Bimetallic Single‑Atom Catalysts for Water Splitting

Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by single-atom catalysts(SACs),which exhibit unique and intricate interactions between atomically dispersed metal atoms and their supports.Recently,bimetallic SACs(bimSACs)have garnered significant attention for leveraging the synergistic functions of two metal ions coordinated on appropriately designed supports.BimSACs offer an avenue for rich metal–metal and metal–support cooperativity,potentially addressing current limitations of SACs in effectively furnishing transformations which involve synchronous proton–electron exchanges,substrate activation with reversible redox cycles,simultaneous multi-electron transfer,regulation of spin states,tuning of electronic properties,and cyclic transition states with low activation energies.This review aims to encapsulate the growing advancements in bimSACs,with an emphasis on their pivotal role in hydrogen generation via water splitting.We subsequently delve into advanced experimental methodologies for the elaborate characterization of SACs,elucidate their electronic properties,and discuss their local coordination environment.Overall,we present comprehensive discussion on the deployment of bimSACs in both hydrogen evolution reaction and oxygen evolution reaction,the two half-reactions of the water electrolysis process.

Role of methoxy and C_(α)-based substituents in electrochemical oxidation mechanisms and bond cleavage selectivity of β-O-4 lignin model compounds

In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.

硅基发光材料研究进展

硅基发光材料是光电子集成的基础材料。发光多孔硅是硅基发光材料的一个新进展，已实现了硅基光电子集成，随着多孔硅研究的深化和纳米科学的发展，硅基发光材料正向纳米方向开拓。与此同时，在新的理论认识与技术条件下，硅材料改性，杂质发光，缺陷工程和硅基异质外延也呈现出新的发展趋势。硅基发光材料的发光波段已覆盖了从红外，可见到紫外的宽阔范围，正在为全色显示和光电子集成奠定材料和技术基础。

两步法编织复合材料空心断面梁的刚度性能

基于层合板类推法和一阶剪切变形位移理论 ,分析了两步法编织复合材料空心断面梁的刚度。导出了此类构件拉伸、弯曲、扭转、剪切及各种耦合刚度系数的计算公式。这些刚度系数被表为纤维与基体的类型、纤维编织角、纤维体积百分比。

Synthesis of Alkylene-linked Dimers of (-)-Huperzine A

Six alkylene-linked dimers of (-)-huperzineA (6) were prepared. All these dimers are less potent than (-)-Hup A in inhibition of AChE.

Protective effects of lipoic acid-niacin dimers against blue light-induced oxidative damage to retinal pigment epithelium cells

AIM: To evaluate the protective effects of lipoic acid-niacin(N2 L) dimers against blue light(BL)-induced oxidative damage to human retinal pigment epithelium(hRPE) cells in vitro.METHODS: h RPE cells were divided into a control group(CG), a BL group, an N2 L plus BL irradiation group, an α-lipoic acid(ALA) plus BL group, an ALA-only group, and an N2 L-only group. hRPE cellular viability was detected by performing 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium(MTT) bromide assays, and apoptosis was evaluated by annexin-V-PE/7-AAD staining followed by flow cytometry. Ultrastructural changes in subcellular organelles were observed by transmission electron microscopy. Reactive oxygen species formation was assayed by flow cytometry. The expression levels of the apoptosis-related proteins BCL-2 associated X protein(BAX), B-cell leukmia/lymphoma 2(BCL-2), and caspase-3 were quantified by Western blot analysis.RESULTS: BL exposure with a light density of 4±0.5 mW/cm2 exceeding 6 h caused hRPE toxicity, whereas treatment with a high dose of N2 L(100 mol/L) or ALA(150 mol/L) maintained cell viability at control levels. BL exposure caused vacuole-like degeneration, mitochondrial swelling, and reduced microvillus formation;however, a high dose of N2 L or ALA maintained the ultrastructure of hRPE cells and their organelles. High doses of N2 L and ALA also protected hRPE cells from BL-induced apoptosis, which was confirmed by Western blot analysis: BCL-2 expression significantly increased, while BAX and caspase-3 expression slightly decreased compared to the CG.CONCLUSION: High-dose N2 L treatment(>100 mol/L) can reduce oxidative damage in degenerating hRPE cells exposed to BL with an efficacy similar to ALA.

