Single atom doping induced charge-specific distribution of Cu1-TiO_(2) for selective aniline oxidation via a new mechanism

Utilizing single atom sites doping into metal oxides to modulate their intrinsic active sites,achieving precise selectivity control in complex organic reactions,is a highly desirable yet challenging endeavor.Meanwhile,identifying the active site also represents a significant obstacle,primarily due to the intricate electronic environment of single atom site doped metal oxide.Herein,a single atom Cu doped TiO_(2)catalyst(Cu_(1)-TiO_(2)) is prepared via a simple“colloid-acid treatment”strategy,which switches aniline oxidation selectivity of TiO_(2) from azoxybenzene to nitrosobenzene,without using additives or changing solvent,while other metal or nonmetal doped TiO_(2) did not possess.Comprehensive mechanistic investigations and DFT calculations unveil that Ti-O active site is responsible for triggering the aniline to form a new PhNOH intermediate,two PhNOH condense to azoxybenzene over TiO_(2) catalyst.As for Cu_(1)-TiO_(2),the charge-specific distribution between the isolated Cu and TiO_(2) generates unique Cu_(1)-O-Ti hybridization structure with nine catalytic active sites,eight of them make PhNOH take place spontaneous dissociation to produce nitrosobenzene.This work not only unveils a new mechanistic pathway featuring the PhNOH intermediate in aniline oxidation for the first time but also presents a novel approach for constructing single-atom doped metal oxides and exploring their intricate active sites.

The effect of single-tree selction system on soil properties in an oriental beech stand of Hyrcanian forest, north of Iran

A case study was conducted in beech forests of northern Iran to determine the effect of the created gaps on some soil properties in beech stand. Changes of soil properties in small （60-150 mE）, medium （151-241 mE）, large （242-332 m^2） and very large （333-550 m^2） gaps, as well as under closed stands were studied eight years after-the gap creation. Soil samples were taken from three depths, 0-10, 10-20 and 20-30 cm. The gaps were different from their around undisturbed stands in terms of the following soil parameters： Mg^＋2 concentration of 0-10 cm at medium gap size, bulk density of 10-20 cm at very large gap size as well as K^＋ and Ca^＋2 concentrations at 20-30 cm at small and large gap sizes, respectively. Furthermore, the size of the gaps had no effect on soil characteristics through the whole profile. Water saturation percent （Sp %） at 0-10cm as well as P and Mg^＋2 at 20--30 cm was different amongst undisturbed stands around different gap sizes. The center and the edges of the gap were different only in terms of organic carbon at the depth of 10-20 cm. Significant differences were observed between gaps and closed canopy regarding P and Ca^＋2 at depth 0--10 cm and 10-20 cm, respectively. It can be concluded that applied silvicultural system for harvesting trees which created these gaps might be suitable for conservation and forest management in the region.

Identification of Multiple Alleles at the Wx Locus and Development of Single Segment Substitution Lines for the Alleles in Rice

The microsatellite markers 484/485 and 484/W2R were used to identify the multiple alleles at the Wx locus in rice germplasm. Fifteen alleles were identified in 278 accessions by using microsatellite class and G-T polymorphism. Among these alleles, （CT）12-G, （CT）15-G, （CT）16-G, （CT）17-G, （CT）18-G and （CT）21-G have not been reported. Seventy-two single-segment substitution lines （SSSLs） carrying different alleles at the Wx locus were developed by using Huajingxian 74 with the （CT）11-G allele as a recipient and 20 accessions containing 12 different alleles at the Wx locus as donors. The estimated length of the substituted segments ranged from 2.2 to 77.3 cM with an average of 17.4 cM.

Piezoelectric transducer parameter selection for exciting a single mode from multiple modes of Lamb waves

Excitation and propagation of Lamb waves by using rectangular and circular piezoelectric transducers surface- bonded to an isotropic plate are investigated in this work. Analytical stain wave solutions are derived for the two transducer shapes, giving the responses of these transducers in Lamb wave fields. The analytical study is supported by a numericM simulation using the finite element method. Symmetric and antisymmetric components in the wave propagation responses are inspected in detail with respect to test parameters such as the transducer geometry, the length and the excitation frequency. By placing only one piezoelectric transducer on the top or the bottom surface of the plate and weakening the strength of one mode while enhancing the strength of the other modes to find the centre frequency, with which the peak wave amplitude ratio between the SO and A0 modes is maximum, a single mode excitation from the multiple modes of the Lamb waves can be achieved approximately. Experimental data are presented to show the validity of the analyses. The results are used to optimize the Lamb wave detection system.

