A General Photoactive H-Bonding EDA Complex Model Drives the Selective Hydrothiolation and Hydroxysulfenylation of Carbonyl Activated Alkenes.

Excitation of photoactive electron donor-acceptor (EDA) complexes to generate radical is a promising approach in radical chemistry. In this study, we introduce a new model of H-bonding EDA complexes for the selective hydrothiolation and hydroxysulfenylation of carbonyl-activated alkenes with diverse thiols under visible light conditions. The reliability of this H-bonding EDA complex model has been confirmed by meticulous experimental and theoretical calculations. Mechanistic investigations have revealed the significant influence of the solvent in determining whether the excitation of photoactive H-bonding EDA complex leads to charge transfer (CT) or energy-charge transfer (En-CT), thereby controlling Markovnikov and anti-Markovnikov selectivity. Notably, the Quantum Theory of Atoms in Molecules (QTAIM) analysis clearly shows that the excited state of the C＝O---H-S EDA complex involves closed-shell partially covalent interactions.

Ag@AuNP-Functionalized Capillary-Based SERS Sensing Platform for Interference-Free Detection of Glucose in Urine Using SERS Tags with Built-In Nitrile Signal.

A Ag@AuNP-functionalized capillary-based surface-enhanced Raman scattering (SERS) sensing platform for the interference-free detection of glucose using SERS tags with a built-in nitrile signal has been proposed in this work. Capillary-based SERS capture substrates were prepared by connecting 4-mercaptophenylboronic acid (MBA) to the surface of the Ag@AuNP layer anchored on the inner wall of the capillaries. The SERS tags with a built-in interference-free signal could then be fixed onto the Ag@AuNP layer of the capillary-based capture substrate based on the distinguished feature of glucose, which can form a bidentate glucose-boronic complex. Thus, many "hot spots" were formed, which produced an improved SERS signal. The quantitative analysis of glucose levels was realized using the interference-free SERS intensity of nitrile at 2222 cm-1, with a detection limit of about 0.059 mM. Additionally, the capillary-based disposable SERS sensing platform was successfully employed to detect glucose in artificial urine, and the new strategy has great potential to be further applied in the diagnosis and control of diabetes.

Dual Activation Strategy to Achieve C-C Cleavage of Cyclobutanes: Development and Mechanism of Rh and Zn Cocatalyzed [4 + 2] Cycloaddition of Yne-Vinylcyclobutanones.

Reported here is the Rh and Zn cocatalyzed [4 + 2] cycloaddition of newly designed yne-vinylcyclobutanones, which can generate 5/6 or 6/6 bicyclic products with an all-carbon quaternary bridgehead center. The reaction has a broad scope and can realize chirality transfer from enantioenriched substrates to the cycloadducts. The key to the success of this [4 + 2] reaction is the introduction of a vinyl group to cyclobutanones, which helps the C-C cleavage of vinylcyclobutanones via oxidative addition. This C-C cleavage step is synergistically aided by Zn coordination to the carbonyl group of vinylcyclobutanones. Of the same importance, visual kinetic analysis and computational studies have been carried out to support the dual activation in the rate-determining C-C cleavage, to derive the rate law of the [4 + 2] reaction, to understand another role of Zn in helping the in situ generation of the cationic Rh catalyst and preventing catalyst deactivation, and to analyze the key transition states and intermediates involved.

Atom Substitution Defects of Hexagonal Boron Phosphide Suppress Charge Recombination.

Point defects, during e-h recombination, are a key factor in impacting optoelectronic device performance. Using nonadiabatic molecular dynamics (NAMD), here we investigate the nonradiative recombination of pristine, missing atom defects, including phosphorus vacancies (VP) and phosphorus and boron vacancies (VBP), and atom substitution defects, containing boron on the phosphorus site (BP) and phosphorus on the boron site (PB) of 2D monolayer hexagonal boron phosphide (h-BP). Carrier dynamics in the pristine h-BP and the defect engineered systems reveal that atom substitution defects BP and PB can suppress e-h nonradiative recombination. This is caused by the introduction of several low-frequency phonons in defect states. Electron-phonon coupling between the electronic state and these low-frequency phonons shortens the decoherence time and the nonadiabatic coupling. Also, the atom substitution systems with one defect state introduce fewer carrier recombination channels. Such a mechanism can be extended to other 2D materials with the same structure as h-BP.

