Electronic Structures, DNA-binding, SAR, and Spectral Properties of Ruthenium Methylimidazole Complexes [Ru（MeIm）4L]^2＋（L=iip,tip,2ntz）

Theoretical studies on the electronic and geometric structures, the trend in DNA-binding affinities as well as the the structure-activity relationship （SAR） of a series of water-soluble Ru（II） methylimidazole complexes, i.e. [Ru（Mehn）4iip]^2＋ （1） （MeIm=l-methylimidazole, iip=2-（1H-imidazo-4-group）-lH-imidazo[n,5-f][1,10]phenanthroline）, [Ru（MeIm）4tip]^2＋ （2） （tip=2-（thiophene-2-group）-lH-imidazo[4,5-f] [i,10]phenanthroline）, and [Ru（Melm）42ntz]^2＋ （3） （2ntz=2-（2-nitro-l,3-thiazole-5-group）-lH-imidazo[4,5-f][1,10]phenanthroline）, were car- ried out using the density functional theory （DFT）. The electronic structures of these Ru（II） complexes were analyzed on the basis of their geometric structures optimized in aqueous solution, and the trend in the DNA-binding constants （Kb） was reasonably explained. The results show that the replacement of imidazole ligand by thiophene ligand can effectively improve the DNA-binding affinity of the complex. Meanwhile, it was found that introduc- ing the stronger electronegative N atom and NO2 group on terminal loop of intercalative ligand can obviously reduce the complex＇s LUMO and HOMO-LUMO gap energies. Based on these findings, the designed complex [Ru（MeIm）42ntz]^2＋ （3） can be expected to have the greatest Kb value in complexes 1-3. In addition, the structure-activity relationships and antitumor mechanism were also carefully discussed, and the antimetastatic activity of the designed complex 3 was predicted. Finally, the electronic absorption spectra of this series of complexes in aqueous solution were calculated, simulated and assigned using DFT/TDDFT methods as well as conductor-like polarizable continuum model （CPCM）, and were in good agreement with the experimental results.

Transformations of biomass-based levulinate ester into γ-valerolactone and pyrrolidones using carbon nanotubes-grafted N-heterocyclic carbene ruthenium complexes

As a renewable biomass-based compound with wide applications in food additives,fine chemical synthesis and fuels,γ-valerolactone(GVL)has attached much attention.While,pyrrolidones are widely used in pharmaceutical,agrochemical,material industrial and other chemical production.In this research,we demonstrated transformations of biomass-based ethyl levulinate(EL)into GVL and pyrrolidones by using heterogeneous catalysts(CNT-Ru-1)with N-heterocyclic carbene ruthenium(NHC-Ru)complex grafted on multi-walled carbon nanotube(CNT).The Ru catalyst showed high efficiency on EL hydrogenation to GVL with both EL conversion and GVL yield exceeding 99%.Moreover,the Ru catalyst readily promoted reductive amination of EL in the presence of various amines for pyrrolidone synthesis.Finally,the Ru catalyst was also applicable to hydrogenation of various carbonyl compounds for the synthesis of the corresponding alcohols with excellent catalytic performance.The research provides insight for heterogenizing the homogeneous noble metal-based catalysts with high catalytic active for biomass-based transformations.

Oxidation of Alcohols Catalyzed by Ruthenium Complexes with Iodosylbenzene as Oxidant

Five ruthenium complexes such as Phen-Ru-Phen, Phen-Ru-Bipy, Phen-Ru-Quin, Quin-Ru-Quin and Bipy-Ru-Quin (where Phen=1, 10-phenanthroline, Quin=8-hydroxyquinoline, Bipy=2, 2′-bipyridine) were synthesized and used as catalysts for the oxidation of benzylic and primary aliphatic alcohols with iodosylbenzene as oxidant. The oxidations were carried out at room temperature, affording the corresponding aldehydes and ketones with high selectivity.

New Ruthenium Complexes of Fullerene C60&C70

The new complexes [Ru(NO)(PPh3)]2(h2-Cm)(m=60 1 or 70 2) have been prepared by heating a solution of C60(or C70) with [Ru(NO)2(PPh3)2] in toluene. They have been characterized by elemental analysis, IR, UV/VIS, XPS, 13C and 31P NMR spectroscopy. The photovaltaic effect for the new compounds has been studied.