An mmWave Dual-Band Integrated Substrate Gap Waveguide Single Cavity Filter with Frequency Selectivity

A novel dual-band ISGW cavity filter with enhanced frequency selectivity is proposed in this paper by utilizing a multi-mode coupling topology.Its cavity is designed to control the number of modes,and then the ports are determined by analyzing the coupling relationship between these selected modes.By synthesizing the coupling matrix of the filter,a nonresonating node(NRN)structure is introduced to flexibly tune the frequency of modes,which gets a dualband and quad-band filtering response from a tri-band filter no the NRN.Furthermore,a frequency selective surface(FSS)has been newly designed as the upper surface of the cavity,which significantly improves the bad out-of-band suppression and frequency selectivity that often exists in most traditional cavity filter designs and measurements.The results show that its two center frequencies are f01=27.50 GHz and f02=32.92GHz,respectively.Compared with the dual-band filter that there is no the FSS metasurface,the out-of-band suppression level is improved from measured 5 dB to18 dB,and its finite transmission zero(FTZ)numbers is increased from measured 1 to 4 between the two designed bands.Compared with the tri-band and quadband filter,its passband bandwidth is expanded from measured 1.17%,1.14%,and 1.13% or 1.31%,1.50%,0.56%,and 0.57% to 1.71% and 1.87%.In addition,the filter has compact,small,and lightweight characteristics.

Cobalt Single Atom-Catalyzed Formation of LiOH in Li-O_(2)Batteries via the Direct 4-Electron Oxygen Reduction Pathway

The formation of LiOH as the discharge product instead of Li_(2)O_(2)in Li-O_(2)batteries(LOBs)is highly desirable due to the associated drawbacks of Li_(2)O_(2)-based chemistry,which involves the generation of reactive oxygen intermediates responsible for substantial side reactions.However,the current challenge lies in the formation pathway of LiOH,which typically requires the chemical hydrolysis of the hazardous LiO_(2)or Li_(2)O_(2)intermediate,posing risks to the battery components.Herein,we report a direct 4e–electrochemical approach to LiOH enabled by a single atom catalyst(SAC)consisting of CoN_(3)moieties embedded in graphene(CoN_(3)-G),while Li_(2)O_(2)is formed on the metal-free nitrogen-doped graphene(NG).The direct 4e–LiOH pathway significantly reduces the parasitic reactions,resulting in negligible damage to the electrolyte and cathode.This stands in strong contrast to the conventional 2e–Li_(2)O_(2)pathway mediated by NG and the indirect LiOH pathway by MnO_(2).Theoretical calculations further clarify that the presence of CoN_(3)sites enhances the adsorption of oxygen-containing intermediates like*OLiO and*Li_(2)O_(2),promoting the protonation of*Li_(2)O_(2)and the cleavage of the O–O bond to form LiOH.This work demonstrates a promising strategy to modulate the reaction pathways in LOBs and broadens the applications of SACs.

Development of a 50K SNP Array for Japanese Flounder and Its Application in Genomic Selection for Disease Resistance

Single nucleotide polymorphism(SNP)armays are a powerful genotyping tool used in genetic research and genomic breeding programs.Japanese flounder(Paralichthys olivaceus)is an economically-important aquaculture flatfish in many countries.However,the lack of high-efficient genotyping tools has impeded the genomic breeding programs for Japanese flounder.We developed a 50K Japanese flounder SNP array,"Yuxin No.1,"and report its utility in genomic selection(GS)for disease resistance to bacterial pathogens.We screened more than 42,.2 million SNPs from the whole-genome resequencing data of 1099 individuals and selected 48697 SNPs that were evenly distributed across the genome to anchor the array with Affymetrix Axiom genotyping technology.Evaluation of the array performance with 168 fishs howed that 74.7%of the loci were successfully genotyped with high call rates(>98%)and that the poly-morphic SNPs had good cluster separations.More than 85%of the SNPs were concordant with SNPs obtained from the whole-genome resequencing data.To validate"Yuxin No.1"for GS,the arrayed geno-typing data of 27 individuals from a candidate population and 931 individuals from a reference popula-tion were used to calculate the genomic estimated breeding values(GEBVs)for disease resistance toEdwardsiella tarda.There was a 21.2%relative increase in the accuracy of GEBV using the weighted geno-mic best linear unpiased prediction(wGBLUJP),compared to traditional pedigree-based best linear unbi-ased prediction(ABLUP),suggesting good performance of the'Yuxin No.1"SNP array for GS.In summary,we developed the"Yuxin No.1"50K SNP array,which provides a useful platform for high-quality geno-typing that may be beneficial to the genomic selective breeding of Japanese flounder.

