基于相移偏折法的高反射表面面形测量技术

利用单相机所采集的图像实现了对光滑高反射表面面形的直接检测.首先利用相机获取参考平面在标准平面镜中的镜像,然后通过参考平面上的点与归一化成像平面上图像点之间的密集折返对应关系,求得待测镜面的深度距离,从而实现对高反射表面面形的测量.通过光线追迹将该测量过程转化为求解物空间中关于两对应光线束之间的相交问题.以相位为载体获取面形梯度分布,求得该表面的法向量场,并求解相应的反射光线束.通过光线追迹对该光线束与相应入射光线束求“交点”检测高反射表面.对标准平面镜进行实验检测,测量得到的面形平面度为0.19 mm.采用传统方法与本文所提方法对汽车后视镜进行检测,所得检测结果对应点之间的平均距离为0.15 mm,验证了本文方法检测镜面面形的有效性.     

XPS and resistive studies on thin films of a copper(II)‐based coordination polymer deposited on functionalized interdigital electrodes

A symmetrical 2‐thiopyrimidine based molecule with an expanded π‐electron system is synthesized and used to form a self‐assembled monolayer (SAM) on gold surfaces. Utilizing chemical vapor deposition a monolayer of (3‐mercaptopropyl)triethoxysilane is formed on silicon dioxide substrates. Both of these SAM coated substrates are characterized by X‐ray photoelectron spectroscopy and the growth of a coordination polymer built up from 5,5′‐(ethyne‐1,2‐diyl)bis(2‐hydroxyacetophenone) and copper(II) on dual SAM coated transducers is studied. After the deposition procedure on interdigital electrodes the electrical properties of the polymer are investigated performing resistive measurements. A significant change of the resistance, which depends on the surrounding atmosphere, proves the sensing behavior of the synthesized coordination polymer. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 335–344     

Rational Topological Design for Fluorescence Enhancement upon Aggregation of Distyrylfuran Derivatives

A series of 2,5‐distyrylfuran derivatives bearing pentafluorophenyl‐ and cyanovinyl units have been synthesized for aggregation‐induced emission (AIE). The effect of the type and extent of the supramolecular connections on the AIE of the furan derivatives were examined and correlated with their X‐ray crystal structures. It was found that the simultaneous presence of cyano and perfluorophenyl units strongly enhances the fluorescence upon aggregation. Single‐crystal X‐ray diffraction analysis confirmed that C?H???F, F???F, C?H???nitrile, Ar???Ar_F (Ar=aryl, Ar_F=fluoroaryl), and nitrile???Ar_F intra‐ and intermolecular interactions drive the topology of the molecule and that solid‐state supramolecular contacts favor AIE of the furan derivatives.     

Structure determination of KScS2, RbScS2 and KLnS2 (Ln = Nd,Sm, Tb,Dy, Ho,Er, Tm and Yb) and crystal–chemical discussion

The title structures of KScS₂ (potassium scandium sulfide), RbScS₂ (rubidium scandium sulfide) and KLnS₂ [Ln = Nd (potassium neodymium sufide), Sm (potassium samarium sulfide), Tb (potassium terbium sulfide), Dy (potassium dysprosium sulfide), Ho (potassium holmium sulfide), Er (potassium erbium sulfide), Tm (potassium thulium sulfide) and Yb (potassium ytterbium sulfide)] are either newly determined (KScS₂, RbScS₂ and KTbS₂) or redetermined. All of them belong to the α‐NaFeO₂ structure type in agreement with the ratio of the ionic radii r³⁺/r⁺. KScS₂, the member of this structural family with the smallest trivalent cation, is an extreme representative of these structures with rare earth trivalent cations. The title structures are compared with isostructural alkali rare earth sulfides in plots showing the dependence of several relevant parameters on the trivalent cation crystal radius; the parameters thus compared are c, a and c/a, the thicknesses of the S—S layers which contain the respective constituent cations, the sulfur fractional coordinates z(S²⁻) and the bond‐valence sums.     

Sulfono‐γ‐AApeptides as a New Class of Nonnatural Helical Foldamer

Foldamers offer an attractive opportunity for the design of novel molecules that mimic the structures and functions of proteins and enzymes including biocatalysis and biomolecular recognition. Herein we report a new class of nonnatural helical sulfono‐γ‐AApeptide foldamers of varying lengths. The crystal structure of the sulfono‐γ‐AApeptide monomer S6 illustrates the intrinsic folding propensity of sulfono‐γ‐AApeptides, which likely originates from the bulkiness of tertiary sulfonamide moiety. The two‐dimensional solution NMR spectroscopy data for the longest sequence S1 demonstrates a 10/16 right‐handed helical structure. Optical analysis using circular dichroism further supports well‐ defined helical conformation of sulfono‐γ‐AApeptides in solution containing as few as five building blocks. Future development of sulfono‐γ‐AApeptides may lead to new foldamers with discrete functions, enabling expanded application in chemical biology and biomedical sciences.     

Ba3V2S4O3: A Mott Insulating Frustrated Quasi‐One‐Dimensional S=1 Magnet

Through a solid‐state reaction, a practically phase pure powder of Ba₃V₂S₄O₃ was obtained. The crystal structure was confirmed by X‐ray single‐crystal and synchrotron X‐ray powder diffraction (P6₃, a=10.1620(2), c=5.93212(1) Å). X‐ray absorption spectroscopy, in conjunction with multiplet calculations, clearly describes the vanadium in charge‐disproportionated V^IIIS₆ and V^VSO₃ coordinations. The compound is shown to be a strongly correlated Mott insulator, which contradicts previous predictions. Magnetic and specific heat measurements suggest dominant antiferromagnetic spin interactions concomitant with a weak residual ferromagnetic component, and that intrinsic geometric frustration prevents long‐range order from evolving.     

