Mechanically Strong Janus Poly(N-isopropylacrylamide)/Graphene Oxide Hydrogels as Thermo-responsive Soft Robots

Simple preparation of stimuli-responsive hydrogels with good mechanical properties and mild stimuliresponsiveness is essential for their applications as smart soft robots.Mechanically strong Janus poly(Nisopropylacrylamide)/graphene oxide (PNIPAM/GO) nanocomposite hydrogels with stimuli-responsive bending behaviors are prepared through a simple one-step method by using molds made of a Teflon plate and a glass plate.Residual oxygen in the air bubbles on the Teflon plate surface affects the polymerization and hence the cross-linking density,leading to the different swelling/deswelling rates of the two sides of the gels.Therefore,the hydrogels exhibit bending/unbending behaviors upon heating/cooling in water.The incorporation of GO nanosheets dramatically enhances the mechanical properties of Janus hydrogels.Meanwhile,the photo-responsive property of the GO nanosheets also imparts the hydrogels with remotecontrollable deformation under IR irradiation.The application of the Janus PNIPAM/GO hydrogels as thermo-responsive grippers is demonstrated.     

Confining effect on the bearing capacity of circular footings on a purely cohesive soilEffet du confinement sur la capacité portante d'une fondation circulaire sur un sol purement cohérent

The bearing capacity of axially symmetrical footings acting on a purely cohesive soil foundation contained by a rigid wall at a finite distance is investigated within the framework of the Yield design theory. Following the same tracks as in a preceding paper devoted to strip footings, the analysis is performed by referring to already existing results concerning the bearing capacity of a circular footing on a soil layer with limited thickness. It comes out that the bearing capacity factor determined by Eason and Shield for a rough circular footing on an unlimited soil foundation is increased by a correction factor that increases when the diameter of the container decreases. Comparison with the results obtained for strip footings acting on a purely cohesive soil in the same conditions shows that the confining effect is significantly lower for a circular footing than for a strip footing. To cite this article: J. Salençon, C. R. Mecanique 330 (2002) 521–525.     

High-pressure investigations under CO/H2 of rhodium complexes containing hemispherical diphosphites

The two rhodium complexes [Rh(acac)(L(R))] (L(R)=(S,S)-5,11,17,23-tetra-tert-butyl-25,27-di(OR)-26,28-bis(1,1'-binaphthyl-2,2'-dioxyphosphanyloxy)calix[4]arene; 6: R=benzyl, 7: R=fluorenyl), each based on a hemispherical chelator forming a pocket about the metal centre upon chelation, are active in the hydroformylation of 1-octene and styrene. As expected for this family of diphosphanes, both complexes resulted in remarkably high selectivity towards the linear aldehyde in the hydroformylation of 1-octene (l/b≈15 for both complexes). Linear aldehyde selectivity was also observed when using styrene, but surprisingly only 6 displayed a marked preference for the linear product (l/b=12.4 (6) vs. 1.9 (7)). A detailed study of the structure of the complexes under CO or CO/H(2) in toluene was performed by high-pressure NMR (HP NMR) and FT-IR (HP-IR) spectroscopies. The spectroscopic data revealed that treatment of 6 with CO gave [Rh(acac)(CO)(η(1)-L(benzyl))] (8), in which the diphosphite behaves as a unidentate ligand. Subsequent addition of H(2) to the solution resulted in a well-defined chelate complex with the formula [RhH(CO)(2)(L(benzyl))] (9). Unlike 6, treatment of complex 7 with CO only led to ligand dissociation and concomitant formation of [Rh(acac)(CO)(2)], but upon addition of H(2) a chelate complex analogous to 9 was formed quantitatively. In both [RhH(CO)(2)(L(R))] complexes the diphosphite adopts the bis-equatorial coordination mode, a structural feature known to favour the formation of linear aldehydes. As revealed by variable-temperature NMR spectroscopy, these complexes show the typical fluxionality of trigonal bipyramidal [RhH(CO)(2)(diphosphane)] complexes. The lower linear selectivity of 7 versus 6 in the hydroformylation of styrene was assigned to steric effects, due to the pocket in which the catalysis takes place being less adapted to accommodate CO or larger olefins and, therefore, possibly leading to facile ligand decoordination. This interpretation was corroborated by an X-ray structure determination carried out for 7.     

Properties of Ionic Liquid Confined in Porous Silica Matrix

Porous silica matrices of different pore sizes with confined ionic liquid (1‐butyl‐3‐methylimidazolium hexafluorophosphate) [BMIM] [PF₆] were prepared by sol‐gel technique using a tetraethyl orthosilicate (TEOS) precursor with an aim to study the changes in physico‐chemical properties of ionic liquid on confinement. It is found that on confinement 1) melting point decreases, 2) fluorescence spectra shows a red shift and 3) the vibrational bands are affected particularly those of imadazolium ring, which interacts more with the walls of the silica matrix. Preliminary theoretical calculations suggest that SiO₂ matrix interact more with the heterocyclic group of [BMIM] cation than the tail alkyl chain end group resulting in significant changes in the aromatic vibrations.     

