Exfoliation of Organically Modified Montmorillonite Driven by Molecular Diffusion in Maleated Polypropylene

This work is focused on the factors influencing the intercalation of maleated polypropylene (PPMA) into organically modified montmorillonite (OMMT). Two kinds of PPMA were used to explore the optimal candidate for effective intercalation into OMMT. The grafting degree of maleic anhydride and the viscosity of PPMA have effects on the diffusion of polymer molecules. Moreover, the loading level of surfactant was varied to optimize the modification of montmorillonite because the appropriate loading level can provide a balance between interlayer distance and steric hindrance. The kind of surfactant changes the interaction between OMMT and PPMA, and accordingly the intercalation of PPMA is different, resulting in the discrepancy of the intercalation of PPMA.

Self-assembly of T-shaped rod-coil block copolymer melts

Self-assembled behavior of T-shaped rod-coil block copolymer melts is studied by applying self-consistent-field lattice techniques in three-dimensional space. Compared with rod-coil diblock copolymers with the anchor point positioned at one end, the copolymers with the anchor point at the middle of the rod exhibit significantly different phase behaviors. When the rod volume fraction is low, the steric hindrance of the lateral coils prevents the rods stacking into strip or micelle as that in rod-coil diblock copolymers. The competition between interfacial energy and entropy results in the formation of lamellar structures and the increasing thickness of the lamellar layer with increasing rod volume fraction.

Sensitive and Selective Sensor for Biothiols in the Cell Based on the Recovered Fluorescence of the CdTe Quantum Dots-Hg(II) System

Herein, a sensitive and selective sensor for biothiols based on the recovered fluorescence of the CdTe quantum dots (QDs)-Hg(II) system is reported. Fluorescence of QDs could be quenched greatly by Hg(II). In the presence of biothiols, such as glutathione (GSH), homocysteine (Hcy), and cysteine (Cys), however, Hg(H) preferred to react with them to form the Hg(II)-S bond because of the strong affinity with the thiols of biothiols rather than quenching the fluorescence of the QDs. Thus, the fluorescence of CdTe QDs was recovered. The restoration ability followed the order GSH > Hcy > Cys due to the decreased steric hindrance effect. A good linear relationship was obtained from 0.6 to 20.0 mu mol L-1 for GSH and from 2.0 to 20.0 mu mol L-1 for Cys, respectively. The detection limits of GSH and Cys were 0.1 and 0.6 mu mol L-1, respectively. In addition, the method showed a high selectivity for Cys among the other 19 amino acids. Furthermore, it succeeded in detecting biothiols in the Hela cell.

Platinum-macrocycle co-catalyst for electro-oxidation of formic acid

In this work, a new promoter, tetrasulfophthalocyanine (FeTSPc), one kind of environmental friendly material, was found to be very effective in both inhibiting self-poisoning and improving the intrinsic catalysis activity, consequently enhancing the electro-oxidation current during the electro-oxidation of formic acid. The cyclic voltammograms test showed that the formic acid oxidation peak current density has been increased about 10 times compared with that of the Pt electrode without FeTSPc. The electrochemical double potential step chronoamperometry measurements revealed that the apparent activity energy decreases from 20.64 kJ mol(-1) to 17.38 kJ mol(-1) after Pt electrode promoted by FeTSPc. The promoting effect of FeTSPc may be owed to the specific structure and abundant electrons of FeTSPc resulting in both the steric hindrance of the formation of poisoning species (CO) and intrinsic kinetic enhancement. In the single cell test, the performance of DFAFC increased from 80 mW cm(-2) mg(-1) (Pt) to 130 mW cm(-2) mg(-1) after the anode electrode adsorbed FeTSPc.

