Study on the Single Crystals of Poly(3-octylthiophene) Induced by Solvent-Vapor Annealing

Needle-like single crystals of poly(3-octylthiophene) (P3OT) have been prepared by tetrahydrofuran-vapor annealing. The morphology and structure of the crystals were characterized with optical microscopy, scanning electron microscopy, atomic force microscopy, transmission electron microscopy, and wide-angle X-ray diffraction. It is observed that the P3OT molecules are packed with the backbones parallel to the length axis of the crystal and the alkyl side chains perpendicular to the substrate. The field effect transistor based on the P3OT single crystal exhibited a charge carrier mobility of 1.54 x 10(-4) cm(2)/(Vs) and on/off current ratio of 37, and the molecular orientation of the crystal is ascribed to account for the device performance. The time-dependent morphological evolution demonstrated that the crystals underwent Ostwald ripening when annealed.

Synthesis and characterization of monodisperse spherical core-shell structured SiO2@Y3Al5O12 : Ce3+/Tb3+ phosphors for field emission displays

Nanocrystalline Y3Al5O12: Ce3+/Tb3+ ( average crystalline size 30 nm) phosphor layers were coated on non-aggregated, monodisperse and spherical SiO2 particles by the sol-gel method, resulting in the formation of core-shell structured SiO2@Y3Al5O12:Ce3+/Tb3+ particles. X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, photoluminescence, cathodoluminescence spectra, as well as lifetimes were utilized to characterize the core-shell structured SiO2@Y3Al5O12: Ce3+/Tb3+ phosphor particles. The obtained core-shell structured phosphors consist of well-dispersed submicron spherical particles with a narrow size distribution. The thickness of the Y3Al5O12:Ce3+/Tb3+ shells on the SiO2 cores ( average size about 500 nm, crystalline size about 30 nm) could be easily tailored by varying the number of deposition cycles (100 nm for four deposition cycles). Under the excitation of ultraviolet and low-voltage electron beams (1-3 kV), the core-shell SiO2@Y3Al5O12:Ce3+/ Tb3+ particles show strong yellow-green and green emission corresponding to the 5d-4f emission of Ce3+ and D-5(4)-F-7(J) ( J = 6, 5, 4, 3) emission of Tb3+, respectively.

Structural diversity of lanthanide-amino acid complexes under near physiological pH conditions and their recognition of single-stranded DNA

We reported here four structures of lanthanide-amino acid complexes obtained under near physiological pH conditions and their individual formula can be described as [Tb-2(DL-Cys)(4)(H2O)(8)]Cl-2 (1), [Eu-4(mu(3)-OH)(4)(L-Asp)(2)(L-HAsp)(3)(H2O)(7)] Cl center dot 11.5H(2)O (2), [Eu-8-(L-HVal) (16)(H2O)(32)]Cl-24 center dot 12.5H(2)O (3), and [Tb-2(DL-HVal)(4)(H2O)(8)]Cl-6 center dot 2H(2)O (4). These complexes showed diverse structures and have shown potential application in DNA detection. We studied the interactions of the complexes with five single-stranded DNA and found different fluorescence enhancement, binding affinity and binding stoichiometry when the complexes are bound to DNA.

Evaluation of different culture conditions for high-level soluble expression of human cyclin A(2) with pET vector in BL21 (DE3) and spectroscopic characterization of its inclusion body structure

In this paper, we evaluated various parameters of culture condition affecting high-level soluble expression of human cyclin A, in Escherichia coli BL21(DE3), and demonstrated that the highest protein yield was obtained using TB(no glycerol) + 0.5% glucose medium at 25 degrees C. By single immobilized metal ion affinity chromatography, we got highly purified human cyclin A(2) with a yield ranged from 20 to 30 mg/L. By amyloid-diagnostic dye ThT binding and Fourier transform infrared spectroscopy, we observed a significant decrease in alpha-helix content and an increase in beta-sheet structure in cyclin A(2) inclusion body in comparison to its native protein, and confirmed the resemblance of the internal organization of cyclin A(2) inclusion body and amyloid fibrils.