Multiscale modelling and simulation of single crystal superalloy turbine blade casting during directional solidification process

As the key parts of an aero-engine,single crystal(SX)superalloy turbine blades have been the focus of much attention.However,casting defects often occur during the manufacturing process of the SX turbine blades.Modeling and simulation technology can help to optimize the manufacturing process of SX blades.Multiscale coupled models were proposed and used to simulate the physical phenomena occurring during the directional solidification(DS)process.Coupled with heat transfer(macroscale)and grain growth(meso-scale),3D dendritic grain growth was calculated to show the competitive grain growth at micro-scale.SX grain selection behavior was studied by the simulation and experiments.The results show that the geometrical structure and technical parameters had strong influences on the grain selection effectiveness.Based on the coupled models,heat transfer,grain growth and microstructure evolution of a complex hollow SX blade were simulated.Both the simulated and experimental results show that the stray grain occurred at the platform of the SX blade when a constant withdrawal rate was used in manufacturing process.In order to avoid the formation of the stray crystal,the multi-scale coupled models and the withdrawal rate optimized technique were applied to the same SX turbine blade.The modeling results indicated that the optimized variable withdrawal rate can achieve SX blade castings with no stray grains,which was also proved by the experiments.

Molecular Markers for Tm-2 Alleles of Tomato Mosaic Virus Resistance in Tomato

Tomato mosaic virus (ToMV) is one of the most infectious virus diseases in tomato (Solanum lycopersicum L). The practical and effective method of controlling this disease is through genetic control by using major resistance genes. So far, three genes Tm-1, Tm-2 and Tm-22 conferring resistance to ToMV have been reported and utilized in tomato culti-var development. Marker assisted selection (MAS) has become very important and useful tool in selection of ToMV re-sistant tomato lines or hybrids. The objective of this research was to identify allele-specific PCR-based, cleaved ampli-fied polymorphic sequence (CAPS), and allele-derived single nucleotide polymorphism (SNP) markers for Tm-2 loci. Four allele-specific PCR-based markers were identified: one for Tm-2, one for Tm-22, and two for the susceptible allele tm-2. Three allele-derived CAPS markers were identified, which can identify and distinguish three alleles, tm-2, Tm-2 and Tm-22 in tomato germplasm. Three SNP markers were developed specific for Tm-2 locus. These markers will pro-vide breeders with a tool in selection of Tm-2 and Tm-22 resistance genes in tomato breeding program.

CO_(2) reduction reaction pathways on single‐atom Co sites:Impacts of local coordination environment

Single‐atom catalysts have been proposed as promising electrocatalysts for CO_(2) reduction reactions(CO_(2)RR).Co‐N_(4) active sites have attracted wide attention owing to their excellent CO selectivity and activity.However,the effect of the local coordination environment of Co sites on CO_(2) reduction reaction pathways is still unclear.In this study,we investigated the CO_(2) reduction reaction pathways on Co‐N_(4) sites supported on conjugated N_(4)‐macrocyclic ligands with 1,10‐phenanthroline subunits(Co‐N_(4)‐CPY)by density functional theory calculations.The local coordination environment of single‐atom Co sites with N substituted by O(Co‐N_(3)O‐CPY)and C(Co‐N_(3)C‐CPY)was studied for comparison.The calculation results revealed that both C and O coordination break the symmetry of the primary CoN_(4) ligand field and induce charge redistribution of the Co atom.For Co‐N_(4)‐CPY,CO was confirmed to be the main product of CO_(2)RR.HCOOH is the primary product of Co‐N_(3)O‐CPY because of the greatly increased energy barrier of CO_(2) to*COOH.Although the energy barrier of CO_(2) to*COOH is reduced on Co‐N_(3)C‐CPY,the desorption process of*CO becomes more difficult.CH3OH(or CH_(4))are obtained by further*CO hydrogenation reduction when using Co‐N_(3)C‐CPY.This work provides new insight into the effect of the local coordination environment of single‐atom sites on CO_(2) reduction reaction pathways.

