Effect of electrolyte type on the electrokinetic behavior of sulfonated polystyrene model colloids

Sulfonated polystyrene latex particles were prepared by a two-stage shot-growth emulsion polymerization process in the absence of emulsifier. Sodium styrene sulfonate (NaSS) was used as an ionic co-monomer to produce a series of latex particles with the same particle size but with different surface charge densities. The electrophoretic mobility of this functionalized model colloid was studied in the presence of various types of inorganic electrolytes. The _e curves of these latexes exhibit a pronounced maximum at high electrolyte concentrations: 5·10^–2 M for 11 electrolytes and 10^–2 M for 21 and 12 electrolytes. When a 31 electrolyte (LaCl₃) was used, the electrophoretic mobility changed to positive values at high concentration due to the specific adsorption of lanthanum species. The experimental results for the electrokinetic characterization of these sulfonated polystyrene model colloids suggest that the surface of the particles is covered by a layer of oligomers or polymer chains which shift the shear plane toward the bulk solution, increasing the anomalous surface conductance of the polystyrene microsphere-electrolyte solution interface.     

Optimal allocation of replicas in parallel tempering simulations

We have studied the efficiency of parallel tempering simulations for a variety of systems including a coarse-grained protein, an atomistic model polypeptide, and the Lennard-Jones fluid. A scheme is proposed for the optimal allocation of temperatures in these simulations. The method is compared to the existing empirical approaches used for this purpose. Accuracy associated with the computed thermodynamic quantities such as specific heat is also computed and their dependence on the trial-exchange acceptance rate is reported.     

How does product isotope effect prove the operation of a two-state "rebound" mechanism in C-H hydroxylation by cytochrome P450?

C-H hydroxylation is a fundamental process. In Nature it is catalyzed by the enzyme cytochrome P450, in a still-debated mechanism that poses a major intellectual challenge for both experiment and theory; currently, the opinions keep swaying between the original single-state rebound mechanism, a two-oxidant mechanism (where ferric peroxide participates as a second oxidant, in addition to the primary active species, the high-valent iron-oxo species), and two-state reactivity (TSR) mechanism (where two spin states are involved). Recent product isotope effect (PIE) measurements for the trans-2-phenyl-methyl cyclopropane probe (1), led Newcomb and co-workers (Newcomb, M.; Aebisher, D.; Shen, R.; Esala, R.; Chandrasena, P.; Hollenberg, P.; Coon, M. J. J. Am. Chem. Soc. 2003, 125, 6064-6065) to rule out TSR in favor of the two-oxidant scenario, since the direction of the PIE was at odds with the one predicted from calculations on methane hydroxylation. The present report describes a density functional theoretical study of C-H hydroxylation of the Newcomb probe, 1, leading to rearranged (3) and unrearranged (2) products. Our study shows that the reaction occurs via TSR in which the high-spin pathway gives dominant rearranged products, whereas the low-spin pathway favors unrearranged products. The calculated PIE(2/3) values based on TSR are found to be in excellent agreement with the experimental data of Newcomb and co-workers. This match between experiment and theory makes a strong case that the reaction occurs via TSR mechanism.     

The deformation of dextran molecules. Causes and consequences in ultrafiltration

The transfer of dextran T70 solutions through a skinned polysulfone hollow fiber membrane was studied with and without applied pressure. The molecular weight distributions of dextran in the feed and in the permeate were obtained by high pressure liquid chromatography. Two different phenomena appear to play important roles with regard to solute transfer. One is related to the shear stress imposed by the flow at the pore entrances, i.e. to permeate flux, and the other is related to the influence of solute concentration on the expansion of the macromolecular chains. These phenomena explain the observed variations with operating conditions of the overall rejection coefficient.     

Effect of acid treatment on the properties of an activated carbon

The enhancement of the activity of a carbon treated with HF is due to the drastic diminution of its inorganic impurities, which produces an increase of the surface area of the carbon, a stronger Pt-C interaction and a higher Pt dispersity.

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, HF, , , Pt-C Pt.