Competition of lamellar orientation in thin films of a symmetric poly(styrene)-b-poly(L-lactide)diblock copolymer in melt state

We have studied the lamellar orientation in thin films of a model diblock copolymer, symmetric poly(styrene)-b-poly(L-lactide) (PS-PLLA), in the melt state on supported silicon wafer surface. In this system, while the PLLA block prefers to wet the polymer/substrate interface, the polymer/air as well as polymer/polymer interface is neutral for both blocks due to the similar surface energies of PS and PLLA in melt state. Our results demonstrate that the interplay of the interfaces during phase separation results in a series of structures before approaching the equilibrium state. Lamellar orientation of thin films with different initial film thicknesses at different annealing stages has been investigated using atomic force microscopy (AFM), transmission electronic microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). It is found that in the early stage (annealing time t < 10 min), the polymer/substrate interface dominates the structure evolution, leading to a parallel lamellar structure with holes or islands formed depending on the initial film thickness. Later on, the neutral air interface becomes important and leads to a transition of lamellar orientation from parallel to perpendicular. It is interesting to see that for films with thickness h > 2L, where L is the bulk lamellar period, the lamellar orientation transition can occur independently in different parallel lamellar domains due to the neutrality of polymer/polymer interface.

基质晶体的真空紫外光谱研究

初步总结了基质晶体中吸收带位置的规律 ,即氧化物 (CaO∶Eu ,Y2 O3∶Eu ,≈ 2 0 0nm) >多铝酸盐 (BaMgAl1 0 O1 7∶Eu ,≈ 175nm)≥硅酸盐 (Ca2 SiO4 ∶Tb ,160～ 170nm) >硼酸盐 [(Y ,Gd)BO3∶Eu ,15 0～ 160nm]≥钒酸盐 (YVO4 ∶Eu ,≈ 15 5nm)≈正磷酸盐 [(La,Gd)PO4 ∶Eu ,≈ 15 5nm] >五磷酸盐 (TbP5O1 4∶Eu ,≈ 13 5nm) >二磷酸盐 [Sr3(PO4 ) 2 ∶Eu或K3Tb(PO4 ) 2 ∶Eu ,≈ 12 5nm] >氟化物 (LaF3∶Eu或LiYF4 ∶Eu ,≈ 12 0nm)。基质吸收带的位置主要取决于基质的阴离子、阴离子基团 ,以及基质的组成、结构和键能 ,也受基质中阳离子的影响。这一初步规律将有助于人们寻找优质的新型紫外晶体和新型等离子体平板显示器件用的荧光粉。

Morphology and structure of poly(di-n-butylsilane) single crystals prepared by controlling kinetic process of solvent evaporation

The silicon backbone conformation in poly(di-n-butylsilane) (PDBS) has been shown to be a 7/3 helix at ambient conditions, which is in marked contrast to the near-planar conformation of its homologous polymers with side chain lengths of one to three or six to eight carbon atoms. In this work, both the 7/3 helical and near-planar chain conformations are achieved by controlling the solvent evaporation rate around room temperature. The chain conformation and crystal structure obtained in this method have been correlated to the crystal morphology by wide-angle X-ray diffraction, transmission electron microscopy, electron diffraction, optical microscopy, atomic force microscopy, and UV absorption spectrum. The lath-shaped single crystals obtained at 12 degreesC correspond to an orthorhombic form with near-planar chain conformation whereas the lozenge-shaped single crystals obtained at 30 degreesC (in coexistence with the lath-shaped crystals) are orthohexagonal with a 7/3 helix.

Effects of casting solvents on the formation of inverted phase in block copolymer thin films

Previously, an inverted phase (the minority blocks comprising the continuum phase) was found in solution-cast block copolymer thin films. In this study, the effect of casting solvents on the formation of inverted phase has been studied. Two block copolymers, poly(styrene-b-butadiene) (SB) (M-w = 73 930 Da) and poly(styrene-b-butadiene-b-styrene) (SBS) (M-w = 140 000 Da), with comparable block lengths and equal polystyrene (PS) weight fraction (similar to30 wt %) were used. The copolymer thin films were cast from different solvents, toluene, benzene, cyclohexane, and binary mixtures of benzene and cyclohexane. Toluene and benzene are good solvents for both PS and PB, but have a preferential affinity for PS, while cyclohexane is a good solvent for PB but a Theta solvent for PS (T-Theta = 34.5 degreesC). The differential solvent affinity for PS and PB was estimated in terms of a difference between the polymer-solvent interaction parameter, chi, for each block. Under an extremely slow solvent evaporation rate, the time-dependent phase behavior during such a solution-to-film process was examined by freeze-drying the samples at different stages, corresponding to different copolymer concentrations, rho.

