Combining anodic alcohol oxidative coupling for C-C bond formation with cathodic ammonia production.

Electrocatalytic oxidation of alcohols using heterogeneous catalysts is a promising aqueous, energy-efficient and environmentally friendly approach, especially for coupling different alcohols to prolong the carbon chain via co-oxidation. Precisely regulating critical steps to tailor electrode materials and electrolyte composition is key to selectively coupling alcohols for targeted synthesis. However, selectively coupling different alcohols remains challenging due to the lack of effective catalyst and electrolyte design promoting specific pathways. Herein, we demonstrate a paired electrolysis strategy for combining anodic oxidative coupling of ethanol (EtOH) and benzyl alcohol (PhCH2OH) to synthesize cinnamaldehyde (CAL) and cathodic ammonia production. The strategies involve: (i) utilizing the salt-out effect to balance selective oxidation and coupling rates; (ii) developing platinum-loaded nickel hydroxide electrocatalysts to accelerate intermediate coupling kinetics; (iii) introducing thermodynamically favorable nitrate reduction at the cathode to improve coupling selectivity by avoiding hydrogenation of products while generating valuable ammonia instead of hydrogen. We achieved 85% coupling selectivity and 278 µmol/h NH3 productive rate at 100 mA/cm2 with a low energy input (∼1.63 V). The membrane-free, low energy, scalable approach with a wide substrate scope highlights promising applications of this methodology. This work advances heterogeneous electrocatalytic synthesis through rational design principles that integrate anodic oxidative coupling with cathodic nitrate reduction reactions, having synergistic effects on efficiency and selectivity.

Synthesis and Application Dichalcogenides as Radical Reagents with Photochemical Technology.

Dichalcogenides (disulfides and diselenides), as reactants for organic transformations, are important and widely used because of their potential to react with nucleophiles, electrophilic reagents, and radical precursors. In recent years, in combination with photochemical technology, the application of dichalcogenides as stable radical reagents has opened up a new route to the synthesis of various sulfur- and selenium-containing compounds. In this paper, synthetic strategies for disulfides and diselenides and their applications with photochemical technology are reviewed: (i) Cyclization of dichalcogenides with alkenes and alkynes; (ii) direct selenylation/sulfuration of C-H/C-C/C-N bonds; (iii) visible-light-enabled seleno- and sulfur-bifunctionalization of alkenes/alkynes; and (iv) Direct construction of the C(sp)-S bond. In addition, the scopes, limitations, and mechanisms of some reactions are also described.

High-Frequency Normalizing Flow for Image Rescaling.

It is desirable to develop efficient image rescaling methods to transmit digital images with different resolutions between devices and assure visual quality. In image downscaling, the inevitable loss of high-frequency information makes the reverse upscaling highly ill-posed. Recent approaches focus on joint learning of image downscaling and upscaling (e.g., rescaling). However, existing methods still fail to recover satisfactory high-frequency signals when upscaling. To solve it, we propose high-frequency flow (HfFlow), which learns the distribution of high-frequency signals during rescaling. HfFlow is an overall invertible framework with a conditional flow on the high-frequency space to compensate for the information lost during downscaling. To facilitate finding the optimal upscaling solution, we introduce a reference low-resolution (LR) manifold and propose a cross-entropy Gaussian loss (CGloss) to force the downscaled manifold closer to the reference LR manifold and simultaneously fulfill recovering missing details. HfFlow can be generalized to other scale transformation tasks such as image colorization with its excellent rescaling capacity. Qualitative and quantitative experimental evaluations demonstrate that HfFlow restores rich high-frequency details and outperforms state-of-the-art rescaling methods in PSNR, SSIM, and perceptual quality metrics.

The effect of repetitive transcranial magnetic stimulation on the negative symptoms of chronic schizophrenia and serum brain-derived neurotrophic factor. / Wplyw powtarzalnej przezczaszkowej stymulacji magnetycznej na negatywne objawy schizofrenii i surowiczy neurotroficzny czynnik pochodzenia mózgowego.

OBJECTIVES: This study aims to investigate the therapeutic effect of repetitive transcranial magnetic stimulation (rTMS) on the negative symptoms of chronic schizophrenia and serum brainderived neurotrophic factor (BDNF). METHODS: A total of 86 patients with chronic schizophrenia hospitalised from March to October 2019 were randomly assigned to the active rTMS group or the sham rTMS group, with 43 patients in each group. All patients were administered paliperidone orally at a dose of 3-6 mg/d, and rTMS treatment was given to the active rTMS group. The Positive and Negative Syndrome Scale (PANSS) score and the serum BDNF concentration were calculated in both groups at baseline and after two and four weeks of treatment. RESULTS: There were no statistically significant differences in the PANSS scores and serum BDNF concentrations between the two groups before treatment (p > 0.05). However, after four weeks of treatment, the change in the score on the negative symptom scale in the active rTMS group was greater than in the sham rTMS group (p < 0.05), and the serum BDNF levels in the active rTMS group were higher than in the sham rTMS group (p < 0.05). CONCLUSIONS: Four weeks of continuous rTMS treatment can effectively improve the negative symptoms of schizophrenia, and the serum concentration of BDNF increases as the duration of rTMS treatment increases.

