a low detection limit due to good light-trapping capability of the hollow sphere and strong localized surface plasmon resonance (LSPR) effect of AgNPs. Furthermore, it shows outstanding photocatalytic performance and realizes in situ SERS monitoring of the 4-nitrobenzenethiol (4-NTP) to 4-aminothiophenol (4-ATP) catalysis reaction. The finite-difference time-domain (FDTD) simulations confirm that 3D Ti3C2–AgNP hollow structures have stronger hot spots than 3D solid structures and higher SERS sensitivity for molecule detection. Therefore, it promises to be an excellent bifunctional material for highly sensitive SERS detection and the in situ monitoring of catalytic reactions