Variable Selection of Partially Linear Single-index Models

In this article, we study the variable selection of partially linear single-index model(PLSIM). Based on the minimized average variance estimation, the variable selection of PLSIM is done by minimizing average variance with adaptive l1 penalty. Implementation algorithm is given. Under some regular conditions, we demonstrate the oracle properties of aLASSO procedure for PLSIM. Simulations are used to investigate the effectiveness of the proposed method for variable selection of PLSIM.

Effect of selective cutting type on the chainsaw productivity in Caspian Forests

Time and motion studies were conducted to evaluate the impact of selective cutting type on Chainsaw productivity in Caspian forests, the selective cutting performed as single and group selection cutting in the region. The selective cutting was performed on a 42-ha tract with an average slope of 30%. The results indicate that felling time for per tree is most affected by diameter at breast height, the distance among harvested trees in single-tree selection method and diameter at breast height in group selection method. The production rate in single and group selection cutting were 21.2 m^3·h^-1 and 28.4 m^3·h^-1 for one person, respectively. Considering the gross and net production rate in single and group selection cutting, the unit cost was 1.11 USD.m^-3 and 0.88 USD.m^-3, respectively. The results indicate that group selection cutting can be more profitable than single-tree selection method.

Automatic Variable Selection for Single-Index Random Effects Models with Longitudinal Data

We consider the problem of variable selection for the single-index random effects models with longitudinal data. An automatic variable selection procedure is developed using smooth-threshold. The proposed method shares some of the desired features of existing variable selection methods: the resulting estimator enjoys the oracle property;the proposed procedure avoids the convex optimization problem and is flexible and easy to implement. Moreover, we use the penalized weighted deviance criterion for a data-driven choice of the tuning parameters. Simulation studies are carried out to assess the performance of our method, and a real dataset is analyzed for further illustration.

基于有源消弧暂态衰减信息的配电网接地故障跟踪检测方法

现有配电网单相接地故障检测技术缺乏消弧过程的故障程度跟踪与选线能力。该文充分利用消弧过程中的暂态信息,建立考虑线路参数不对称的集总参数等效模型,论证消弧过程零序电压衰减直流特征的物理意义,提出考虑快速消弧的配电网故障检测新方法,对于低、高阻接地故障均有较高的检测灵敏度。实际应用中,仅需观测消弧全补偿电流投切过程中零序电压及零序电流波形,即可实现过渡电阻测量、故障程度跟踪与故障选线,具有瞬时性故障实时跟踪、故障检测与故障消弧同步进行的优势,操作简单、易于实现。仿真实验证实了方法的有效性,为配电网故障检测提供了新的理论依据。