Hydrophosphorylation of electron-deficient alkenes and alkynes mediated by convergent paired electrolysis.

A straightforward and practical strategy for hydrophosphorylation of electron-deficient alkenes and alkynes to access γ-ketophosphine oxides, enabled by a convergent paired electrolysis (CPE) in the absence of a metal, base, and redox reagent, has been described. Mechanistic studies have revealed that the diarylphosphane oxides play the dual role of a phosphorus radical precursor and hydrogen donor in this transformation.

An electrochemical gram-scale protocol for pyridylation of inert N-heterocycles with cyanopyridines.

Here, we present a protocol to decyanopyridate inert N-heterocycles access to N-fused heterocycles via the mechanism of dual proton-coupled electron transfer (PCET). We describe a detailed guide to performing an electrochemical gram-scale protocol for decyanopyridation of inert N-heterocycles. The desired pyridylated quinolone is synthesized in a 5.0 mmol scale with a yield of 76%. The protocol is limited to cyanopyridines. For complete details on the use and execution of this protocol, please refer to Niu et al. (2022).

Two-dimensional ZnO/BlueP van der Waals heterostructure used for visible-light driven water splitting: A first-principles study.

Solar driven water splitting for hydrogen generation has been considered as an important method for collecting clean energy. Herein, based on first-principles calculations, we propose that ZnO/BlueP van der Waals heterostructure can realize overall water splitting reaction for hydrogen generation. Strikingly, the band-gap of 1.83 eV is appropriate, and band alignments straddle the water redox potentials, ensuring the occurrence of hydrogenevolutionreaction and oxygen evolution reaction. Charge density distribution and carrier mobility exhibit significant charge separation and transfer. Visible-light response is improved compared with those of the isolated monolayers. Moreover, hydrogenevolutionreaction is actually realized on the ZnO layer, while oxygen evolution reaction is implemented on the BlueP layer. Through the investigation of the adsorption and dissociation reactions of H2O, we observe that two neighboring H*s prefer to combine to form H2 by overcoming a lowered energy barrier of 0.75 eV. Strain effect indicates that the lateral compressive strain of -4% to 0% and the vertical tensile strain of 0% to +6% can effectively tune band-gap and band alignments. The results indicate that ZnO/BlueP vdW heterostructure is probable highly efficient photoelectric material used for visible-light driven water splitting for hydrogen generation.

Electrochemical ammonium-cation-assisted pyridylation of inert N-heterocycles via dual-proton-coupled electron transfer.

A straightforward and practical strategy for pyridylation of inert N-heterocycles, enabled by ammonium cation and electrochemical, has been described. This protocol gives access to various N-fused heterocycles and bidentate nitrogen ligand compounds, through dual-proton-coupled electron transfer (PCET) and radical cross-coupling in the absence of exogenous metal and redox reagent. It features broad substrate scope, wide functional group tolerance, and easy gram-scale synthesis. Various experiments and density functional theory (DFT) calculation results show the mechanism of dual PCET followed by radical cross-coupling is the preferred pathway. Moreover, ammonium salt plays the dual role of protonation reagent and electrolyte in this conversion, and the resulting product 9-(pyridin-4-yl)acridine compound can be used for fluorescence recognition of Fe2+ and Pd2+ with high sensitivity.

Research on the Prediction of A-Share "High Stock Dividend" Phenomenon-A Feature Adaptive Improved Multi-Layers Ensemble Model.

