Characteristic lengths and the structure of salt free polyelectrolyte solutions. A small angle neutron scattering study

We have studied salt free semi dilute polyelectrolyte solutions by small angle neutron scattering. Specific labelling associated with an extrapolation method has allowed the separation of the form factor of a single polyelectrolyte chainS ₁(q) and the structure factorS ₂(q). Two lengths are deduced from these two factors: the persistence lengthb _t which characterizes the electrostatic interactions along the chain by a fitting ofS ₁(q) with calculation of the scattering function for a wormlike chain, and fromS ₂(q),q _m ^–1 which characterizes the interactions between chains. These two lengths vary in the same way with the concentration of polyions (b _t C _p ^–1/2 ,q _m ^–1 C _p ^–1/2 ) and a constant relation exists between them: only one length is then necessary to describe the structure of polyelectrolyte soltuion on this semidilute concentration range.Laboratoire Commun CEA-CNRS.     

Kinetic simulation of living carbocationic polymerizations. II. Simulation of living isobutylene polymerization using a mechanistic model

This paper discusses the kinetic simulation of TiCl₄--coinitiated living carbocationic isobutylene (IB) polymerizations governed by dormant-active equilibria, using a mechanistic model. Two kinetic models were constructed from the same underlying mechanism: one using a commercial simulation software package (Predici^®), and the other using the method of moments. Parameter estimation from experimental batch reactor data with Predici yielded a rate constant of propagation k_p = 4.64 × 10⁸ ± 2.75 × 10⁸ L/mol s, with no constraints imposed. This agrees with k_p data measured with diffusion clock and competition methods, but disagrees with kinetically obtained k_p values. Estimation of rate constants with Predici^® and the GREG parameter estimation software packages revealed that it was difficult to estimate the complete set of kinetic parameters, due to correlated effects of the parameters on model predictions. Estimability analysis confirmed that some of the strongly correlating parameters could not be estimated simultaneously using the available experimental data. Using k_p = 6 × 10⁸ ± 2.75  × 10⁸ L/mol s measured by Mayr, and using starting estimates of other rate constants defined by experimentally observed correlations, yielded the set of rate constants required for the simulations. Both kinetic models yielded good agreement with experimental data, with the exception of M_w values that slightly diverged from the theoretically predicted ‘M_w−M_n = constant’ relationship. This may indicate the occurrence of a minor side reaction. However, the k_p/k₋₁ = 17.5 L/mol average run length calculated from measured and simulated MWD data agrees well with earlier literature values.     

大气相干长度的昼夜观测

 介绍了利用差分像运动测量法测量光波到达角起伏方差来确定大气相干长度的方法，阐述了一种能对大气相干长度进行昼夜测量的日夜两用型大气相干长度仪的测量原理与结构,经过长期昼夜观测分析得知: 整层大气湍流强度有随时间变化的趋势，这种趋势与近地面层的湍流强度的时间变化特征基本吻合，即在日出后和日没前两段时间内的相干长度值远大于其它时间段内的值。     

Is bismuth subsalicylate an effective nontoxic catalyst for plga synthesis?

Poly(d,l ‐lactide‐co‐glycolide) (PLGA) copolyesters are commonly used in biomedical applications. Researches were carried out on nontoxic or low‐toxic catalysts that are enough efficient to provide short polymerization times, adequate microstructure chains and similar properties than the commercial PLGA materials. In this study, PLGA were synthesized by ring‐opening copolymerization (ROP) using three different catalysts. Stannous octoate is the first catalyst we used, as it is very efficient, even its toxicity is still on debate. Two others low‐toxic catalysts [zinc lactate and bismuth subsalicylate (BiSS)] were also evaluated. The comparison of these ROP was realized in terms of kinetics and control of the polymerization. Then, the influence of the catalyst on the PLGA microstructure chains is reported. Finally, abiotic hydrolytic degradation rate is studied. Results described in this article show that BiSS is one very attractive catalyst to produce low toxic PLGA for biomedical applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1130–1138     

Tuning the mesogenic properties of 5-alkoxy-2-(4-alkoxyphenyl)pyrimidine liquid crystals: the effect of a phenoxy end-group in two sterically equivalent series

Two sterically equivalent series of phenoxy-terminated 5-alkoxy-2-(4-alkoxyphenyl)pyrimidine liquid crystals were synthesised, and their mesogenic properties were characterised by polarised optical microscopy and differential scanning calorimetry (DSC). The phenoxy end-group causes a significant increase in melting point and inhibits – at least partially – the mesomorphism of these materials relative to the parent isomers; in most cases, the broad enantiotropic SmC phase formed by the parent isomers is suppressed by the addition of the phenoxy end-group. However, detailed analyses by small-angle X-ray scattering and monodomain 2D X-ray scattering suggest that these compounds form a SmA phase with a partially intercalated bilayer structure in which the phenoxy end-groups are nanosegregated. Such an intercalated bilayer structure might enable the tuning of smectogenic properties by appropriate substitution of the phenoxy end-groups.     

