Aggregate restructuring by polymer solvency effects

This study investigates the aggregation in cyclohexane of silica particles initially stabilized by grafted polystyrene and destabilized by temperature reduction. It complements an earlier study by Zhu and Napper (P.W. Zhu, D.H. Napper, Phys. Rev. E 50 (1994) 1360) in which the aggregation of polystyrene latex particles with tethered poly(N-isopropyl acrylamide) (PNIPAM) in water was investigated. Their dynamic light scattering results showed that both the rate of aggregation and the aggregate fractal dimension increased with a sufficient decrease in the PNIPAM adlayer solvency, achieved by means of either salt (NaNO3) addition or temperature rise. This result stands in contrast to those obtained when an electrostatically stabilized colloid is destabilized, i.e., that the more rapidly aggregates are formed, the lower the resulting fractal dimension. The authors explained their results in terms of the effects of both salt effects and increased temperature on the extent of the hydrophobic interactions between the adlayer-covered surfaces in the water. The present study examines a sterically-stabilized colloid in a nonaqueous solvent, where neither salt effects nor hydrophobic effects play a role. Temperature is decreased to bring the system from better-than-theta-conditions to worse-than-theta-conditions. Power-law aggregation kinetics are observed at 15.7 degrees C by dynamic light scattering. The particles first undergo reduced rate aggregation, producing low-fractal-dimension aggregates, which after some time, restructure into more compact aged clusters. The fractal dimension of these aged clusters increases with increasing initial aggregation rate, consistent with results seen by Zhu and Napper, but without the presence of hydrophobic effects. The ability of the polymer-grafted particles to rearrange suggests aggregation into a secondary minimum, with the ability to slide over one another to achieve a more energetically favorable, denser configuration. The reversible nature of the aggregation is verified by additional experiments gradually bringing the system from worse-than-theta-conditions back to better-than-theta-conditions, with an attendant decrease in aggregate fractal dimension, and ultimately full redispersion.     

A new multistep finite difference pair for the Schrödinger equation and related problems

In this paper and for the first time in the literature, we introduce a new three-stages symmetric six-step finite difference pair with optimal phase and stability properties. The basic characteristics of the new finite difference pair are:

1. 1.
   Is a symmetric hybrid six-step method,
    
2. 2.
   Is of three stages
    
3. 3.
   Is of twelfth algebraic order,
    
4. 4.
   Has vanished the phase-lag,
    
5. 5.
   Has vanished the derivatives of the phase-lag up to order four.
    

For this new finite difference pair we present a detailed analysis which consists of the following:

1. 1.
   The development of the new three-stages symmetric six-step finite difference pair
    
2. 2.
   The presentation of the local truncation error of the new finite difference pair
    
3. 3.
   A comparative error analysis of the new finite difference pair with other finite difference pairs of the same family: the the classical finite difference pair of the family (i.e. the finite difference pair with constant coefficients), the recently developed finite difference pairs of the same family with vanished phase-lag and its first derivative, the recently developed scheme of the same family with vanished phase-lag and its first and second derivatives and finally with the recently developed finite difference algorithm of the same family with vanished phase-lag and its first, second and third derivatives .
    
4. 4.
   A stability and an interval of periodicity analysis and
    
5. 5.
   Finally, the evaluation of the accuracy and computational efficiency of the new three-stages symmetric six-step finite difference pair for the solution of the Schrödinger equation.
    

The theoretical and numerical analysis of the produced new three-stages symmetric six-step finite difference pair, which are presented in this paper, show the effectiveness of the new scheme compared with other known or recently developed algorithms of the literature.

     

Determination and characterization of diuretics in human urine by liquid chromatography coupled to pneumatically assisted electrospray ionization mass spectrometry.

The aim of this work was to develop a method for the characterization and determination of diuretics in human urine samples by liquid chromatography (LC) coupled to pneumatically assisted electrospray ionization (ES) mass spectrometry (MS). The diuretics studied were substances forbidden by the IOC such as trichlormethiazide, furosemide, canrenoic acid, benzthiazide, bendroflumethiazide, bumetanide, etacrynic acid and spironolactone. For this purpose, the operational parameters of electrospray, such as counter electrode voltage, capillary voltage, sample cone voltage and source temperature, were optimized in order to obtain the best signal stability and the highest sensitivity for the greatest number of diuretic agents. The optimized separation method was successfully coupled with the MS system to analyze the above-mentioned diuretics extracted from spiked urine samples by a liquid extraction and clean-up procedure at basic pH, using ethyl acetate as solvent and the salting-out effect (NaCl). The mass spectra obtained provide adequate information for identification purposes. Positive urine samples obtained from athletes were also analyzed. The presence of these substances in human urine was confirmed by this method, making LC/ES-MS an analytical tool to be considered in the area of antidoping control.     