纤维肌痛综合征生物标记物的筛选及免疫细胞浸润分析

背景:纤维肌痛综合征作为常见风湿病,其发病与中枢敏化及免疫异常有关,但具体过程尚未阐明,缺乏特异性诊断标志物,不断探索该病的发病机制具有重要的临床意义。目的:基于加权基因共表达网络分析(WGCNA)等生物信息学方法和机器学习算法筛选纤维肌痛综合征潜在的诊断相关标志基因,并分析其免疫细胞浸润特征。方法:对来自基因表达综合数据库(GEO)的纤维肌痛综合征数据集转录谱进行差异分析和WGCNA分析,整合筛选出差异共表达基因,进一步采用机器学习套索回归(LASSO)算法、支持向量机递归特征消除(SVM-RFE)机器学习算法来识别核心生物标志物,并绘制受试者工作特征(ROC)曲线以评估诊断价值。最后,采用单样本基因集富集分析(ssGSEA)和基因集富集分析(GSEA)评估纤维肌痛综合征的免疫细胞浸润情况及通路富集。结果与结论:①对GSE67311数据集按照log2|(FC)|>0,P<0.05的条件进行差异分析后获得8个下调的差异表达基因;进行WGCNA分析后获得正相关性最高(r=0.22,P=0.04)的模块(MEdarkviolet)内含基因497个,负相关性最高(r=-0.41,P=6×10-5)的模块(MEsalmon2)内含基因19个;将差异表达基因与WGCNA的2个高相关性模块基因取交集,获得7个基因。②对上述7个基因进行LASSO回归算法筛选出4个基因,进行SVM-RFE机器学习算法筛选出5个基因,两者取交集后确定了3个核心基因,分别为重组1号染色体开放阅读框150蛋白(germinal center associated signaling and motility like,GCSAML)、整合素β8(Integrin beta-8,ITGB8)和羧肽酶A3(carboxypeptidase A3,CPA3);绘制3个核心基因的ROC曲线下面积分别为0.744,0.739,0.734,提示均具有很好的诊断价值,可作为纤维肌痛综合征的生物标志物。③免疫浸润分析结果显示,与对照组相比纤维肌痛综合征患者记忆B细胞、CD56 bright NK细胞和肥大细胞显著下调(P<0.05),且与上述3个生物标志物显著正相关(P<0.05)。④富集分析结果提示,纤维肌痛综合征的富集途径包括9条,主要与嗅觉传导、神经活性配体-受体相互作用及感染等通路密切相关。⑤上述结果显示,纤维肌痛综合征的发生发展与多基因参与、免疫调节异常及多个通路失调有关,但这些基因与免疫细胞之间的相互作用,以及它们与各通路之间的关系尚需进一步研究。

电子束选区熔化单轨道成型不平直的形成机制研究

电子束选区熔化(electron beam selective melting,EBM)技术因其具有能量利用率高、制造的零件强度高以及残余应力小等制造优势而发展迅速,但在成型过程中单轨道两侧出现的不平直会严重降低零件的加工质量和各种性能。采用离散单元法(discrete element method,DEM)建立三维介观粉末床模型,数值模拟了EBM熔化金属粉末的过程,并对不同工艺参数下单轨道成型的截面进行了详细对比分析,发现扫描速度、扫描功率以及粉末粒径对单轨道成型的不平直度影响较大,研究结果揭示了单轨道成型过程中两侧熔体产生凸出、凹陷和空隙等不平直特征的形成机制。

基于拐点密集区凹凸波动特性的直流配网故障检测方法

基于模块化多电平换流器(modular multilevel converter,MMC)的柔性直流配电网具有不存在换相失败等优点。但换流器存在低惯性、弱阻尼等特性,导致故障电流上升速度快且峰值高,对系统危害极大。针对直流配电网发生单极接地故障难以准确选择故障馈线的问题,提出了一种基于拐点密集区凹凸波动特性的直流配网故障检测方法。首先,利用变分模态分解算法对各馈线零模电流进行分解,选取特征分量。然后,计算特征分量的二阶导数,选择拐点密集区并进行归一化处理,得到各馈线的凹凸波动性。最后,判定凹凸波动性与其他馈线相异的线路为故障线路。仿真结果表明,所提方法能够快速识别故障馈线,且受过渡电阻、采样频率、数据窗和噪声等因素影响小。

基于改进Hough变换的消弧线圈接地配电网故障选线新方法

针对配电网在电压过零点和高阻故障时刻选线不准确的问题,提出一种适用于谐振接地系统单相接地故障的选线新方法,利用优化后的变分模态分解对各馈线零序功率进行处理,遴选出与原始零序功率相关强度最高的本征模态函数IMF(k),将IMF(k)转换为JPG格式的二维图像,再利用Hough变换检测技术,得到故障起始阶段IMF(k)的拟合直线及夹角;对各支路模态量拟合直线夹角进行比对处理,将最小综合相关系数值对应的馈线确定为故障馈线;仿真结果表明:该方法不受接地电阻、故障相角、噪声干扰、数据缺失等因素的影响,验证了所提方法的有效性。