Ethylene-propylene copolymerization with bis(beta-enaminoketonato) titanium complexes activated with modified methylaluminoxane

Ethylene-propylene copolymerization, using [(Ph)NC(R-2)CHC(R-1)O](2)TiCl2 (R-1 = CF3, Ph, or t-Bu; R-2 = CH3 or CF3) titanium complexes activated with modified methylaluminoxane as a cocatalyst, was investigated. High-molecular-weight ethylene-propylene copolymers with relatively narrow molecular weight distributions and a broad range of chemical compositions were obtained. Substituents R-1 and R-2 influenced the copolymerization behavior, including the copolymerization activity, methylene sequence distribution, molecular weight, and polydispersity. With small steric hindrance at R-1 and R-2, one complex (R-1 = CF3; R-2 = CH3) displayed high catalytic activity and produced copolymers with high propylene incorporation but low molecular weight. The microstructures of the copolymers were analyzed with C-13 NMR to determine the methylene sequence distribution and number-average sequence lengths of uninterrupted methylene carbons.

Characterization and properties of biodegradable poly(hydroxyalkanoates) and 4,4-dihydroxydiphenylpropane blends: Intermolecular hydrogen bonds, miscibility and crystallization

Intermolecular hydrogen bonds, miscibility, crystallization and thermal stability of the blends of biodegradable poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(3HB-3HHx)] with 4,4-dihydroxydiphenylpropane (DOH2) were investigated by FTIR, C-13 Solid state NMR, DSC, WAXD and TGA. Intermolecular hydrogen bonds were found in both blend systems, which resulted from the carbonyl groups in the amorphous phase of both polyesters and the hydroxyl groups of DOH2. The intermolecular interaction between P(3HB-3HHx) and DOH2 is weaker than that between PHB and DOH2 owing to the steric hindrance of longer 3HHx side chains. Because of the effect of the hydrogen bonds, the chain mobility of both PHB and P(3HB-3HHx) components was limited after blending with DOH2 molecules. Single glass transition temperature depending on the composition was observed in all blends, indicating that those blends were miscible in the melt. The addition of DOH2 suppressed the crystallization of PHB and P(3HB-3HHx) components. Moreover, the crystallinity of PHB and P(3HB-3HHx) components also decreased with increasing DOH2 content in the blends.

Systematic study of the transfer of amino acids across the water/1,2-dichloroethane interface facilitated by dibenzo-18-crown-6

Facilitated ion transfer reactions of 20 amino acids with di.benzo-18-crown-6 (DB18C6) at the water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nano-pipets were investigated systematically using cyclic voltammetry. It was found that there were only 10 amino acids, that is, Leu, Val, Ile, Phe, Trp, Met, Ala, Gly, Cys, Gln (in brief), whose protonated forms as cations can give well-defined facilitated ion transfer voltammograms within the potential window, and the reaction pathway was proven to be consistent with the transfer by interfacial complexation/dissociation (TIC/TID) mechanisms. The association constants of DB 18C6 with different amino acids in the DCE (beta(0)), and the kinetic parameters of reaction were evaluated based on the steady-state voltammetry of micro- or nano-pipets, respectively The experimental results demonstrated that the selectivity of complexation of protonated amino acid by DB18C6 compared with that of alkali metal cations was low, which can be attributed to the vicinal effect arising from steric hindrance introduced by their side group and the steric bulk effect by lipophilic stabilization.

Separation of heavy rare earth elements with extraction resin containing 1-hexyl-4-ethyloctyl isopropylphosphonic acid

This paper presents the results of the adsorption of heavy rare earth ions (Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(III)) from hydrochloric acid solutions at 30 degreesC by the extraction resin containing 1-hexyl-4-ethyloctyl isopropylphosphonic acid (HEOPPA), which has higher steric hindrance, higher selectivities and lower extraction and stripping acidity than di(2-ethylhexyl)phosphoric acid (DERPA) or 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (HEH/EHP). The dependence of acid concentration, flow rate and amounts of rare earth ions sorbed on the separation of Er-Tm, Tm-Yb and Er-Tm-Yb mixtures has been studied. The baseline chromatographic separation of Er-Tm-Yb mixture has been observed. Satisfactory results with purity and yield of Tm2O3>99.71% and >71.25%, Er2O3>99-81% and >94.17%, and Yb2O3>99.74% and >89.83%, respectively, have been obtained. The parameters such,as resolution, separation factors and efficiencies have been determined as a function of acidity, loading of rare earth elements and flow rates. The stoichiometry of the extraction of rare earth ions has been suggested as well.

