以磷化铁为添加剂沿(111)面生长磷掺杂金刚石大单晶

掺杂是调控金刚石性能的一种重要手段。本文采用温度梯度法,在5.6 GPa、1 312 ℃的条件下,选用Fe₃P作为磷源进行磷掺杂金刚石大单晶的合成。金刚石样品的显微光学照片表明,随着Fe₃P添加比例的增加,金刚石晶体的颜色逐渐变深,包裹体数量逐渐增加,晶形由板状转变为塔状直至骸晶。金刚石晶形的变化表明Fe₃P的添加使生长金刚石的V形区向右偏移,这是Fe₃P改变触媒特性的缘故。红外光谱分析表明,Fe₃P的添加使金刚石晶体中氮含量上升,这说明磷的进入诱使氮原子更容易进入金刚石晶格中。激光拉曼光谱测试表明,随着Fe₃P添加比例的增加,所合成的掺磷金刚石的拉曼峰位变化不大,其半峰全宽(FWHM)值变大,这说明磷的进入使得金刚石晶格畸变增加。XPS测试结果显示,随着Fe₃P添加比例的增加,金刚石晶体中磷相对碳的原子百分含量也会增加,这意味着添加Fe₃P所合成的金刚石晶体中有磷存在。     

Polymer complexes. LXXVI. Synthesis,characterization, CT‐DNA binding,molecular docking and thermal studies of sulfoxine polymer complexes

Novel polymer complexes of 8‐hydroxyquinoline‐5‐sulfonic acid hydrate ( H ₂ L ) with Cu²⁺, Co²⁺ and Ni²⁺ chloride were prepared and characterized. Microanalysis, magnetic susceptibility, IR spectra, electron spin resonance, mass spectra, X‐ray, molar conductance, thermal, and UV–Vis spectra studies have been used to confirm the structure of the prepared polymer complexes. The molecular and electronic structures of the hydrogen bond conformers for ligand ( H ₂ L ) were optimized theoretically and the quantum chemical parameters were calculated. On the basis of elemental and IR data, the chemical structure of metal chelates commensurate that the tri‐dentate (H₂L) coordinate to metal chlorides through oxygen atom of phenolic OH and oxygen atom of SO₃‐H group by replacing H atoms and nitrogen of the quinoline ring. The magnetic studies suggested the octahedral geometrical structure for all produced polymer complexes with general formula {[ML (OH₂)₃] .xH₂O}_n (M = Cu²⁺, x = 1.; Co²⁺, x = 2 and Ni²⁺, x = 2) in molar ratio (1:1). Coats–Redfern and Horowitz–Metzger methods have been used for calculating the activation thermodynamic parameters of the thermal decomposition for H ₂ L and its polymer complexes. The interaction between H ₂ L and its transition metal complexes with the calf thymus DNA (CT‐DNA) was determined by UV–Vis spectra. Binding efficiency between H ₂ L with the receptors of the prostate cancer (PDB code 2Q7L Hormone) and the breast cancer (PDB code 1JNX Gene regulation) was studied by molecular docking. The inhibition behaviour of H ₂ L against the corrosion of carbon steel / HCl (2 M) solution was studied by weight loss, Tafel polarisation, electrochemical impedance spectroscopy (EIS) and electrochemical frequency modulation (EFM) techniques. The adsorption isotherm was found to be Friendlish isotherm. The morphology of inhibited carbon steel? s surface was studied using scanning electron microscope (SEM) and energy dispersive X‐ray spectroscopy (EDS).     

RAFM钢TIG焊和电子束焊疲劳性能实验和分析模拟

利用ANSYS 对低活化铁素体马氏体(RAFM)钢进行非熔化极气体保护焊(TIG 焊)与电子束焊的抗疲劳模拟分析，再利用SDS200 电液伺服疲劳试验机对TIG 焊和电子束焊的两种RAFM 钢试件进行实验。通过施加相同梯度负荷对TIG 焊和电子束焊试件进行焊缝的疲劳性能实验。与实验结果对比分析，结果显示电子束焊优于 TIG 焊，但在一定负载下可以用TIG 焊代替电子束焊。     

组合式十字形钢管混凝土柱偏压力学性能试验研究

设计了一种由槽钢和方形钢管拼焊形成的组合式十字形钢管混凝土柱,将其灵活地布置在框架结构的中节点,可使柱肢与填充墙等厚,有效地提高建筑使用面积。共制作了6根组合式十字形钢管混凝土柱试件,考虑了偏心距和长细比两种变化参数。通过对其进行偏心受压试验研究,考察了试件的破坏形态和荷载-挠度曲线,并分析了其在不同偏心距和长细比下的荷载-应变曲线发展规律。结果表明:组合式十字形钢管混凝土柱中钢管和槽钢对混凝土的约束作用强,表现为较高的延性系数;偏心距或长细比越大,试件的极限承载力及弹性刚度越小,且偏心距越大延性越好,长细比对延性影响不显著;在受拉侧纵向应变基本上符合平截面假定,在受压侧纵向应变不符合平截面假定。     

Experimental and computational studies of naphthyridine derivatives as corrosion inhibitor for N80 steel in 15% hydrochloric acid

The inhibition effect of three naphthyridine derivatives namely 2-amino-4-(4-methoxyphenyl)-1,8-naphthyridine-3-carbonitrile (ANC-1), 2-amino-4-(4-methylphenyl)-1,8-naphthyridine-3-carbonitrile (ANC-2) and 2-amino-4-(3-nitrophenyl)-1,8-naphthyridine-3-carbonitrile (ANC-3) as corrosion inhibitors for N80 steel in 15% HCl by using gravimetric, electrochemical techniques (EIS and potentiodynamic polarization), SEM, EDX and quantum chemical calculation. The order of inhibition efficiency is ANC-1>ANC-2>ANC-3. Potentiodynamic polarization reveals that these inhibitors are mixed type with predominant cathodic control. Studied inhibitors obey the Langmuir adsorption isotherm. The quantum calculation is in good agreement with experimental results.     