Thickness-dependent molecular chain and lamellar crystal orientation in ultrathin poly(di-n-hexylsilane) films

The molecular chain and lamellar crystal orientation in ultrathin films (thickness < 100 nm) of poly(di-n-hexylsilane) (PDHS) on silicon wafer substrates have been investigated by using transmission electronic microscopy, wide-angle X-ray diffraction, atomic force microscopy, and UV absorption spectroscopy. PDHS showed a film thickness-dependent molecular chain and lamellar crystal orientation. Lamellar crystals grew preferentially in flat-on orientation in the monolayer ultrathin films of PDHS, i.e., the silicon backbones were oriented along the surface-normal direction. By contrast, the orientation of lamellar crystals was preferentially edge-on in ultrathin films thicker than ca. 13 nm, i.e., the silicon backbones were oriented parallel to the substrate surface. We interpret the different orientations of molecular chain and lamellar crystal as due to the reduction of the entropy of the polymer chain near the substrate surface and the particularity of the crystallographic (001) plane of flat-on lamellae, respectively. A remarkable influence of the orientations of the silicon backbone on the UV absorption of these PDHS ultrathin films was observed due to the one-dimensional nature of sigma-electrons delocalized along the silicon backbone.

Conducting probe atomic force microscopy investigation of anisotropic charge transport in solution cast PBD single crystals induced by an external field

2-(4-Biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxdiazole (PBD) is a good electron-transporting material and can form single crystals from solution. In this work, solution cast PBD single crystals with different crystallographic axes (b, c) perpendicular to the Au/S substrates in large area are achieved by controlling the rate of solvent evaporation in the presence and absence of external electrostatic field, respectively. The orientation of these single crystals on Au/S substrate was characterized by transmission electron microscopy (TEM) and atomic force microscopy (AFM). Conducting probe atomic force microscopy (CP-AFM) was used to measure the charge transport characteristics of PBD single crystals grown on Au/S substrates. Transport was measured perpendicular to the substrate between the CP-AFM tip and the Au/S substrate. The electron mobility of 3 x 10(-3) cm(2)/(V s) for PBD single crystal along crystallographic b-axis is determined. And the electron mobility of PBD single crystal along the c-axis is about 2 orders of magnitude higher than that along the b-axis due to the anisotropic charge transport at the low voltage region.

Luminescent Langmuir-Blodgett films based on Tiron-terbium

The luminescent ultrathin Langmuir-Blodgett (LB) films containing Tb-2(C6H3S2O8)(2) (Tiron-Tb) were successfully obtained. The modifications of compression isotherms of dimethyldioctadecylammonium bromide (DODA) have been observed when the Tiron-Tb complex was dissolved in the subphase. The effect of Tiron-Tb in the subphase on Langmuir films of DODA has been studied. Low-angle X-ray diffraction result indicates that the LB films have a good periodic layered structure. The UV and IR spectra results show the Tiron-Tb complex is incorporated into LB films layer-by-layer and the LB films are homogeneously deposited. The LB films containing Tiron-Tb can emit strong green luminescence, and the luminescence signal can be detected from a single layer. The luminescence properties of LB films have been discussed compared with those of the solutions.

含苯并咪唑基配体的稀土配合物的合成、结构及量子化学研究

合成了未见文献报道的N,N,N',N'-四[(2-苯并咪唑)甲基]乙二胺的丁基取代衍生物(BuEDTB)与稀土硝酸盐的配合物[M(BuEDTB)(NO3)2]·NO3·4H2O[M=La(1),Eu(2),Tb(3)],并用X射线衍射法测定了1的结构.晶体属三方晶系,空间群P3221,晶胞参数a=1.41353(9)nm,c=2.6264(4)nm;V=4.5447(9)nm3,Dc=1.189g/cm3,Z=3,F(000)=1686,μ=0.758 mm-1,R=0.0562,wR=0.1488.乙二胺上两个N原子及四个苯并咪唑各有一个N原子参与配位,两个硝酸根以双齿形式与稀土离子配位,第三个硝酸根不与金属离子配位.用ab initio HF方法研究了BuEDTB的电子结构.

Structure and electrochemical characteristics of RENi3 alloy

The RENi3 (RE = La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Y) series compounds have been prepared by arc melting constituent elements under Ar atmosphere. X-ray diffraction (XRD) analysis reveals that the as-prepared alloys have different lattice parameters and cell volumes, depending on different rare earth (RE) element. The electrochemical characteristics, including the electrochemical capacity, P-C isotherms, high rate chargeability (HRC) and high-rate dischargeability (HRD), of these alloys have been studied through the charge-discharge recycle testing at different temperatures, charge currents and discharge currents. The results show that YNi3 has the largest cell volume, smallest density, and moreover, it shows more satisfactory electrochemical characteristics than other alloys, including discharge capacity, HRC, HRD and low temperature dischargeablity.