Rare earth separation with 1-hexyl-4-ethyloctyl isopropylphosphonic acid extractant

A new extractant 1-hexyl-4-ethyloctyl isopropylphosphonic acid (HHEOIPP or HA) in heptane was employed to extract rare earths from hydrochloric acid medium. The dependence of extraction distribution ratio on equilibrium aqueous pH and the concentration of extractant were investigated. On the basis of slope analysis,it was proposed that two different kinds of extracted species were formed. For rare earth elements (La similar to Ho) the extracted species was LnA(3)(HA)(3) and for heavy rare earth elements (Er similar to Lu) the species was LnClA(2)(HA)(3). The steric hindrance plays an important role in forming the species. The extraction constants and separation factors of the adjacent rare earths were calculated too. Compared with HDEHP and HEH/EHP, HHEOIPP is a valuable extractant with high separation selectivity. The "tetrad effect" between K-ex and atomic number was observed.

Effect of end substitution on optical properties and molecular orientation of distyrylbenzene derivatives in thin film

Three distyrylbenzene (DSB) derivatives were vacuum-evaporated on a (001) surface of KBr. DSB derivative molecules formed nuclei by interaction between the electron donative methoxyl group and Br- ion of the substrate crystal and oriented their longitudinal axis obliquely to the substrate surface. The peak shift between the emission peaks of solution and film decreased depending on the number of substituent. This phenomenon was originated to reduction of molecular interaction between neighboring molecules by steric hindrance of end substituents. (C) 2000 Elsevier Science S.A. All rights reserved.

Metallocene polyethylenes with broad or bimodal molecular weight distribution

Seven new binuclear titanocenes with different linking bridges, unsubstituted or substituted on the Cp rings, were synthesized and tested for their effect on ethylene polymerization in the presence of MAO. The polyethylenes thus obtained had broad MWD or even bimodal GPC curves, as compared with that from two reference mononuclear titanocenes. This is explained by the difference in degree of steric hindrance around the active center sites imposed by the bulky substituted ligands assuming different configurations in the rotation of the catalyst molecules. Lower polymerization temperatures alleviate the effect of these configuration differences, as reflected in change in MW and (M) over bar(w)/(M) over bar(n). This effect is not caused by decomposition or disproportionation of the binuclear titanocenes as evidenced by the stability of the catalyst.

ON THE SIGNIFICANCE OF WAVELENGTH POSITIONING ACCURACY IN MULTICOMPONENT ANALYSIS TECHNIQUES FOR THE CORRECTION OF LINE INTERFERENCES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

The present paper reports some definite evidence for the significance of wavelength positioning accuracy in multicomponent analysis techniques for the correction of line interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). Using scanning spectrometers commercially available today, a large relative error, DELTA(A) may occur in the estimated analyte concentration, owing to wavelength positioning errors, unless a procedure for data processing can eliminate the problem of optical instability. The emphasis is on the effect of the positioning error (deltalambda) in a model scan, which is evaluated theoretically and determined experimentally. A quantitative relation between DELTA(A) and deltalambda, the peak distance, and the effective widths of the analysis and interfering lines is established under the assumption of Gaussian line profiles. The agreement between calculated and experimental DELTA(A) is also illustrated. The DELTA(A) originating from deltalambda is independent of the net analyte/interferent signal ratio; this contrasts with the situation for the positioning error (dlambda) in a sample scan, where DELTA(A) decreases with an increase in the ratio. Compared with dlambda, the effect of deltalambda is generally less significant.