Pd-Catalyzed Cross-Coupling of Sb-Aryl Stibines with Halogenomethyl Arenes to Give Unsymmetirc Diarylmethanes.

Herein, we describe a general method for the synthesis of unsymmetric diarylmethanes from (hetero)aryl methyl halides and Sb-aryl stibines. This protocol shows a broad substrate scope and a good functional group tolerance. Drug molecules, including beclobrate 3al and bifemelane 3as, and drug derivatives, including celecoxib 3p, ibuprofen 3ao, and probenecid 3ap, were efficiently synthesized on a gram scale. The possible mechanism is proposed on the basis of the results of control experiments.

MACA Fast and Efficient Method for Detecting H2O2 by a Dual-Locked Model Chemosensor.

A pentafluorobenzene-containing fluorescent probe GW-1 was designed and synthesized for monitoring hydrogen peroxide. The probe's fluorescence was activated by a dual-locked model system that consists of a spiro location and a target analyte, which avoids the "alkalizing effect." The smart GW-1 exhibited high selectivity toward hydrogen peroxide over other reactive oxygen species (ROS) by a dual-controlled molecular switch. These features are favorable for H2O2 sensing and pH changes in bioanalytical and biomedical applications.

QTL mapping of root traits in wheat under different phosphorus levels using hydroponic culture.

BACKGROUND: Phosphorus (P) is an important in ensuring plant morphogenesis and grain quality, therefore an efficient root system is crucial for P-uptake. Identification of useful loci for root morphological and P uptake related traits at seedling stage is important for wheat breeding. The aims of this study were to evaluate phenotypic diversity of Yangmai 16/Zhongmai 895 derived doubled haploid (DH) population for root system architecture (RSA) and biomass related traits (BRT) in different P treatments at seedling stage using hydroponic culture, and to identify QTL using 660 K SNP array based high-density genetic map. RESULTS: All traits showed significant variations among the DH lines with high heritabilities (0.76 to 0.91) and high correlations (r = 0.59 to 0.98) among all traits. Inclusive composite interval mapping (ICIM) identified 34 QTL with 4.64-20.41% of the phenotypic variances individually, and the log of odds (LOD) values ranging from 2.59 to 10.43. Seven QTL clusters (C1 to C7) were mapped on chromosomes 3DL, 4BS, 4DS, 6BL, 7AS, 7AL and 7BL, cluster C5 on chromosome 7AS (AX-109955164 - AX-109445593) with pleiotropic effect played key role in modulating root length (RL), root tips number (RTN) and root surface area (ROSA) under low P condition, with the favorable allele from Zhongmai 895. CONCLUSIONS: This study carried out an imaging pipeline-based rapid phenotyping of RSA and BRT traits in hydroponic culture. It is an efficient approach for screening of large populations under different nutrient conditions. Four QTL on chromosomes 6BL (2) and 7AL (2) identified in low P treatment showed positive additive effects contributed by Zhongmai 895, indicating that Zhongmai 895 could be used as parent for P-deficient breeding. The most stable QTL QRRS.caas-4DS for ratio of root to shoot dry weight (RRS) harbored the stable genetic region with high phenotypic effect, and QTL clusters on 7A might be used for speedy selection of genotypes for P-uptake. SNPs closely linked to QTLs and clusters could be used to improve nutrient-use efficiency.

HMGB1 Turns Renal Tubular Epithelial Cells into Inflammatory Promoters by Interacting with TLR4 During Sepsis.

Our study was undertaken to investigate whether the inflammatory mediator high-mobility group box 1 (HMGB1) can enter the renal tissue and urine and what is the functional change of renal tubular epithelial cells (TECs) interacting with HMGB1 during sepsis. We found that the transcription levels of interleukin 1 (IL-1) and interleukin 6 (IL-6) mRNA in TECs increased significantly during sepsis and these processes can be blocked by splenectomy. We also found out HMGB1 accumulated in the renal tissue and entered urine during sepsis and toll-like receptor 4 (TLR4) was expressed by TECs. In vitro, we demonstrated that HMGB1 induced MAPK and NF-κB activation and G1 cell cycle arrest in TECs. We also found that the mRNA transcription levels of IL-1, IL-6, and tissue inhibitor of metalloproteinases 2 (TIMP2) increased significantly and the IL-1, IL-6, and TIMP2 can be secreted by TECs stimulated by HMGB1. In contrast, LPS RS can block all of the processes above in vitro. In vivo, the increase of the mRNA transcription level of TIMP2 was also observed. These data indicate that HMGB1 accumulates in renal tissue and enters the urine and the interaction between HMGB1 and TLR4 turns TECs into inflammatory promoters during sepsis.

(E)-N'-(2-Chloro-benzyl-idene)-1-methyl-4-nitro-1H-pyrrole-2-carbohydrazide.