Synthesis and Characterization of Ferroceneterminated Ruthenium Phenylacetylide Complexes with Alligator Clips

Ferrocene-terminated trans-Ru(dppm)2 (dppm=Ph2PCH2PPh2)-containing molecular wires with alligator clips were prepared. They are suitable for self-assembly on gold electrode to investigate the influence of metal incorporation on the electron transportation property of the molecular wires.

The DUF579 proteins GhIRX15s regulate cotton fiber development by interacting with proteins involved in xylan synthesis

Cotton provides the most abundant natural fiber for the textile industry.The mature cotton fiber largely consists of secondary cell walls with the highest proportion of cellulose and a small amount of hemicellulose and lignin.To dissect the roles of hemicellulosic polysaccharides during fiber development,four IRREGULAR XYLEM 15(IRX15)genes,GhIRX15-1/-2/-3/-4,were functionally characterized in cotton.These genes encode DUF579 domain-containing proteins,which are homologs of AtIRX15 involved in xylan biosynthesis.The four GhIRX15 genes were predominantly expressed during fiber secondary wall thickening,and the encoded proteins were localized to the Golgi apparatus.Each GhIRX15 gene could restore the xylan deficient phenotype in the Arabidopsis irx15irx15l double mutant.Silencing of GhIRX15s in cotton resulted in shorter mature fibers with a thinner cell wall and reduced cellulose content as compared to the wild type.Intriguingly,GhIRX15-2 and GhIRX15-4 formed homodimers and heterodimers.In addition,the GhIRX15s showed physical interaction with glycosyltransferases GhGT43C,GhGT47A and GhGT47B,which are responsible for synthesis of the xylan backbone and reducing end sequence.Moreover,the GhIRX15s can form heterocomplexes with enzymes involved in xylan modification and side chain synthesis,such as GhGUX1/2,GhGXM1/2 and GhTBL1.These findings suggest that GhIRX15s participate in fiber xylan biosynthesis and modulate fiber development via forming large multiprotein complexes.

Identification and characterization of FpRco1 in regulating vegetative growth and pathogenicity based on T-DNA insertion in Fusarium pseudograminearum

Fusarium pseudograminearum is a devastating pathogen that causes Fusarium crown rot(FCR)in wheat and poses a significant threat to wheat production in terms of grain yield and quality.However,the mechanism by which F.pseudograminearum infects wheat remains unclear.In this study,we aimed to elucidate these mechanisms by constructing a T-DNA insertion mutant library for the highly virulent strain WZ-8A of F.pseudograminearum.By screening this mutant library,we identified nine independent mutants that displayed impaired pathogenesis in barley leaves.Among these mutants,one possessed a disruption in the gene FpRCO1 that is an ortholog of Saccharomyces cerevisiae RCO1,encoding essential component of the Rpd3S histone deacetylase complex in F.pseudograminearum.To further investigate the role of FpRCO1 in F.pseudograminearum,we employed a split-marker approach to knock out FpRCO1 in F.pseudograminearum WZ-8A.FpRCO1 deletion mutants exhibit reduced vegetative growth,conidium production,and virulence in wheat coleoptiles and barley leaves,whereas the complementary strain restores these phenotypes.Moreover,under stress conditions,the FpRCO1 deletion mutants exhibited increased sensitivity to NaCl,sorbitol,and SDS,but possessed reduced sensitivity to H_(2)O_(2)compared to these characteristics in the wild-type strain.RNA-seq analysis revealed that deletion of FpRCO1 affected gene expression(particularly the downregulation of TRI gene expression),thus resulting in significantly reduced deoxynivalenol(DON)production.In summary,our findings highlight the pivotal role of FpRCO1 in regulating vegetative growth and development,asexual reproduction,DON production,and pathogenicity of F.pseudograminearum.This study provides valuable insights into the molecular mechanisms underlying F.pseudograminearum infection in wheat and may pave the way for the development of novel strategies to combat this devastating disease.