Micro-patterning of vapor-phase polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) using ink-jet printing/soft lithography

Highly conductive and transparent poly(3,4-ethylenedioxythiophene) (PEDOT) thin films can be prepared effectively via vapor-phase polymerization (VPP) with the addition of imidazole (Im) based derivatives. The addition of Im that has one and/or two alkyl substituents significantly improved the electrical conductivity of PEDOT thin films. In an effort to develop a facile PEDOT micro-patterning method, we investigated ink-jet printing and soft lithography. The procedure of oxidant patterning with a weak base followed by VPP of a 3,4-ethylenedioxythiophene (EDOT) monomer provides an effective and simple method for micro-patterning of an intrinsic conductive polymer (ICP).     

聚酰亚胺薄膜表面粗糙度的影响因素

 采用热蒸发气相沉积聚合方法（VDP）制备了聚酰亚胺(PI)薄膜,研究了设备、衬底温度、升温过程和单体配比因素对PI薄膜表面形貌的影响。利用干涉显微镜和扫描电镜对薄膜表面形貌进行了分析;利用原子力显微镜测定了薄膜表面粗糙度。结果表明：设定蒸发源-衬底距离为74 cm时可成连续膜;蒸发源采用一段升温和多段升温时,膜表面均方根粗糙度分别为291.23 nm和61.99 nm;采用细筛网可防止原料的喷溅;均苯四甲酸二酐和4,4′-二氨基二苯醚（PMDA和ODA）单体沉积速率比值为0.9∶1时,膜表面均方根粗糙度值可减小至3.30 nm;沉积衬底温度保持30 ℃左右时,膜表面均方根粗糙度为4.01 nm, 随温度的上升,膜表面质量会逐渐变差。     

Facile synthesis of thiol-stabilized CdSexTe1−x nanocrystals

CdSe_xTe_1−x nanocrystals (x=0.25, 0.40, 0.50, 0.60 and 0.75) were synthesized using thioglycerol as a stabilizing agent. The composition of the CdSe_xTe_1−x nanocrystals was precisely controlled by tuning the precursor (Se/Te) ratio. The structural, morphological and optical properties of the nanocrystals were analyzed using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), diffused reflectance spectroscopy (DRS) and photoluminescence (PL) measurements. It is found that the Se/Te ratio significantly affects the properties of the resultant CdSe_xTe_1−x nanocrystals. XRD pattern of the CdSe_xTe_1−x nanocrystals revealed cubic, hexagonal and mixed phases depending on the ratio of Se:Te. Surface morphology of the CdSe_xTe_1−x nanocrystals showed nanoclusters of sizes ∼50 nm, with the adjacent cluster interlinking each other. DRS revealed the size dependence band gap energy prevailing in the CdSe_xTe_1−x nanocrystals from 1.52 to 2.66 eV due to the optical bowing effect. PL measurements exhibited band edge emission in the visible spectral region, and are red shifted with increase in Se concentration. The facile route employed in the present work to synthesis the CdSe_xTe_1−x nanocrystals in an aqueous medium is simple and controllable, and the strategy presented will be handy in preparing diverse semiconducting nanocrystals.     

菲涅耳波带板应用于聚变靶的高分辨X射线成像分析

在惯性约束核聚变研究中,为了实现1μm高空间分辨keV-X射线成像,文中发展了菲涅耳波带板(FZP)直接成像的分析方法,并通过数值计算研究了FZP的成像特性.针对钛K_α线(光子能量4.51 keV,波长0.275 nm),提出了FZP参数,对制作技术的要求较低.研究了靶尺度的影响.FZP的有效视场使它能够对数毫米大尺度靶实现高分辨成像.还研究了入射光的光谱带宽对成像的影响.FZP的色差有助于单色成像,但是带宽超过限度会导致像的反衬度降低.这些结果表明FZP应用于聚变点火靶的高空间分辨X射线成像的能力,也为应用提出了要求. 关键词： X射线成像 惯性约束核聚变 菲涅耳波带板     

Peptide-induced patterning of gold nanoparticle thin films

In this work, the use of patterned proteins and peptides for the deposition of gold nanoparticles on several substrates with different surface chemistries is presented. The patterned biomolecule on the surface acts as a catalyst to precipitate gold nanoparticles from a precursor solution of HAuCl₄ onto the substrate. The peptide patterning on the surfaces was accomplished by physical adsorption or covalent attachment. It was shown that by using covalent attachment with a linker molecule, the influence of the surface properties from the different substrates on the biomolecule adsorption and subsequent nanoparticle deposition could be avoided. By adjusting the reaction conditions such as pH or HAuCl₄ concentration, the sizes and morphologies of deposited gold nanoparticle agglomerates could be controlled. Two biomolecules were used for this experiment, 3XFLAG peptide and bovine serum albumin (BSA). A micro-transfer molding technique was used to pattern the peptides on the substrates, in which a pre-patterned poly(dimethylsiloxane) (PDMS) mold was used to deposit a lift-off pattern of polypropylmethacrylate (PPMA) on the various substrates. The proteins were either physically adsorbed or covalently attached to the substrates, and an aqueous HAuCl₄ solution was applied on the substrates with the protein micropatterns, causing the precipitation of gold nanoparticles onto the patterns. SEM, AFM, and Electron Beam Induced Current (EBIC) were used for characterization.