Rhenium carbonyl complexes with monodentate-coordinated diphosphines: activation of terminal phosphino groups towards amine-oxide oxidation

Terminal phosphino groups of [Re₂(CO)₉(η¹-P-P)] (P-P = diphosphines) are activated towards oxidation by Me₃NO. The respective reactions of Me₃NO with [Re₂(CO)₉{η¹-P(o-anisyl)₂(CH₂)₃PPh₂}], [Re₂(CO)₉{η¹-PPh₂(CH₂)₃P(o-anisyl)₂}] and [Re₂(CO)₉(η¹-trans-PPh₂CHCHPPh₂)] were studied to investigate the mechanism of this oxidation. The results are consistent with an intramolecular pathway involving a cyclic intermediate, without exchange of the coordinated and terminal phosphino groups. A mechanism which involves an interaction of the terminal phosphino group with a carbonyl ligand is proposed. In sharp contrast to eq-[Re₂(CO)₉(η¹-P-P)] (P-P = Ph₂P(CH₂)_nPPh₂, n = 1-6), eq-[Re₂(CO)₉(η¹-trans-PPh₂CHCHPPh₂)] appears to be indefinitely stable towards equatorial → axial isomerization at room temperature, thus, allowing its crystal structure to be determined.     

Tetraphenylethene-Embedded Pillar[5]arene and [15]Paracyclophane: Distorted Cavities and Host–Guest Binding Properties

Two aggregation-induced emission (AIE) macrocycles (DMP[5]-TPE and PCP[5]-TPE) were prepared by embedding Tetraphenylethene (TPE) unit into the skeletons of Dimethoxypillar[5]arene (DMP[5]) and [15]Paracyclophane ([15]PCP) at meso position, respectively. In crystal, the PCP[5]-TPE showed a distorted cavity, and the incubation of hexane inside the DMP[5]-TPE cavity caused a distinct change in the molecular conformation compared to PCP[5]-TPE. There was no complexation between PCP[5]-TPE and 1,4-dicyanobutane (DCB). UV absorption experiments showed the distorted cavity of DMP[5]-TPE hindered association with DCB.     

Pattern-dependent tunable adhesion of superhydrophobic MnO2 nanostructured film

Tuning the adhesive force on a superhydrophobic MnO(2) nanostructured film was achieved by fabricating different patterns including meshlike, ball cactus-like, and tilted nanorod structures. The marvelous modulation range of the adhesive forces from 130 to nearly 0 μN endows these superhydrophobic surfaces with extraordinarily different dynamic properties of water droplets. This pattern-dependent adhesive property is attributed to the kinetic barrier difference resulting from the different continuity of the three-interface contact line. This finding will provide the general strategies for the adhesion adjustment on superhydrophobic surfaces.     

Extraction behavior of copper(II) ion with a hydrophobic amino-functionalized ionic liquid

We have prepared the hydrophobic amino-functionalized ionic liquid (IL) 1-(2-aminoethyl)-3-butylimidazolium hexafluorophosphate and investigated its extraction behavior for copper(II) ion as a model cation. The IL, due to the presence of an amino group, is capable of complexing Cu(II) in a ratio of 6:1. The parameters affecting the extraction efficiency were optimized. The IL-based liquid–liquid microextraction was successfully applied to the analysis of Cu(II) in an environmental water standard reference material. The results are promising in terms of liquid–liquid microextraction, separation, and preconcentration of Cu(II).

Synthesis, Crystal Structure and Magnetic Behaviour of {[Yb(1,4-BDC)1.5(H2O)4]·H2O}n (1,4-BDC?=?1,4-benzenedicarboxylate)

Abstract  

The title complex {[Yb(1,4-BDC)_1.5(H₂O)₄]·H₂O}_n (1) (1,4-BDC = 1,4-benzenedicarboxylate) has been hydrothermally synthesized and structurally characterized by the single crystal X-ray diffraction. Crystals of compound 1 belongs to the triclinic crystal system, space group P-1; a = 7.549(3) ?, b = 10.072(4) ?, c = 10.470(4) ?, α = 87.810(4)°, β = 82.531(4)°, γ = 86.306(4)°, V = 787.3(5) ?³, Z = 2. The Yb(III) atoms are linked by the deprotonated 1,4-BDC ligands in two kinds of bridging modes. Four Yb(III) atoms at each corner (nodes) and four 1,4-BDC ligands at each edge (spacers) form a edge–sharing 36-membered rings. The rhombohedral Yb₄(1,4-BDC)₄ arranged in an alternating fashion to construct a 1D ladder-like chain along the c axis. Two neighboring chains are linked to each other in a parallel fashion to construct 3D supramolecular structure by O–H···O hydrogen bonds and π–π stacking interactions. In addition, the properties of thermogravimetric analysis and magnetic behaviors of the complex have been also discussed.     