Optimizing Connections:Applied Shortest Path Algorithms for MANETs

This study is trying to address the critical need for efficient routing in Mobile Ad Hoc Networks(MANETs)from dynamic topologies that pose great challenges because of the mobility of nodes.Themain objective was to delve into and refine the application of the Dijkstra’s algorithm in this context,a method conventionally esteemed for its efficiency in static networks.Thus,this paper has carried out a comparative theoretical analysis with the Bellman-Ford algorithm,considering adaptation to the dynamic network conditions that are typical for MANETs.This paper has shown through detailed algorithmic analysis that Dijkstra’s algorithm,when adapted for dynamic updates,yields a very workable solution to the problem of real-time routing in MANETs.The results indicate that with these changes,Dijkstra’s algorithm performs much better computationally and 30%better in routing optimization than Bellman-Ford when working with configurations of sparse networks.The theoretical framework adapted,with the adaptation of the Dijkstra’s algorithm for dynamically changing network topologies,is novel in this work and quite different from any traditional application.The adaptation should offer more efficient routing and less computational overhead,most apt in the limited resource environment of MANETs.Thus,from these findings,one may derive a conclusion that the proposed version of Dijkstra’s algorithm is the best and most feasible choice of the routing protocol for MANETs given all pertinent key performance and resource consumption indicators and further that the proposed method offers a marked improvement over traditional methods.This paper,therefore,operationalizes the theoretical model into practical scenarios and also further research with empirical simulations to understand more about its operational effectiveness.

Half-sandwich Ruthenium Complexes with Naphthalene-based Schiff Base Ligands:Syntheses,Characterization and Catalytic Activities for the Reduction of Nitroarenes

Three half-sandwich ruthenium（II） p-cymene complexes containing naphthalenebased Schiff base ligands [Ru（p-cymene）LCl]（2 a～2 c） have been synthesized and characterized. Both Schiff-base ligands and ruthenium complexes were fully characterized by ^1H and ^13C NMR spectra, mass spectrometry and infrared spectrometry. The molecular structure of ruthenium complex 2 b was confirmed by single-crystal X-ray diffraction methods. For the complex： C（24H23ClN2ORu, Mr = 524.02, monoclinic, space group P21/c, a = 12.3888（4）, b = 17.3296（6）, c = 20.7744（7）A°, β = 92.8000（10）°, V = 4454.8（3） A°^3, Z = 8, Dc = 1.563 g/cm^3, μ = 0.936 mm^-1, F（000） = 2128, S = 1.154, the final R = 0.0309 and w R = 0.0703. Moreover, these ruthenium complexes are active catalysts for the hydrogenation of nitroarenes to aromatic anilines in the presence of sodium tetrahydroborate（NaBH4） reducing agent.

光诱导基于EDA机理构建S-芳基黄原酸酯新策略

黄原酸酯类化合物作为药物化学、农业化学、材料化学中重要的组成部分,一直备受化学家们的关注.寻找简单、高效合成S-芳基取代黄原酸酯的方法引起了研究者广泛的关注.报道了一种可见光诱导下基于硫负离子与噻蒽盐间的EDA(电子供体受体)过程实现C-S键构建的新策略.在温和无金属的条件下,以中等至优良的收率得到了一系列S-芳基黄原酸酯,克级实验与日光实验证明了反应的应用潜力,为黄原酸酯类化合物的合成提供了一种新思路.

化学水浴沉积制备高质量Zn(O,S)薄膜及其性能研究

为获得铜铟镓硒薄膜太阳电池中高质量Zn(O,S)无镉缓冲层薄膜,该研究阐述了柠檬酸三钠作为络合剂制备Zn(O,S)薄膜的成膜机理,系统性研究了该体系下各反应参数对薄膜化学水浴沉积的影响。研究表明,柠檬酸三钠的浓度值显著影响反应类型,异质反应更有利于生成高质量薄膜。同时,柠檬酸三钠与金属离子浓度的比值直接影响成膜质量和成膜速率,适合的pH溶液环境有助于提高Zn(O,S)薄膜沉积的质量。此外,通过工艺参数的优化,获得了电学性能接近传统CdS/CIGS太阳电池的Zn(O,S)/CIGS电池器件。