In the title compound, C13H11ClN4O3, the phenyl and pyrrolyl ring are linked by an ac-yl-hydrazone (R 2C=N-N-CO-R) group, forming a slightly bent mol-ecule: the dihedral angle subtended by the the phenyl and pyrrolyl rings is 8.46 (12)°. In the crystal, the three-dimensional supra-molecular structure is assembled by N-H⋯O hydrogen bonding. Mol-ecular sheets are formed parallel to (101) in a herringbone arrangement by weak van der Waals inter-actions; weak π-π [centroid-centroid phen-yl-phenyl and pyrrol-yl-pyrrolyl distances of 3.7816 (3) and 3.8946 (2) Å, respectively] inter-actions occur between neighbouring sheets.

Tetra-kis[µ-2-(meth-oxy-carbon-yl)benzoato-κ(2) O (1):O (1')]bis-[(acetonitrile-κN)copper(II)](Cu-Cu).

In the binuclear copper(II) title complex, [Cu2(C9H7O4)4(C2H3N)2], an inversion centre is situtated at the mid-point of the Cu-Cu bond. The Cu(II) atom together with its four coordinated O atoms are in a distorted planar square arrangement while the nitro-gen and the other Cu(II) atom are located in apical positions. The whole mol-ecule looks like a paddle-wheel. In the crystal, chains are assembled along the b axis through C-H⋯O hydrogen bonds and slipped π-π inter-actions between the benzene rings of neighbouring mol-ecules [centroid-centroid distance = 3.6929 (3) Šand slippage = 0.641 (1) Å].

TEE monitoring for RA-horizontal paradoxical arterial air embolism during sitting-position surgery.

A 36-year-old woman suffered meningioma in her right cerebellopontine angle. Air embolisms often complicate sitting-position surgeries. Because TEE guides the localization of central venous catheters and promptly locates air embolisms promptly enough for effective treatment, TEE is an effective monitoring method for sitting-position surgeries.

The incremental effect of obstructive sleep apnea syndrome on right and left ventricular myocardial performance in newly diagnosed essential hypertensive subjects.

Obstructive sleep apnea syndrome (OSAS) may predispose patients to congestive heart failure, suggesting a deleterious effect of OSAS on myocardial contractility. We investigated whether essential hypertensive individuals with OSAS are characterized by decreased right and left ventricular myocardial performance. Our study population consisted of 45 consecutive patients with newly diagnosed untreated stage I-II essential hypertension suffering from OSAS (35 men, aged 49+/-8 years) and 48 hypertensives without OSAS, matched for age, sex, level of blood pressure, heart rate, body mass index and smoking status. All subjects underwent polysomnography and echocardiography. Right and left ventricular functions were evaluated using the myocardial performance index (MPI). Right and left ventricular functions were altered in hypertensives with OSAS. The mean right MPI was 0.26+/-0.11 in hypertensives without OSAS and 0.51+/-0.16 in hypertensives with OSAS (P<0.01). The mean left MPI values were 0.29+/-0.07 and 0.44+/-0.13, respectively (P<0.01). Right and left MPI correlated positively and significantly with apnea-hypopnea index (rho=0.40, P=0.002).OSAS is associated with impaired right and left ventricular function. These phenomena were independent of hypertension.

[Effects of elemental sulphur and dicyandiamide on mitigating NO3- -N leaching loss from vegetable soil].

In a pot experiment with allium as test plant and NH4HCO3 as nitrogen source, this paper studied the effects of element sulphur (S0) and dicyandiamide (DCD) on mitigating the NO3- -N leaching loss from soil and on soil inorganic nitrogen (NO3- -N and NH4+ -N) content. The results showed that within the 12 weeks of the experiment, the cumulative leaching loss of soil NO3- -N in treatments S0 + DCD and S0 was 83%-86% and 83% lower, while that of soil NH4+ -N was 16.8-21.0 mg x pot(-1) and 20.4-25.0 mg x pot(-1) higher than CK, respectively, and the cumulative loss of soil (NH4+ + NO3-)-N was 60% lower. By the end of the experiment, soil inorganic nitrogen content in treatments S0 + DCD and S0 was 79.9%-85.4% and 74.9-82.6% higher than CK, respectively. The cumulative leaching loss of inorganic N in treatment S0 + DCD was 4.6%-14.4% and 15.4%-30.1% lower, and the soil inorganic nitrogen content by the end of the experiment was 6.1% and 16.8%-36.0% higher than that of treatments S0 and DCD, respectively. Similar results were obtained when S0 was replaced by Na2S2O3, but not by Na2SO4. The fact that the application of S0 could obviously decrease the NO3- -N leaching loss from soil could be contributed to the inhibitory effects of S2O3(2-) and S4O6(2-) originated from S0 oxidation in soil on the nitrification of NH4+ -N. S0 could retard the decomposition of DCD due to the effect of its oxidized products S2O3(2-) and S4O6(2-), and thus, extend the inhibitory effect of DCD on NH4+ -N nitrification. It is suggested that S0 combined with DCD could be used as an effective nitrification inhibitor to control the NO3- -N leaching loss from vegetable soils.