Effects of temperature on UV-B-induced DNA damage and photorepair in Arabidopsis thaliana

DNA damage in the form of cyclobutane pyrimidine dimers(CPDs) and (6-4) photoproducts(6-4PPs) induced by UV-B radiation in Arabidopsis thaliana at different temperatures was investigated using ELISA with specific monoclonal antibodies. CPDs and 6-4PPs increased during 3 h UV-B exposure, but further exposure led to decreases. Contrary to the commonly accepted view that DNA damage induced by UV-B radiation is temperature-independent because of its photochemical nature, we found UV-B-induction of CPDs and 6-4PPs in Arabidopsis to be slower at a low than at a high temperature. Photorepair of CPDs at 24℃ was much faster than that at 0℃ and 12℃, with 50% CPDs removal during 1 h exposure to white light. Photorepair of 6-4PPs at 12℃ was very slow as compared with that at 24℃, and almost no removal of 6-4PPs was detected after 4 h exposure to white light at 0℃. There was evidence to suggest that temperature-dependent DNA damage and photorepair could have important ecological implications.

Syntheses and Crystal Structures of Bis-[oxo-bis(p-ferrocenylbenzoxy di-n-propyltin)](I) and Bis[oxo-bis(β-ferrocenoylpropionyloxy di-n-propyltin )](II)

Bis-[oxo-bis(p-ferrocenylbenzoxy di-n-propyltin)] I and bis-[oxo-bis(-ferrocenoyl- propionyloxy di-n-propyltin)] II were synthesized and their crystal structures have been determined by X-ray diffraction analysis. The compound I2C6H6 ([(FcC6H4COOSnPr2)2O]22C6H6 or C92H108Fe4O10Sn42C6H6, Mr = 2384.16) is of triclinic, space group P?with a = 12.826(4), b = 13.099(5), c = 17.539(5) ? = 78.229(5), ?= 71.852(5), = 62.746(5)? V = 2483(1) ?, Z = 1, Dc = 1.490 g/cm3, = 0.71073 ? (MoK? =1.611 mm-1 and F(000) = 1128. The structure was refined to R = 0.0491 and wR = 0.1053 for 4690 unique reflections with I > 2(I). The compound IIC6H6 ([(FcCOCH2CH2COOSnPr2)2O]2C6H6 or C80H108Fe4O14Sn4C6H6, Mr = 2115.93) is of triclinic, space group P?with a = 11.260(4), b = 14.126(5), c = 15.961(6) ? = 91.400(6), = 110.654(6), = 104.931(6), V = 2277(1) 3, Z = 1, Dc = 1.510 g/cm3, = 0.71073 ? (MoK? = 1.750 mm-1 and F(000) = 1046. The structure was refined to R = 0.0466 and wR = 0.1138 for 5061 unique reflections with I > 2(I). The two compounds have the similar structures: both are dimers containing centrosymmetric Sn2O2 cores. But there are some differences in the ligating modes between the carboxylate groups and the Sn atoms.

二维超声联合彩色多普勒血流显像诊断卵巢良恶性病变价值

目的:探究二维超声联合彩色多普勒血流显像(CDFI)诊断卵巢良恶性病变的价值。方法:回顾性分析2018年4月-2021年4月本院接受诊治的131例卵巢肿瘤患者临床资料,根据病理组织学结果分为良性组与恶性组。均先以二维超声及CDFI对卵巢肿块超声形态结构、血流状况进行分析获取患者RI值均值、范围及分布情况,统计两种方式对良性病变检出情况,计算诊断效能。结果:131例中检出良性肿瘤86例,其中以浆液瘤、卵巢内膜异位症为主;检出卵巢癌45例,其中以上皮性卵巢癌为主。超声形态结构分析,良性肿瘤多见简单单房、简单多房表现,恶性肿瘤多见单房合并乳头表现;良性肿瘤86例中24例未见血流信号,45例恶性肿瘤内均可见血流信号,恶性组RI值[0.41±0.10(0.25~0.64)]低于良性组[0.53±0.11(0.33~0.74)](P<0.05)。经受术者工作特征曲线分析,RI值鉴别良恶性卵巢肿瘤的曲线下面积为0.794,截断值0.46。二维超声联合CDFI诊断卵巢良恶性病变的敏感度为97.8%,特异度为76.7%,准确度为84.0%。结论:良恶性卵巢肿瘤在二维超声及CDFI检查中表现差异显著,将两种方法联合应用具有良好的鉴别诊断效能。