The determination of aluminium in seawater and freshwater by cathodic stripping voltammetry

Dissolved aluminium in seawater and freshwater is determined by cathodic stripping voltammetry (c.s.v.) preceded by adsorptive collection of complex ions with 1,2-dihydroxyanthraquinone-3-sulphonic acid (DASA) on the hanging mercury drop electrode. Complexation of aluminium by DASA is rapid and no waiting period or heating of the sample is required. Optimal conditions are a DASA concentration of 10^?5 M, a solution pH of 7.1–7.3 and an adsorption potential of ?0.9 V; the c.s.v. scan is done in the differential-pulse mode. The limit of detection is 1 nM aluminium for an adsorption time of 45 s. The total time needed, including 50min deaeration and a standard addition, is 10–15 min per sample. No serious interferences were found; u.v. irradiation is recommended for samples containing high levels of organic materials.     

Electrochemical reduction of oxygen catalyzed by a wide range of bacteria including Gram-positive

Most bacteria known to be electrochemically active have been harvested in the anodic compartments of microbial fuel cells (MFCs) and are able to use electrodes as electron acceptors. The reverse phenomenon, i.e. using solid electrodes as electron donors, is not so widely studied. To our knowledge, most of the electrochemically active bacteria are Gram-negative. The present study implements a transitory electrochemical technique (cyclic voltammetry) to study the microbial catalysis of the electrochemical reduction of oxygen. It is demonstrated that a wide range of aerobic and facultative anaerobic bacteria are able to catalyze oxygen reduction. Among these electroactive bacteria, several were Gram-positive. The transfer of electrons was direct since no activity was obtained with the filtrate. These findings, showing a widespread property among bacteria including Gram-positive ones, open new and interesting routes in the field of electroactive bacteria research.     

Isoelectric focusing of apolipoproteins in immobilized pH gradients: improved determination of apolipoprotein E phenotypes

A method for isoelectric focusing of apolipoprotein E in an immobilized pH gradient with added carrier ampholytes has been developed. This method is an improvement over conventional isoelectric focusing of apolipoprotein E with respect to resolution, reproducibility, and simplicity. Since monosialo isoforms are resolved from the normally cofocusing asialo isoforms, unique patterns are obtained for all 6 common apolipoprotein E phenotypes. The method can also be applied to the screening of apolipoprotein A and C isoforms. Delipidated very low density lipoproteins (VLDL) have been used as the source of apolipoprotein E and C. Apolipoprotein A isoforms were focused directly from detergent-treated serum. Immunodetection of apolipoprotein E using capillary transfer was found to be compatible with the described method.     

Automated multiple-layer spotting for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry of synthetic polymers utilizing ink-jet printing technology

Recently, a new multiple-layer matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) sample spotting technique for poly(ethylene glycol), offering improved analysis possibilities, was described. In this contribution the application of ink-jet printing to automated, multiple-layer MALDI-TOFMS sample preparation of synthetic polymers is presented, allowing accurate deposition of matrix, additive and analyte solutions. The new sample preparation technique was evaluated for poly(ethylene glycol) as well as poly(methyl methacrylate) standards, and optimized settings for both synthetic polymers have been obtained.     

Fluxional behavior of a cadmium zwitterion complex: proton transport and tautomerism in methylene chloride solution

The synthesis and structure of the tautomeric Cd(II) isoindoline zwitterion coordination compound [Cd(4'-MeLH)(NO(3))(2)].CH(3)OH (4'-MeLH = 1,3-bis[2-(4-methylpyridyl)imino]isoindoline) are reported. In methylene chloride solution, tautomer interconversion occurs as the N-H proton moves between the identical imine nitrogen atoms. We report the kinetics of proton transfer as followed by variable temperature (1)H NMR spectroscopy and demonstrate that methanol of solvation and adventitious water facilitate rapid proton transfer.