萤火虫成像联合应变弹性成像校正人工智能S-Detect技术对乳腺囊实性肿块良恶性的诊断价值

目的 探讨萤火虫成像(micropure imaging, MI)联合应变弹性成像(strain elastography, SE)校正人工智能(artificial intelligence, AI)S-Detect技术对乳腺囊实性肿块良恶性的诊断价值。方法 根据145个乳腺囊实性肿块的MI和SE的表现对其S-Detect诊断结果进行校正。以术后病理结果为金标准,计算校正前后的诊断敏感度、特异度、准确度,并绘制两组受试者操作特征(receiver operating characteristic, ROC)曲线,比较曲线下面积。结果 病理良性80个,恶性65个。S-Detect经过校正后,诊断敏感度、特异度、准确度以及ROC曲线下面积均较校正前有所提高。结论 MI与SE联合校正S-Detect的诊断结果,能够提高对乳腺囊实性肿块良恶性的诊断效能。

基于Q-s曲线的大型LNG储罐桩板基础沉降计算方法

试桩Q-s曲线体现了现场桩基荷载和沉降的关系。文章以某LNG储罐桩板基础为背景,提出利用Q-s曲线求出桩端土层变形模量的方法,并考虑桩板共同作用的求解桩板基础沉降的方法。该方法将桩基模拟为非线性弹簧,弹簧刚度取自Q-s曲线,采用MIDAS进行建模求解,可得到设计需要的筏板和桩基的沉降等高线图以及轴力和弯矩图,用于指导设计。与仅考虑线性地弹簧系数的规范方法进行对比,该方法精度更高,与实际情况更加相符。该方法可针对不同位置的桩基输入不同的非线性弹簧,可用于解决复杂不均匀地层桩筏基础沉降计算的问题。

Quantitative Structure Anti-Cancer Activity Relationship (QSAR) of a Series of Ruthenium Complex Azopyridine by the Density Functional Theory (DFT) Method

A series of ruthenium azopyridine complexes have recently been investigated due to their potential cytotoxic activities against renal cancer (A498), lung cancer (H226), ovarian cancer (IGROV), breast cancer (MCF-7) and colon cancer (WIDR). Thus, in order to predict the cytotoxic potentials of these compounds, quantitative structure-activity relationship studies were carried out using the methods of quantum chemistry. Five Quantitative Structure Activity Relationship (QSAR) models were obtained from the determined quantum descriptors and the different activities. The models present the following statistical indicators: regression correlation coefficient R2 = 0.986 - 0.905, standard deviation S = 0.516 - 0.153, Fischer test F = 106.718 - 14.220, correlation coefficient of cross-validation = 0.985- 0.895 and = 0.010 - 0.001. The statistical characteristics of the established QSAR models satisfy the acceptance and external validation criteria, thereby accrediting their good performance. The models developed show that the variation of the free enthalpy of reaction , the dipole moment μ and the charge of the ligand in the complex Ql, are the explanatory and predictive quantum descriptors correlated with the values of the anti-cancer activity of the studied complexes. Moreover, the charge of the ligand is the priority descriptor for the prediction of the cytotoxicity of the compounds studied. Furthermore, QSAR models developed are statistically significant and predictive, and could be used for the design and synthesis of new anti-cancer molecules.

基于S变换与复值U-Net网络的地震资料高分辨率处理方法

地震资料高分辨率处理方法通过拓展频带范围有效地提高了地震资料的精度。迄今为止,基于深度学习的高分辨率处理方法仅在时域中进行特征提取,忽视了地震数据的频域信息,因而影响高分辨率处理效果。为此,结合深度学习的数据驱动能力与时频分析方法的时频定位能力,提出了一种基于S变换和复值U-Net网络(STCVU-Net)的地震资料高分辨率处理方法。首先,通过褶积模型构建高分辨率与低分辨率的单道地震数据,接着,利用S变换获得不同分辨率地震数据的时频谱并将其作为训练数据,然后基于构建的STCVU-Net对时频谱进行训练和测试,最后,使用迁移学习方法对已训练的网络进行微调并应用于实际数据的处理。STCVU-Net方法充分考虑了地震数据的时域与频域信息,在准确得到地震数据时频谱的同时在时频域中对地震信号进行精准拓频,从而提高了地震资料的分辨率。对比时域端到端的深度学习方法在模型资料和实际工区资料的高分辨率处理结果表明,STCVU-Net方法的高分辨率处理结果更准确,高频信息更丰富,具有较大的实际应用潜力。