LEC法生长富磷掺铁InP单晶晶格应变与残留应力研究

运用原位磷注入合成法在高压单晶炉内合成富磷的InP熔体,并利用液封直拉法(LEC)生长出了3英寸富磷掺Fe的InP单晶.运用高分辨率X射线衍射技术、偏振差分透射谱测试技术、光致荧光谱技术对富磷掺Fe的InP晶片进行了结构、应力及发光特性测试.结果表明,晶格的应变导致了PL发光峰峰位的变化,晶格应变与残留应力测试结果相一致,说明材料生长过程中的热应力是导致样品晶格常数分布不均匀的主要因素.     

Analysis of an interfacial crack in a piezoelectric bi-material via the extended Green’s functions and displacement discontinuity method

Based on the extended Stroh formalism, we first derive the extended Green’s functions for an extended dislocation and displacement discontinuity located at the interface of a piezoelectric bi-material. These include Green’s functions of the extended dislocation, displacement discontinuities within a finite interval and the concentrated displacement discontinuities, all on the interface. The Green’s functions are then applied to obtain the integro-differential equation governing the interfacial crack. To eliminate the oscillating singularities associated with the delta function in the Green’s functions, we represent the delta function in terms of the Gaussian distribution function. In so doing, the integro-differential equation is reduced to a standard integral equation for the interfacial crack problem in piezoelectric bi-material with the extended displacement discontinuities being the unknowns. A simple numerical approach is also proposed to solve the integral equation for the displacement discontinuities, along with the asymptotic expressions of the extended intensity factors and J-integral in terms of the discontinuities near the crack tip. In numerical examples, the effect of the Gaussian parameter on the numerical results is discussed, and the influence of different extended loadings on the interfacial crack behaviors is further investigated.     

Synthesis and properties of organic-inorganic hybrid P(NIPAM-<Emphasis Type="Italic">co</Emphasis>-AM-<Emphasis Type="Italic">co</Emphasis>-TMSPMA) microgels

Utilizing the hydrolysis and condensation of the methoxysilyl moieties, organic-inorganic hybrid poly(N-isopropylacrylamide-co-acrylamide-co-3-(trimethoxysilyl)propylmethacrylate) P(NIPAM-co-AM-co-TMSPMA) microgels were prepared via two different methods. The first method was that the microgels were post-fabricated from the crosslinkable linear P(NIPAM-co-AM-co-TMSPMA) terpolymer aqueous solutions above the lower critical solution temperature (LCST) of the terpolymer. For the second method, the microgels were directly synthesized by conventional surfactant free emulsion copolymerization of NIPAM, AM, and TMSPMA. The hydrodynamic diameter and stability of the resultant P(NIPAM-co-AM-co-TMSPMA) microgels strongly depend on the pH and temperature of the microgel aqueous solution. The hydrodynamic diameters of the microgels decreased with increasing the measuring temperature. The phase transition temperature of the microgels was found to be around 34°C, which was independent of the initial terpolymer concentration and shifted to lower temperature with increasing the preparation temperature. Increasing the initial amount of AM will enhance the instability of the microgels at high pH values. Moreover, the P(NIPAM-co-AM-co-TMSPMA) microgels obtained from the linear terpolymer had more homogeneous microstructures as compared with the corresponding NIPAM/AM/TMSPMA microgels prepared by one step emulsion copolymerization as revealed by light scattering measurements.     

Roughness measurement of metals using a modified binary speckle image and adaptive optics

This paper proposes an integrated roughness measurement system that is based on adaptive optics (AO) and binary analysis of speckle pattern images. The aim of this study was to demonstrate the necessity for AO compensation in regions containing both heat and fluid flow turbulences. A speckle image was obtained by projecting a laser beam onto the specimen surface, and the laser pattern image reflected from the surface was binarized to experimentally correlate the intensity with the surface roughness. In the absence of the AO correction scheme, induced turbulences can severely increase the residual rms error from 0.14 to 1.4 μm. After a real-time closed-loop AO correction, we can reduce the wavefront root mean square (rms) error to 0.12 μm, which not only compensates for the aberration error from induced disturbances but also improves the overall performance of the optical system. In addition, an AO system having different gains was investigated, and a threshold gain value was found to be able to steadily compensate for the wavefront errors in less than 2 s. Measurement results of five steel samples having roughness ranging from 0.2 to 3.125 μm (0.3λ and 5λ, where λ is the diode laser wavelength) demonstrate an excellent correlation between the intensity distribution of binary images and average roughness with a correlation coefficient of 0.9982. Furthermore, the proposed AO-assisted system is in good agreement with the stylus method and less than 9.73% error values can be consistently obtained.