三维相干技术在白家海地区构造解释中的应用

随着地震技术的深入发展,地震资料解释相继也得到了进一步的发展,由相干技术公司（CTC）和Amoco公司发明代表性相干体技术,主要是利用三维地震数据体中地震信号相干值的变化来描述地层、岩性等的横向非均匀性,从而研究断层、微断裂的空间展布、地质构造的异常以及岩性的空间分布特征,为地震资料解释奠定了更好的方法基础。在前人资料的基础之上,本文主要研究了三维相干体技术在白家海地区断层识别中的应用与实现,并通过相关函数来突出地震数据中出现断层时的数据的不均匀性,接着对相干数据体作时间切片,进而将断层更加清晰的显示。

Antioxidant Nature Adds Further Therapeutic Value: An Updated Review on Natural Xanthones and Their Glycosides

Plants have so much to offer as far as the discovery of new bioactive molecules is concerned.Among the several classes of phytochemicals,xanthones offer greater structural diversity and pharmacological value.They are variable but definitely antioxidant in nature.Thus they are attractive targets for natural product and medicinal chemists.Xanthones and their glycosides possess broad spectrum interesting biological activities,such as cytotoxic,anti-inflammatory,antioxidant,anti-bacterial,neuroprotective,anti-HIV,enzyme inhibition,and hypoglycemic.The radical scavenging ability of these molecules accounts for most of their added therapeutic values.This paper intended to serve as a guide for future endeavors in quest for these molecules.Structure-Activity Relationship(SAR)and mechanism of action is given for better understanding of their role as pharmacological agents.The most recent advances in the isolation of bioactive xanthones and their glycosides were presented here.This paper will assist in directed approaches towards the discovery of analogues of xanthones.

清代翡翠的化学成分及谱学特征研究

清代翡翠一直备受人们的喜爱,但是目前其研究较少,近年有些商家以B货、C货翡翠冒充清代翡翠,并尝试混淆视听。本文采用激光剥蚀电感耦合等离子体质谱仪、红外光谱仪、X射线粉末衍射仪、激光拉曼光谱仪、荧光光谱仪和扫描电子显微镜等仪器对腾冲某地出土的清代翡翠样品进行测试分析。LA-ICP-MS结果显示清代翡翠样品中Sr/Ba大于1,Eu正异常。拉曼光谱显示深绿色样品含有绿辉石,XRD显示深绿色样品主要矿物是硬玉和次要矿物是绿辉石。红外光谱显示所有样品均在2923 cm-1和2852 cm-1处存在蜡的吸收峰,没有胶及染料,说明非现代B货、C货翡翠。经过红外光谱二阶导数计算,蜡的含量较少,可能是通过加工时上蜡的步骤引入。扫描电子显微镜Mapping显示有机物C聚集在矿物裂隙中。三维荧光光谱结果显示,所有样品的荧光中心主要集中425 nm(λex)/460 nm(λem)附近,次要集中在370 nm(λex)/433 nm(λem)附近。经测试石蜡的三维荧光中心与清代翡翠的主要荧光中心相同,次要荧光中心为土壤腐殖酸。本文清代翡翠样品是以硬玉为主的天然A货翡翠,含有蜡并且由蜡和土壤腐殖酸共同导致了荧光。

Modified RNA with a Phosphate-Methylated Backbone. A Serious Omission in Our (Retracted) Study at HIV-1 RNA Loops and Integrated DNA. Specific Properties of the (Modified) RNA and DNA Dimers

After the recent publication in the Journal of Biophysical Chemistry entitled “Retracted HIV Study Provides New Information about the Status of the in Vitro Inhibition of DNA Replication by Back-bone Methylation”, it is of importance to review the results of Buck’s group on the synthesis and conformation analyses of phosphate-methylated RNAs in order to afford information on the absence of a further investigation with regard to this de facto acceptable approach. In fact these compounds belong to the very first group of RNAs with a modified neutral backbone by phosphatemethylation. In contrast to the corresponding phosphate-methylated DNAs with a frozen B-conformation, the phosphate-methylated RNAs show an A-conformation. The latter is a prerequisite for duplex formation with (complementary) (natural) RNA. A number of experiments support this fundamental statement. After the HIV study was retracted, the overall results concerning the phosphate-methylated RNAs were published without mentioning Buck’s initial proof of concept and his contributions. Generally, the (modified) dimer RNAs and DNAs possess a number of specific biophysical properties. A novel explanation is given for conflicting structural determinations.