Syntheses, Crystal Structures and Properties of Two New W-Ag 1D Chain Complexes: [W_2Ag_2S_8·Ca(DMF)_6]_n and [WAgS_4·Na(DMF)_3]_n

Two new complexes, [W2Ag2S8?Ca(DMF)6]n 1 and [WAgS4?Na(DMF)3]n 2, have been synthesized and characterized. Single-crystal X-ray analyses show both 1 and 2 have {WAgS4}n anion linear chains, but 1 has a discrete [Ca(DMF)6]2+ cation while 2 is a linear chain. UV-Visible-Near-IR spectroscopy data show that the bandgaps of the two complexes are 1.86 and 1.99 eV, respectively. Electrical conductivity measurements reveal the conductivities of 1 and 2 are 10?7 and 10?8 Scm?1, respectively and they exhibit thermally activated temperature depen- dence, which may be attributed to semiconductors.

The role of DJ-1 complexes and catecholamine metabolism： relevance for familial and idiopathic Parkinson＇s disease

Autosomal recessive mutations in the PARK7 gene,which encodes for the protein DJ-1,result in a loss of function and are a cause of familial Parkinson’s disease（PD）,while increased wild-type DJ-1protein levels are associated with some forms of cancer.Several functions of DJ-1 have been described,with the greatest evidence indicating that DJ-1 is a redox-sensitive protein involved in the regulation of oxidative stress and cell survival.

A Novel Octanuclear Molecular Loop Formed by Linkage of Oxo-centered Triruthenium Cluster Units

A novel dimeric complex [Ru3 (μ3-O)(μ-CH3COO)(CO)]2(μ-dppf)(μ-odppf)(dppf = 1, 1'-bis(diphenylphosphio)ferrocene, odppf = 1, 1'-bis(oxodiphenylphosphoranyl)ferrocene) (1) of oxo-centered triruthenium-aectate cluster units was synthesized and characterized by X-ray crystallography. Compound 1 exhibits a cyclic structure formed by linkages of two triruthenium cluster units Ru3 (μ3-O)(μ-CH3COO)6(CO) through dppf and odppf ligands, respectively. The diameter of the molecular loop is ca. 1.0 nm.

Synthesis and Catalytic Activity of a Two-core Ruthenium Carbene Complex: a Unique Catalyst for Ring Closing Metathesis Reaction

The reaction of a ruthenium carbide complex RuCl2（C：）（PCy3）2 with [H（Et2O）x]＋[BF4]- at a molar ratio of 1：2 produced a two-core ruthenium carbene complex, {[RuCl（=CHPCy3）（PCy3）]2（μ-Cl）3}＋·[BF4]-, in the form of a yellow-green crystalline solid in a yield of 94%. This two-core ruthenium complex is a selective catalyst for ring closing metathesis of unsubstituted terminal dienes. More importantly, no isomerized byproduct was observed for N-substrates when the two-core ruthenium complex was used as the catalyst at an elevated temperature（137 °C）, indicating that the complex is a chemo-selective catalyst for ring closing metathesis reactions.

Asymmetric hydrogenation of aromatic ketones using new chiral-bridged diphosphine/diamine-Ru(Ⅱ) complexes

A series of chiral secondary alcohols were easily prepared by means of asymmetric hydrogenation of prochiral aromatic ketones using a new（（Rax）-BuP）/（R,R）-DPEN-Ru（Ⅱ） complex catalyst system.The hydrogenation of 2-methylacetophenone in n-butanol （t-BuOK/Ru =45.6/1,S/C = 500,20 atm.of H2,20℃,48 h） afforded（S）-1-（2＇-methylphenyl）ethanol in 92%ee and〉99% conversion.