SnCl_(2)促进的Pt1/PS-PPh_(2)催化剂高选择性催化高碳烯烃氢甲酰化反应

氢甲酰化作为工业上制备醛、醇等含氧化合物的重要反应,广泛应用于制备洗涤剂、增塑剂、表面活性剂和香料等.目前,氢甲酰化反应主要使用HCo(CO)_(4),HCo(CO)_(3)(PR_(3))和HRh(CO)(PPh_(3))_(2)等配合物作为催化剂.尽管Co基催化剂可以将高碳烯烃、内烯烃以及支链烯烃高选择性地转化为直链醛,但其反应条件(5-30 MPa,140-200℃)较苛刻,且容易发生烯烃加氢等副反应.相比之下,Rh催化剂的活性比Co基催化剂高1-2个数量级,且反应条件较为温和.但Rh储量稀少,价格昂贵,而且对于高碳烯烃氢甲酰化反应,Rh催化剂难以分离和循环使用.因此,研究者开展了其他金属催化剂的研究,其中Pt-Sn催化剂因其出色的区域选择性而备受关注.但目前Pt-Sn催化剂多局限于均相催化体系,而且Sn助剂的作用尚不明确.本文采用商业化三苯基膦嫁接的聚苯乙烯小球为载体,通过浸渍法制备了SnCl_(2)-Pt_(1)/PS-PPh_(2)单原子催化剂,考察了其在长链-烯烃氢甲酰化反应中的催化性能,并研究了Sn的促进作用.首先,以1-己烯氢甲酰化为探针反应,对催化剂的组成以及反应条件进行了优化.当Pt/P/Sn=1/2/5时,催化剂表现出最高的催化活性,在90-120℃和4-6 MPa合成气条件下,催化剂转化频率(TOF)为40 h^(-1),产物醛的正异比>42.随后,考察了催化剂的底物适用性.结果表明,C6-C12的高碳烯烃均可被高选择性地转化为相应的醛(正异比>20).然而,在循环使用实验中,由于SnCl_(2)不能稳定锚定在载体上,第二次循环时催化活性降低.但通过补加SnCl_(2),催化活性可以完全恢复.高压热过滤实验及元素检测结果表明,反应过程中Pt没有流失.X射线吸收光谱(XAFS)表征结果表明,反应后Pt仍以单原子形式存在,说明Pt1/PS-PPh_(2)具有良好的稳定性.通过准原位X-射线吸收谱、Mössbauer谱和红外光谱表征对反应过程中Pt和Sn的电子性质和配位结构进行了研究.结果表明,SnCl_(2)在反应过程中逐渐转化为Sn(dioxane)Cl3-物种(1,4-二氧六环为反应溶剂),并与Pt原子形成Pt-Sn键.当反应体系中没有Sn时,Pt(II)会被合成气过度还原并发生团聚.当没有膦配体时,Pt原子也会发生聚集,而且SnCl_(2)会在Pt(II)的催化作用下发生水解生成SnO.因此Sn(dioxane)Cl3-与膦配体共同抑制了Pt(I)在反应过程中的还原与聚集.最后,通过XAFS表征深入研究了反应机理.分析结果表明,CO在催化剂上具有较强的吸附作用,而H_(2)则可能以异裂的方式在催化剂上被活化.据此提出可能的反应机理:首先,H_(2)在催化剂上活化先形成Pt-H物种;随后,烯烃插入Pt-H,形成Pt-烷基物种;接着,CO迁移并插入,生成Pt-酰基物种;最后,经过还原消除步骤,得到最终的产物醛.综上,本文制备了一种对高碳烯烃氢甲酰化反应具有良好催化性能的SnCl_(2)-Pt1/PS-PPh_(2)单原子催化剂,为低成本非Rh基催化剂的开发提供借鉴.同时,揭示了催化体系中Sn的促进作用,为通过Lewis酸来调控催化剂的性能提供了参考.

单原子催化剂催化生物质衍生物选择性加氢的研究进展

生物质是以碳源形式存在的可再生资源,其平台化合物及衍生物的升级利用可得到能源和精细化工产品。多相催化剂在生物质资源的转化中起到重要作用,其中不乏纳米催化剂和单原子催化剂的参与。由于木质纤维素的含氧量较高,不能直接作为工业应用原料,因此需要还原反应来降低其含氧量。加氢反应是降低木质纤维素衍生分子中O C比、提高H C比的重要方法。本研究将综合讨论单原子催化剂在呋喃类、α,β-不饱和醛酮和木质素类平台化合物选择性加氢中的应用。