Effect of spacer length on mesomorphic behaviours of chiral liquid crystal compounds containing (-)-menthyl

ABSTRACT

A homologous series of new chiral liquid crystal compounds, MnBEB (n = 4–10), was prepared by covalently linking a chiral (–)-menthyl with biphenyl-benzoate via a dicarboxylic spacer of varying length and parity. A combination of analysis methods, such as FT-IR, ¹H NMR spectra, differential scanning calorimetry (DSC), polarised optical microscopy (POM) and X-ray diffraction was carried out to systematically investigate their phase structures and phase transition behaviours. The length and parity of the flexible spacers has a profound influence on the T_m and T_c and a modest odd-even effect is observed for the chiral liquid crystal compounds MnBEB. Only compound M4BEB developed an N* phase with selectively reflection on heating and a blue phase on cooling process. In addition, increasing the length of the flexible spacers tends to narrow the temperature range of the N* phase and widen the smectic phase, moreover, the pitch becomes longer with the spacer increases.     

Important unanswered questions—1970

This paper was given as the opening address at the 1970 Albany International Conference on Radiation Effects in Semiconductors, and it attempts to establish a general overview of the field by concentrating on recent research developments and important unanswered questions. The continuing importance of impurity-defect interactions, of microscopic defect identification, and of the necessity for more theoretical calculations are emphasized. The rapid development of the field of ion implantation and its close relationship with radiation effects studies are pointed out. It is predicted that research in compound semiconductors will increase rapidly with close beneficial interaction with ion implantation studies.     

Issue Information

Three‐dimensional direct numerical simulation results of flow past a circular cylinder are influenced by numerical aspects, for example the spanwise domain length and the lateral boundary condition adopted for the simulation. It is found that inappropriate numerical set‐up, which restricts the development of intrinsic wake structure, leads to an over‐prediction of the onset point of the secondary wake instability (Re_cr). A best practice of the numerical set‐up is presented for the accurate prediction of Re_cr by direct numerical simulation while minimizing the computational cost. The cylinder span length should be chosen on the basis of the intrinsic wavelength of the wake structure to be simulated, whereas a long span length is not necessary. For the wake transitions above Re_cr, because the wake structures no longer follow particular wavelengths but become disordered and chaotic, a span length of more than 10 cylinder diameters (approximately three times the intrinsic wavelength) is recommended for the simulations to obtain wake structures and hydrodynamic forces that are not strongly restricted by the numerical set‐up. The performances of the periodic and symmetry lateral boundary conditions are compared and discussed. The symmetry boundary condition is recommended for predicting Re_cr, while the periodic boundary condition is recommended for simulating the wake structures above Re_cr. The general conclusions drawn through a circular cylinder are expected to be applicable to other bluff body configurations. Copyright © 2017 John Wiley & Sons, Ltd.     

Effects of graft length and density of well‐defined graft polymers on the thermoresponsive behavior and self‐assembly morphology

A series of well‐defined thermoresponsive graft polymers with different lengths and graft densities, poly(glycidyl methacrylate)‐graft‐poly(N‐isopropylacrylate) (PGMA‐g‐PNIPAM), were successfully prepared by combination of controlled/living free radical polymerization and click chemistry. Effects of grafting length and density on the thermoresponsive behavior, aggregating mean diameter, and self‐assembly morphology are systematically investigated. The thermosensitive characteristics of graft polymers in aqueous solution prove that the length and graft density had positive co‐relationship with the lower critical solution temperature value and mean diameter of micelles as well as the size distribution, while the effect of graft length of polymers is more significant than that of density. Transmission electron microscopy analysis shows that the conformations of PGMA₄₅‐g‐PNIPAM₂₀ and PGMA₄₅‐g‐PNIPAM₄₆ with longer length and bigger grafting density in aqueous solutions are spherical nanoparticles with the increasing trend of the diameters, while that of PGMA₄₅‐g‐PNIPAM_{(73, 50%)} shows a spherical‐like morphology, which indicates that the graft length and density have a significant effect on the mean diameter of micelle but not on the self‐assembly morphology. These results reveal that to obtain desired thermoresponsive behavior and self‐assembly morphology of functional polymers, it is essential to design and fabricate the structure of graft polymers with proper length and graft density. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2442–2453     

Synthesis and Characterization of Amphiphilic Copolymer Acrylic Acid-co-p-Chloromethylstyrene

The free radical copolymerization of acrylic acid (M₁) with p-chloromethylstyrene (M₂) in dioxane and in the presence of α,α′-azobisisobutyronitrile (AIBN) at 65°C is reported. Copolymer compositions of six copolymer samples obtained from feed ratios of M₁:M₂ = 95.2:4.8 to 21.4:78.6 were determined by ¹H-NMR. The reactivity ratios of AA/p-CMS copolymerization system calculated by the F-R method were r ₁ = 0.50 ± 0.06 and r ₂ = 1.52 ± 0.15, almost the same as r ₁ = 0.43 ± 0.21 and r ₂ = 1.31 ± 0.14 by the extended K-T method. On the basis of the reactivity ratios of two monomers, the sequence length distribution in the AA/p-CMS copolymers was obtained. For f₂ = 4.77%, the monomer unit of p-CMS is individually separated in the chain of AA; for f₂ = 35.53%, the alternating tendency prevails and a large number of mono-sequences are formed. The number-average ( _n) and weight-average ( _w) molecular weights were determined by gel permeation chromatography. The effect on molecular weights of feed composition is also discussed. In the presence of constant initiator concentration, the gradual increase in the ratio of M₂:M₁ (from14.7:85.3 to 78.6:21.4) was accompanied by a decrease in molecular weights ( _n from 11907 to 3961).