Since the "high stock dividend" of A-share companies in China often leads to the short-term stock price increase, this phenomenon's prediction has been widely concerned by academia and industry. In this study, a new multi-layer stacking ensemble algorithm is proposed. Unlike the classic stacking ensemble algorithm that focused on the differentiation of base models, this paper used the equal weight comprehensive feature evaluation method to select features before predicting the base model and used a genetic algorithm to match the optimal feature subset for each base model. After the base model's output prediction, the LightGBM (LGB) model was added to the algorithm as a secondary information extraction layer. Finally, the algorithm inputs the extracted information into the Logistic Regression (LR) model to complete the prediction of the "high stock dividend" phenomenon. Using the A-share market data from 2010 to 2019 for simulation and evaluation, the proposed model improves the AUC (Area Under Curve) and F1 score by 0.173 and 0.303, respectively, compared to the baseline model. The prediction results shed light on event-driven investment strategies.

1,2-Hydroboration of Pyridines by Organomagnesium.

Hydroboration of pyridine derivatives at room temperature with earth-abundant and biocompatible magnesium catalysts ligated by phosphinimino amides is developed. Fine turnover frequency (TOF) and distinguished 1,2-regioselectivity have been achieved. The exclusive chemoselective carbonyl hydroboration happens with competitive TOF. A HBpin assisted mechanism is deduced by the reaction rate law, activation parameters, and kinetic isotope effect (KIE) in combination with DFT calculations. To our knowledge, this is the first example of pyridine 1,2-dearomatization by Mg-based catalysts.

DFT study on the mechanism of bimetallic Pd-Zn-catalyzed cycloaddition of alkynyl aryl ethers with internal alkynes.

The reaction mechanism of bimetallic Pd-Zn-catalyzed cycloaddition of alkynyl aryl ethers with internal alkynes has been studied theoretically. Besides cycloaddition reaction, the dimerization of alkynyl aryl ethers was also considered. Both C6H5OC[triple bond, length as m-dash]CSiiPr3 and C6H5OC[triple bond, length as m-dash]CSiMe3 were chosen as the substrates. The reactions involve C-H activation of the substrate, acetic acid rotation, H transformation, MeC[triple bond, length as m-dash]CMe or substrate insertion into the Pd-phenyl bond and reductive elimination steps. It is found that cycloaddition is favored for C6H5OC[triple bond, length as m-dash]CSiiPr3, while dimerization is preferred for C6H5OC[triple bond, length as m-dash]CSiMe3, because the steric repulsion between two bulky SiiPr3 groups is relatively large and the steric repulsion between two small SiMe3 groups is relatively small. In addition, besides C6H5OC[triple bond, length as m-dash]CSiiPr3, four other substrates C6H5CH2C[triple bond, length as m-dash]CSiiPr3, C6H5C(O)C[triple bond, length as m-dash]CSiiPr3, C6H5SC[triple bond, length as m-dash]CSiiPr3 and C6H5N(H)C[triple bond, length as m-dash]CSiiPr3 have been calculated as the substrates for cycloaddition reaction with MeC[triple bond, length as m-dash]CMe. Among the five substrates, C6H5OC[triple bond, length as m-dash]CSiiPr3 has the lowest energy barrier (29.9 kcal mol-1), consistent with the experimental observation that C6H5OC[triple bond, length as m-dash]CSiiPr3 is the appropriate substrate for successful cycloaddition.

Assessment of the maximum allowed acid deposition load at current stage in China.

Soil acidification caused by acid deposition has been significant in some forests in southern China. We present an approach for assessing the current stage maximum allowed load (SML) of acid deposition for terrestrial system in the country. The main idea was that soil base cation exchange as a finite buffer to acidity was included in the soil acidity mass balance calculation at current acidification stage. We calculated the SML for five forests in southern China. The usual critical loads for the same forests were also calculated by the steady state mass balance model for comparison. The results showed that the SML is a more tolerant limit than the critical load for the forests with soils not acidified seriously at current stage. However, the SML become a more stringent limit to acid deposition when the forest soils have acidified seriously to very low base cation saturation. In this case the SML assessment is beneficial for the soils recovering from a serious acidified state. Based on a national scale database, the SML mapping for non-agricultural soil system in China was carried out.

Insight into Pd-catalyzed branching cyclizations of enediyne-imides towards furo[2,3-b]pyridines: a DFT study.