Exploring Regioselective Bond Cleavage and Cross‐Coupling Reactions using a Low‐Valent Nickel Complex

Recently, esters have received much attention as transmetalation partners for cross‐coupling reactions. Herein, we report a systematic study of the reactivity of a series of esters and thioesters with [{(dtbpe)Ni}₂(μ‐η²:η²‐C₆H₆)] (dtbpe=1,2‐bis(di‐tert‐butyl)phosphinoethane), which is a source of (dtbpe)nickel(0). Trifluoromethylthioesters were found to form η²‐carbonyl complexes. In contrast, acetylthioesters underwent rapid C_acyl?S bond cleavage followed by decarbonylation to generate methylnickel complexes. This decarbonylation could be pushed backwards by the addition of CO, allowing for regeneration of the thioester. Most of the thioester complexes were found to undergo stoichiometric cross‐coupling with phenylboronic acid to yield sulfides. While ethyl trifluoroacetate was also found to form an η²‐carbonyl complex, phenyl esters were found to predominantly undergo C_aryl?O bond cleavage to yield arylnickel complexes. These could also undergo transmetalation to yield biaryls. Attempts to render the reactions catalytic were hindered by ligand scrambling to yield nickel bis(acetate) complexes, the formation of which was supported by independent syntheses. Finally, 2‐naphthyl acetate was also found to undergo clean C_aryl?O bond cleavage, and although stoichiometric cross‐coupling with phenylboronic acid proceeded with good yield, catalytic turnover has so far proven elusive.     

Catalytic Activity of Cationic and Neutral Silver(I)–XPhos Complexes with Nitrogen Ligands or Tolylsulfonate for Mannich and Aza‐Diels–Alder Coupling Reactions

Cationic and neutral silver(I)–L complexes (L=Buchwald‐type biaryl phosphanes) with nitrogen co‐ligands or organosulfonate counter ions have been synthesised and characterised through their structural and spectroscopic properties. At room temperature, both cationic and neutral silver(I)–L complexes are extremely active catalysts in the promotion of the single and double A³ coupling of terminal (di)alkynes, pyrrolidine and formaldehyde. In addition, the aza‐Diels–Alder two‐ and three‐component coupling reactions of Danishefsky’s diene with an imine or amine and aldehyde are efficiently catalysed by these cationic or neutral silver(I)–L complexes. The solvent influences the catalytic performance due to limited complex solubility or solvent decomposition and reactivity. The isolation of new silver(I)–L complexes with reagents as ligands lends support to mechanistic proposals for such catalytic processes. The activity, stability and metal–distal arene interaction of these silver(I)–L catalysts have been compared with those of analogous cationic gold(I) and copper(I) complexes.     

银纳米颗粒对聚合物太阳能电池性能的提高

采用水溶性银纳米颗粒附着在反型太阳能电池的电子传输层上,用以提高有机太阳能电池的短路电流。所制备的器件结构为ITO/ZnO/Ag NPs/P3HT(Poly 3-hexylthiophene):PC_[60]BM/MoO₃/Ag。其金属银纳米颗粒的表面等离激元在410 nm处出现了共振吸收峰,半峰全宽约为60 nm。器件的光电流在可见光范围内均有所增加,短路电流相对于标准器件提高了20.2%,光电转化效率相对提高了17.2%。     

Effect of power-law nonlinearity on ${ \mathcal P }{ \mathcal T }$-symmetric optical system with fourth-order diffraction

Gaussian-type soliton solutions of the nonlinear Schrödinger (NLS) equation with fourth order dispersion, and power law nonlinearity in the novel parity-time (${ \mathcal P }{ \mathcal T }$)-symmetric quartic Gaussian potential are derived analytically and numerically. The exact analytical expressions of the solutions are obtained in the first two-dimensional (1D and 2D) power law NLS equations. By means of the linear stability analysis, the effect of power law nonlinearity on the stability of Gauss type solitons in different nonlinear media is carried out. Numerical investigations do confirm the stability of our soliton solutions in both focusing and defocusing cases, specially around the propagation parameters.     

基于SWT方法的钢绞线索微动疲劳特性分析

为得到钢绞线索丝间接触区的应力场分布并预测微动疲劳裂纹萌生位置和微动疲劳寿命，本文利用参数化方法建立了精细化的钢绞线拉索有限元模型，包括整索模型和不同层丝间接触区域的局部精细化子模型．分析了钢绞线索在两种交变荷载工况下的应力场变化情况，并基于多轴疲劳SWT(Smith-Watson-Topper)临界平面法进行了疲劳特性分析和疲劳寿命预测．主要结论如下：钢绞线索内接触区边缘处的微动幅值较大，中心处几乎没有相对滑动，微动疲劳的初始裂纹萌生点位于接触区域边缘；经不同区域子模型分析比较，在轴向循环荷载作用下，外层钢丝的接触区域比内层钢丝更易发生微动疲劳损伤；在横向位移循环荷载作用下，同层钢丝因位置角度不同而产生了较大的疲劳特性差异，且相比轴向循环拉伸，该工况下最不利单丝的微动疲劳寿命更低；与非接触区域相比，接触区的疲劳寿命大幅降低，微动现象对钢绞线索的抗疲劳性能有明显降低作用．