NMR-STUDIES ON THE COORDINATION OF RARE-EARTHS WITH GLYCYL-DL-VALINE AND THE CONFORMATION OF THEIR COMPLEX IN AQUEOUS-SOLUTION

In this paper lanthanide-induced shifts have been measured for C-13 and H-1 nuclei of glycyl-DL-valine in the presence of three lanthanide cations (La3+, Ho3+ and Yb3+) in aqueous solution. The stability constants of the coordination compounds of rare earths (Ho, Yb) with glycyl-DL-valine have been calculated. The coordination of rare earths with the ligand has been discussed. The simulation for conformation of lanthanide coordination compounds with glycyl-DL-valine shows that the ligand is coordinated to lanthanide ion through oxygen atoms of carboxyl group and the bond length of Ln-O is 0.226 nm. In the coordination compounds glycyl-DL-valine is in extended state with minimal steric hindrance.

The characteristics of BSRs and their derived heat flow on the profile 973 in the northeastern South China Sea

Processing of a recently acquired seismic line in the northeastern South China Sea by Project 973 has been conducted to study the character and the distribution of gas hydrate Bottom-Simulating Reflectors (BSRs) in the Hengchun ridge. Analysis of different-type seismic profiles shows that the distribution of BSRs can be revealed to some extents by single-channel profile in this area, but seismic data processing plays an important role to resolve the full distribution of BSRs in this area. BSR' s in the northeastern South China Sea have the typical characteristics of BSRs on worldwide continental margins: they cross sediment bed reflections, they are generally parallel to the seafloor and the associated reflections have strong amplitude and a negative polarity. The characteristics of BSRs in this area are obvious and the BSRs indicate the occurrence of gas hydrate-bearing sediments in the northeastern South China Sea. The depth of the base of the gas-hydrate stability zone was calculated using the phase stability boundary curve of methane hydrate and gas hydrate with mixture gas composition and compared with the observed BSR depth. If a single gradient geothermal curve is used for the calculation, the base of the stability zone for methane hydrate or gas hydrate with a gas mixture composition does not correspond to the depth of the BSRs observed along the whole seismic profile. The geothermal gradient therefore changes significantly along the profile. The geothermal gradient and heat flow were estimated from the BSR data and the calculations show that the geothermal gradient and heat flow decrease from west to east, with the increase of the distance from the trench and the decrease of the distance to the island arc. The calculated 2 heat flow changes from 28 to 64 mW/m(2), which is basically consistent with the measured heat flow in southwestern offshore Taiwan.

海洋重力资料预处理软件的编制及应用

首先应用Visual Basic 6.0计算机语言，根据我们所熟知的海洋重力数据的处理步骤和海洋重力测量规范内容，开发出一套海洋重力资料整理软件，以便能使资料整理工作成为一体化，提高工作效率，保证数据处理的准确性。应用该软件对南海某工区的实际重力资料进行了处理，得到了满意的处理结果，证明该软件使用方便，计算准确可靠，能够快速准确的处理采集到的重力数据。对数据处理结果进行了分析和应用。 通过分析Eötvös校正值与重力仪读数之间的变化关系，可以对重力仪的动态性能进行分析和评价。得到2级海况条件下重力仪的实际阻尼延迟时间约为60s，比厂方推荐的理论值（110s）更接近实际，有助于减小数据处理过程中的定位误差，提高测量精确度。通过对重力仪的灵敏性进行分析，验证重力仪在测量过程中的准确性和可靠性，为获得精确的数据提供可靠的保障。 对该套规则重力测网数据，分别采用60s阻尼延迟时间和110s阻尼延迟时间进行阻尼延迟校正，然后进行交点差计算和平差处理，得到的结果显示：采用60s阻尼延迟时间对数据进行阻尼延迟校正后得到的测量精度为1.40mGal，经过平差后的测量精度为0.77mGal；而采用110s阻尼延迟时间对数据进行阻尼延迟校正后得到的测量精度为1.62mGal，经过平差后的测量精度为0.96mGal。此结果验证了利用船只机动转向法确定海洋重力仪的实际阻尼延迟时间的必要性和应用价值。 最后，对宋文尧等人的平差方法和刘保华等人的最小二乘平差方法进行了分析比较，从推导原理和计算结果两方面证明了两种方法在规则海洋重力测网平差作用上是等效的。对于不规则重力测网平差，最小二乘平差方法具有强大的优势，且计算机程序运算实现方便。