Antimalarial activity of a novel series of artemisinin-derived 1, 2, 3-triazole dimers

Objective: To obtain suitable artimisinin-based drug candidates with high antimalarial activity.Methods: Three different reaction schemes were used to synthesize a total of 15 artemisininbased compounds.The first synthetic scheme involved the synthesis of diazido aliphatic and aromatic compounds from commercially available dihalides and azido derivatives of artemisinin.The second scheme consisted of the reaction of dibromoaliphatic compounds with sodium azide in dimethylformamide which yielded the desired compounds.Artemisinin-based compounds on treatment with sodium azide and bromotrimethylsilane in dichloromethane produced the most potent compound GB-2.Another potent compound GB-1 was synthesized from artemisinin by treatment with alcohols in the presence of Aberlyst-15 in anhydrous dichloromethane.The third scheme involved the Huisgen 1,3-dipolar cycloaddition between the synthesized aliphatic and aromatic diazides and two alkyne derivatives of artemisinin to obtain the desired artemisinin dimers with average yields.Results: The best in vitro antiplasmodial activity was shown by the compound GB-2 registering IC_(50) value 0.066 μg/mL against chloroquine-sensitive and 0.865 μg/mL against chloroquineresistant strains of Plasmodium falciparum.It suppressed 59.0% parasitaemia in vivo of rodent malaria parasite Plasmodium berghei in Swiss albino model at 50 μg/kg body weight dosage.Molecular docking interactions of Plasmodium falciparum ATP6(PfATP6) protein revealed strong bonding of GB-2 with Thr255 residue which is likely to be the reason for excellent antimalarial activity of this compound.Conclusion: Two compounds GB-1 and GB-2 exhibited excellent in vitro antiplasmodial activity and fair in vivo antimalarial activity.Of the two, GB-2 showed better activity which could be attributed to its strong bonding interactions with Thr255 as evidenced from the molecular docking study.Study helped in identifying artemisinin analogues possessing good antimalarial properties and further research in structural alterations of the selected molecules should be carried out which may result in obtaining potent drug candidates against the malarial parasite.

Deep-ultraviolet surface plasmon resonance of Al and Al_(core)/Al_2O_(3shell) nanosphere dimers for surface-enhanced spectroscopy

The localized surface plasmon resonance properties of Al and Alcore/Al2O3shell nanosphere dimers with Al and Al core nanosphere radii of 20 nm and Al2O3 shell of 2 nm in the deep-ultraviolet region have been studied using the finite difference time domain method. The extinction spectra and the electric field distribution profiles of the two dimers for various gap distances between two individual nanospheres are compared with those of the corresponding monomers to reveal the extent of plasmon coupling. It is found that with the interparticle distance decreasing, a strong plasmon coupling between two Al or Alcore/Al2O3shell nanospheres is observed accompanied by a significant red shift in the extinction spectra at the parallel polarization direction of the incident light related to the dimer axis, while for the case of the perpendicular polarization direction, a weak plasmon coupling arises characterized by a slight blue shift in the extinction spectra. The electric field distribution profiles show that benefiting from the dielectric Al2O3 shell, the gap distance of Alcore/Al2O3shell nanosphere dimers can be tailored to 〈 1 nm scale and results in a very high electric field enhancement. The estimated surface-enhanced Raman scattering enhancement factors suggests that the Alcore/Al2O3shell nanosphere dimers with the gap of 〈 1 nm gave rise to an enhancement as high as 8.1 × 10^7 for interparticle gap = 0.5 nm. Our studies reveal that the Alcore/Al2O3shell nanosphere dimers may be promising substrates for surface-enhanced spectroscopy in the deep-ultraviolet region.

The Stability of Anionic States of Thymine-Glycine Dimers with Excess Electron

It has been demonstrated that low energy electrons(LEEs)can induce serious DNA damages including bases loss and even single and double strand breaks.Experiments also showed that LEE induced DNA damages will be reduced with the presence of amino acids.For understanding of the protection of amino acids to DNA,the stability of 6 kinds of thymine and glycine(T-g)dimers with planar configurations with an excess electron were studied with density functional theory(DFT)method.The results show that,when the excess electron is vertically attached,all the dimers become more active with higher energy.After re-optimization,4 kinds(66.7%)of T-g dimers become more stable than the corresponding neutral states.For the most stable anionic dimer noted as[34-A]-,the excess electron is localized on the thymine,while one proton transfers from glycine to thymine.The proton transformation decreases the activities and prevents further reactions of the excess electron.For other three dimers,there is no chemical topology change.The glycine attracts the excess electron with hydrogen-bonding to the thymine.

