Electrochemically Induced Iron Release of Adsorbed Horse Spleen Ferritin: Quantitation of Iron Using Long Optical Path Length Thin‐Layer Spectroelectrochemistry

In this work, long optical path length thin‐layer electrochemical cell was constructed using indium‐tin oxide on glass as the electrode material. Iron release from ferritin adsorbed on the electrode was induced by applying a negative potential sweep in the presence of 1,10‐phenanthroline. The usefulness of spectroelectrochemistry as a means of determining the quantity of iron released from an adsorbed layer of ferritin is demonstrated.     

A long-time tail for random walk in random scenery

Consider a simple random walk on ^d whose sites are colored black or white independently with probabilityq, resp. 1–q. Walk and coloring are independent. Letn _k be the number of steps by the walk between itskth and (k+1) th visits to a black site (i.e., the length of itskth white run), and let _k =E(n _k )–q ^–1. Our main result is a proof that (*) lim _k k ^d/2 _k = (1 –q)q ^{d/2 – 2}(d/2) ^d/2. Since it is known thatq ^{– 1} _k =E(n ₁ n _{k + 1} B) –E(n ₁ B)E(n _{k + 1} B), withB the event that the origin is black, (*) exhibits a long-time tail in the run length autocorrelation function. Numerical calculations of _k (1k100) ind=1, 2, and 3 show that there is an oscillatory behavior of _k for smallk. This damps exponentially fast, following which the power law sets in fairly rapidly. We prove that if the coloring is not independent, but is convex in the sense of FKG, then the decay of _k cannot be faster than (*).     

Application of HPLC to measure vanadium in environmental,biological and clinical matrices

Vanadate and vanadium compounds exist in many environmental, biological and clinical matrices, and despite the need only limited progress has been made on the analysis of vanadium compounds. The vanadium coordination chemistry of different oxidation states is known, and the result of the characterization and speciation analysis depends on the subsequent chemistry and the methods of analysis. Many studies have used a range of methods for the characterization and determination of metal ions in a variety of materials. One successful technique is high performance liquid chromatography (HPLC) that has been used mainly for measuring total vanadium level and metal speciation. Some cases have been reported where complexes of different oxidation states of vanadium have been separated by HPLC. Specifically reversed phase (RP) HPLC has frequently been used for the measurement of vanadium. Other HPLC methods such as normal phase, anion-exchange, cation-exchange, size exclusion and other RP-HPLC modes such as, ion-pair and micellar have been used to separate selected vanadium compounds. We will present a review that summarizes and critically analyzes the reported methods for analysis of vanadium salts and vanadium compounds in different sample matrices. We will compare various HPLC methods and modes including sample preparation, chelating reagents, mobile phase and detection methods. The comparison will allow us to identify the best analytical HPLC method and mode for measuring vanadium levels and what information such methods provide with regard to speciation and quantitation of the vanadium compounds.     

On the solution characterization of an all-aromatic liquid-crystalline copolyester

Solution characterization of the thermotropic liquid–crystalline copolyester synthesized from terephthalic acid, phenyl hydroquinone, and (1-phenylethyl) hydroquinone (2 : 1 : 1) has been performed. Viscometry, size exclusion chromatography, and light scattering have been carried out under the optimal conditions found for measurement: 85°C in a 50/50 mixture by weight of phenol/1,2,4-trichlorobenzene. The absolute weight-average molecular weight from light-scattering measurements served for calibration of indirect methods of charac-terization (e.g., the limiting viscosity number [η] is related to the molecular weight by [η] = 5.10 × 10^?4 M_w^0.72), and the molecular weight per unit chain length, $ \bar M_L * $, from light scattering and size exclusion chromatography (SEC) is found to be 28 Å^?1, consistent with theoretical expectations. The calculated persistence length q is 28 Å. Moreover, the meth-odology of SEC characterization enables the kinetics of solid-state postpolymerization of this liquid-crystalline copolyester to be studied. © 1993 John Wiley & Sons, Inc.     

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     

Determination Of Formaldehyde And Acetaldehyde Associated To Atmospheric Aerosols By HPLC

Abstract

A rapid new analytical protocol was developed for the determination of formaldehyde and acetaldehyde associated to atmospheric particulate matter, at ng/m³ levels. The aerosols were collected on glass fiber filters (8″×10″) at face velocities ranging from 15 m/min to 23 m/min. Aliquots of 15.4 cm² were sonicated, for 20 min, with 5.0 mL of 0,01% 2,4-dinitrophenylhydrazine (DNPH), 1 % phosphoric acid. The liquid phase was then filtered and the separation and quantification of the corresponding 2,4-dinitrophenylhidrazone (DNPHo) derivatives carried out by reverse phase HPLC. Acetonitrile:water (57:43, v/v) as mobile phase at 1.0 mL/min and absorbance detection at 350 nm and 365 nm for, respectively, formaldehyde-DNPHo (0.04 AUFS) and acetaldehyde-DNPHo (0.01 AUFS) were used. The precision for four different aliquots, from a 8″×10″ glass fiber filter, were under 0.04% for formaldehyde and 14.16 % for acetaldehyde. In Salvador, Bahia, Brazil, formaldehyde and acetaldehyde were determined, respectively, in the range of 6.8 ng/m³ to 27.3 ng/m³ and 9.1 ng/m³ to 54.6 ng/m³.     

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.