A new type of Pd-catalyzed branching cyclizations of enediyne-imides towards furo[2,3-b]pyridines has been investigated with the help of DFT calculations. The role of the solvent DMF was probed based on the theoretical reaction mechanistic study. The chemical selectivity was investigated and found to be determined by the C[double bond, length as m-dash]C rotation step versus the (Cl-H + Pd-C(sp(2))) σ-bond metathesis step. In addition, the solvent effects were also elucidated to clarify why different solvents lead to different products.

[Experiment on pruning of Cistanche deserticola inoculated in artificial Haloxylon ammodendron forest].

At present, the objective of cutting and pruning Cistanche deserticola is to harvest in successive years and enhance the harvesting yield and quality of C. deserticola in the process of the artificial cultivating C. deserticola. An experiment was conducted focusing on cutting and pruning C. deserticola in artificial forests of Haloxylon ammodendron drip-irrigated with saline water at the hinter-land of the Taklimakan desert, according to different growth stages and lengths. The results were following: (1) The effect of cutting on C. deserticola was similar to that of pruning, which resulted in three kinds of morphological types, not related to the bloom and size of C. deserticola. (2) The growth forms were diversified after pruning. Among them, there had sprouting new body, died or maintaining life with no sprouting, mildewed on its surface layer, etc. However, some of new bodies were sprouting from the lower part of the old body. The death rate of bloomed C. deserticola was higher than that of the underground, and the death rate of the 40 cm in stubble height for C. deserticola was higher than those with the stubble height of 20 cm and 5 cm. (3) Most of the diameter of living C. deserticola after pruning was increasing, but some of them changed little. (4) The mildew and rot of C. deserticola and the broken of the roots of the H. ammodendron and the fallen of the point of the inoculated when it was dug, which would cause the death of the C. deserticola. On the other, the yield-increasing effect and the economic benefit of the techniques of the pruning of Cistanche would need further research and evaluate. Therefore, the application of this technique needs to be cautious.

[Introduction and interpretation of abcd classification system for subaxial cervical spine injury].

OBJECTIVE: To introduce and interpret ABCD classification system for subaxial cervical spine injury. METHODS: The literature related to subaxial cervical spine injury classification system was extensively reviewed, analyzed, and summarized so as to introduce the ABCD classification system. RESULTS: The ABCD classification system for subaxial cervical spine injury consists of 3 parts. The first part of the proposed classification is an anatomical description of the injury; it delivers the information whether injury is bony, ligamentous, or a combined one. The second part is the classification of nerve function, spinal stenosis, and spinal instability. The last part is optional and denotes radiological examination which is used to define injury type. Several letters have been used for simplicity to deliver the largest amount of information. And a treatment algorithm based on the proposed classification is suggested. CONCLUSION: The ABCD classification system is proposed for simplification. However further evaluation of this classification is needed.

Dissolved organic sulfur in streams draining forested catchments in southern China.

Dissolved organic sulfur (DOS) is an important fraction for sulfur mobilization in ecosystem. In this work stream waters were sampled in 25 forested sites in southern China to study the dissolved sulfur fractions. Dissolved sulfur was fractionated into dissolved organic sulfur (DOS) and inorganic sulfate (SO4(2-)) for 95 stream water samples. The results showed that the concentration of DOS ranged from 0 to 13.1 mg/L (average 1.3 mg/L) in all the streams. High concentrations of DOS in stream waters were found in the sites with high concentrations of sulfate. DOS constituted less than 60.1% of dissolved sulfur (average 17.9%). Statistical analysis showed that DOS concentration was correlated with SO4(2-) in streams waters and total sulfur in surface layer soils. The results also showed that DOS concentration in stream waters had a seasonal variation, but no trends were found with it. The implication was that the long term sulfur deposition had led the increase of the concentration and fraction of DOS in stream waters in acid rain prevailing regions

Bis(2-hydroxy-imino-methyl-6-methoxy-phenolato-κO,N)nickel(II).

The Ni atom in the title compound, [Ni(C(8)H(8)NO(3))(2)], lies on a center of inversion in a square-planar coordination enviroment. The hydroxyl group of one anion forms a short hydrogen bond to the metal-coordinated O atom of the other anion.