Intra-and Intermolecular Rovibrational States of HCl-H_(2)O and DCl-H_(2)O Dimers from Full-Dimensional and Fully Coupled Quantum Calculations

We report full-dimensional and fully coupled quantum bound-state calculations of the J=1 intra-and intermolecular rovibrational states of two isotopologues of the hydrogen chloride-water dimer,HClH_(2)O(HH)and DCl-H_(2)O(DH).The present study complements our recent theoretical investigations of the J=0 nine-dimensional(9D)vibrational level structure of these and two other H/D isotopologues of this noncovalently bound molecular complex,and employs the same accurate 9D permutation invariant polynomial-neural network potential energy surface.The calculations yield all intramolecular vibrational fundamentals of the HH and DH dimers and the low-energy intermolecular rovibrational states in these intramolecular vibrational manifolds.The results are compared with those of the 9D J=0 calculations of the same dimers.The energy differences between the K=1 and K=0 eigenstates exhibit pronounced variations with the intermolecular rovibrational states,for which a qualitative explanation is provided.

Sythesis of 4,5 -Bisaryl-2-(2,5-Dimethylthiophen-3-yl)imidazoles and Their Dimers

t 4,5 -diphenyl, 4,5 - bis(4 - methylphenyl), 4,5 - bis(4 - methoxyphenyl) - 2 -(2,5 - dAnethylthiophen -3 -yl ) imidazoles were synthesized. Oxidation of the obtained Anidazoles with potassium ferricyanide in water - alcohol solution of alkali gave the corresponding dimers. The structtires of imidazoles were characterized by IR, 1H NMR, mass spectroscopy and elemental analysis. The structures of dimers were characterized by IR, elemental analysis and chromatography

Cell Wall Characteristics of a Maize Mutant Selected for Decreased Ferulates

The cross-linked nature of plant cell walls provides structural integrity for continued growth and development, but limits degradation and utilization by ruminants. In grasses a major cross-linking component is ferulic acid that is incorporated into cell walls as an ester linked residue on arabinoxylans. Ferulates can become coupled to each other and to lignin forming a highly cross-linked matrix of carbohydrates and lignin. Seedling ferulate ester mutants (sfe) were produced in maize using the transposon system and evaluated in feeding trials. The work described here was undertaken to characterize changes in the ferulate cross-linked nature as well as other components of the corn cell wall matrix in leaf, sheath and stem tissues. Total ferulates decreased modestly due to the mutation and were more apparent in leaf tissue (16% - 18%) compared to sheath (+5 to?-6% change) and stem (8% - 9% decrease). The most significant changes were in the ether linked ferulates to lignin, both monomer and dehydrodiferulates (14% to 38% decrease). Other characteristics of the cell wall (lignin, neutral sugar composition) also showed modest changes. The change in total ferulates was modest, but led to improved animal performance. These findings suggest that relatively small changes can have a significant impact upon how well plant materials can be broken down and utilized by ruminants such as dairy cows.

Study of Molecular Polarizabilities and Orientational Order Parameter in the Nematic Phase of 6.O12O.6 and 7.O12O.7

As a part of our systematic study of the physical properties of the compounds of symmetric liquid crystal dimer homologous series, α,ω-bis-(4-n-alkylaniline benzylidene-4’-oxy) alkanes (m.OnO.m), we report here an optical study of two nematogenic compounds of this series viz., 6.O12O.6 and 7.O12O.7 by carrying out the measurement of extraordinary and ordinary refractive indices using modified spectrometer. The molecular polarizability anisotropies are evaluated using Lippincott δ-function model, the molecular vibration method, Haller’s extrapolation method and scaling factor method. The molecular polrizabilities, αe and αo are calculated using Vuks’ isotropic field model and Neugebauer’s anisotropic field model. The orientational order parameter, S, is estimated by using the molecular polarizability values calculated from refractive index and denstity data as well as polarizability anisotropy values calculated as a function of temperature in the nematic phase of both of the dimers. These values are discussed with reference to the order parameter values obtained directly from the optical birefringence, Δn, data without assuming any internal field. A comparison of the order parameter values from all of these methods was carried out in the light of available literature data.