Distinct effect of xenobiotics on the metal‐binding properties of protein molecules

The X‐ray standing‐wave method was applied to study the elemental composition and molecular organization of ordered protein films of alkaline phosphatase exposed to different xenobiotics (drug compounds, lead). Binding of metal ions from triply distilled water to protein molecules has been experimentally observed. Definite differences in the arrangement of impurity metal ions in the films have been established. The considerable enhancement of protein–metal interactions is attributed to partial rearrangement of the protein native structure, induced by xenobiotics.     

A rapid dissolution procedure to aid initial nuclear forensics investigations of chemically refractory compounds and particles prior to gamma spectrometry

A rapid and effective preparative procedure has been evaluated for the accurate determination of low-energy (40–200 keV) gamma-emitting radionuclides (²¹⁰Pb, ²³⁴Th, ²²⁶Ra, ²³⁵U) in uranium ores and uranium ore concentrates (UOCs) using high-resolution gamma ray spectrometry. The measurement of low-energy gamma photons is complicated in heterogeneous samples containing high-density mineral phases and in such situations activity concentrations will be underestimated. This is because attenuation corrections, calculated based on sample mean density, do not properly correct where dense grains are dispersed within a less dense matrix (analogous to a nugget effect). The current method overcomes these problems using a lithium tetraborate fusion that readily dissolves all components including high-density, self-attenuating minerals/compounds. This is the ideal method for dissolving complex, non-volatile components in soils, rocks, mineral concentrates, and other materials where density reduction is required. Lithium borate fusion avoids the need for theoretical efficiency corrections or measurement of matrix matched calibration standards. The resulting homogeneous quenched glass produced can be quickly dissolved in nitric acid producing low-density solutions that can be counted by gamma spectrometry. The effectiveness of the technique is demonstrated using uranium-bearing Certified Reference Materials and provides accurate activity concentration determinations compared to the underestimated activity concentrations derived from direct measurements of a bulk sample. The procedure offers an effective solution for initial nuclear forensic studies where complex refractory minerals or matrices exist. It is also significantly faster, safer and simpler than alternative approaches.     

Structural characterization of disperse black 9 based Cu (II) complex and investigation of its some properties

We obtained the azo‐imine ligand (2,2′‐[4‐(5‐methoxy salicylidene‐4‐iminophenylazo)phenylimino]diethanol) (HL) and its Cu (II) complex (CuL) from the ethanol solution. The complex Cu(L)₂ was obtained as single crystals from the CH₃OH solution and structurally characterized. The electronic and photoluminescence properties of the ligand and its Cu (II) complex were investigated both in DMF solution and solid state. The oxidation and reduction behaviours of the compounds were studied in the solution and found that the redox processes are irreversible. Thermal studies show that the ligand has higher thermal stability than the CuL complex. Single crystals of the complex were obtained from slow evaporation of a DMF solution of the complex. Crystals of the complex showed a diffraction pattern; however, the structure of the complex was able to be solved.     

In vitro biomolecular interaction studies and cytotoxic activities of copper(II) and zinc(II) complexes bearing ONS donor thiosemicarbazones

Among all the bio‐metals, zinc and copper derivatives of ONS donor thiosemicarbazone have aroused great interest because of their potential biological applications. Multisubstituted thiosemicarbazone ligand H₂dspt (3,5‐dichlorosalicylaldehyde‐N⁴‐phenylthiosemicarbazone) derived new ternary complexes like [Zn(dspt)(phen)]?DMF ( 1 ) and [Cu(dspt)(phen)]?DMF ( 2 ), and another thiosemicarbazone, H₂dsct (3,5‐dichlorosalicylaldehyde‐N⁴‐cyclohexylthiosemicarbazone), derived [Cu(dsct)(bipy)]?DMF ( 3 ). These complexes have been characterized by elemental analysis (CHNS), Fourier transform infrared (FT‐IR), ultraviolet–visible (UV–Vis) and proton nuclear magnetic resonance (¹H‐NMR) spectra. The structures of the complexes were obtained by single‐crystal X‐ray diffraction analysis. Compounds 1 and 2 got crystallized in the monoclinic P2₁/c space group. The complexes showed interesting supramolecular interaction, which in turn stabilizes the complexes. The ground state electronic configurations of the complexes were studied using the B3LYP/LANL2DZ basis set, and ESP plots of complexes were investigated. The interaction of the complexes with calf thymus DNA (CT‐DNA) was studied using absorption and fluorescence spectroscopic methods. A UV study of the interaction of the complexes with calf thymus DNA (CT‐DNA) has shown that the complexes can effectively bind to CT‐DNA, and [Cu(dspt)(phen)]·DMF ( 2 ) exhibited the highest binding constant to CT‐DNA (K_b = 3.7 × 10⁴). Fluorescence spectral studies also indicated that Complex 2 binds relatively stronger with CT DNA through intercalative mode, exhibiting higher binding constant (K_q = 4.7 × 10⁵). The DNA cleavage result showed that the complexes are capable of cleaving the DNA without the help of any external agent. Molecular docking studies were carried out to understand the binding of complexes with the molecular target DNA. Complex 2 exhibited the highest cytotoxicity against human breast cancer cell line MD‐MBA‐231 (IC₅₀ = 23.93 μg/mL) as compared to Complex 1 (IC₅₀ = 44.40 μg/mL) .