     

Sensitive spectrophotometric determination of ascorbic acid in fruit juices and pharmaceutical formulations using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (Br-PADAP)

A simple and very sensitive method has been developed for the determination of ascorbic acid based on the oxidation of ascorbic acid to dehydroascorbic acid by iron(III), followed by a complexation of iron(II) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol(Br-PADAP). The iron(II) complex is formed immediately, with absorption maxima at 560 and 748 nm and a molar absorptivity of 1.31 × 10⁵ l mole^–1cm^–1 and 5.69 × 10⁴ l mole^–1cm^–1, respectively. The ascorbic acid determination is possible with a linear range up to 2.4 μg ml^–1, a calibration sensitivity of 0.744 ml μg^–1 at 560 nm and 0.323 ml μg^–1 at 748 nm, and a detection limit of 15 ng ml^–1 and 44 ng ml^–1, respectively. The procedure was used for the ascorbic acid determination in several fruit juices and pharmaceutical formulations. The results demonstrated a good precision (R.S.D. < 1%) and are in agreement with those obtained with others methods. The Br-PADAP method proposed is six times more sensitive than the method using the iron(II)-1,10-phenanthroline system. Received: 7 May 1996 / Revised: 1 July 1996 / Accepted: 8 August 1996     

Quercetin Prevents UV-lnduced Local Immunosuppression, but Does Not Affect UV-lnduced Tumor Growth in SKH-1 Hairless Mice

Abstract— Ultraviolet is thought to induce skin tumors by its dual activity as a mutagenic agent and a suppressor of cell-mediated immunity. In the present study the effects of quercetin, a flavonoid-containing compound, on carcinogenesis and immunosuppression were studied in SKH hairless mice exposed to suberythemal doses of UV for up to 17 weeks. It was found that quercetin did not affect the onset or growth of non-melanoma skin tumors resulting from UV exposure. In contrast, it prevented the suppression in contact hypersensitivity (CHS) to picryl chloride induced by UV. The mechanism of this prevention might be explained by the observation that the decreased number of epidermal Langerhans'cells is partly prevented by the quercetin. Quercetin did not alter the effects of UV in increasing numbers of spleen and lymph node cells, only partly in decreasing the CD8-positive cells in spleen cell populations and decreasing the lym-phoproliferative response of spleen cells to the mitogens concanavalin A and phytohemagglutinin. Thus oral quercetin did not prevent UV-induced carcinogenesis although it restored the skin-associated CHS response probably by protecting the antigen-presenting cells in the skin.     

PHOTOREAaIVITY OF CHLORAMPHENICOL in vitro AND in vivo

Abstract The negative side effects of chlorarnphenicol (CAP) mostly involve blood dyscrasias (e.g. irreversible nondose-dependent aplastic anemia), allergic skin reactions and eye damage. To learn the cause of these side effects, most research focuses on metabolically formed nitroso- and hydroxylamino derivatives in the predisposed patient. In previous investigations it was demonstrated that photochemical decomposition of CAP in vitro by UV-A leads to formation of p-nitrobenzaldehyde (pNB), p-nitrobenzoic acid (pNBA) and p-nitrosobenzoic acid (pNOBA); the latter comprises up to 45 mol% of the starting amount of CAP. Incubation of these photoproducts in rat blood showed that pNB and pNOBA rapidly react and that PNBA is stable under these conditions. Reaction products from pNB (half-life 1.7 min) proved to be pNBA and p-nitrobenzyl alcohol (pNBOH) while pNOBA (half-life 3.7 min) was converted into p-aminobenzoic acid (pABA). Exposure of CAP in rat blood to UV-A yielded the same end products: pNBA, PABA and pNBOH. To estimate the amount of oxidative stress generated in vivo by these compounds, the ability to form methemoglobin (MetHb) in erythrocytes was tested; only pNOBA and p-hydroxylaminobenzoic acid (pHABA), a possible intermediate in the decomposition of pNOBA, proved to be reactive. Ultraviolet-A exposure of rats, after intraperitoneal injection of CAP, led to 3.6 times the basic level of MetHb. In addition, covalent binding of ³H-labeled CAP photoproducts to the skin of the back and to the ears was found, which was 9.1 and 3.2 times higher, respectively, than the dark values. Toxicity toward bone marrow cells of all photoproducts was established in vitro. p-Nitrobenzaldehyde, pNOBA andpHABA were 20, 6 and 6 times more toxic than CAP, respectively. These results show that photodecomposition of CAP in vivo does occur. Its reactive photoproducts are able to cause damage that may lead to (systemic) side effects. The latter is supported by the fact that the nature of the reactive products, nitroso- and hydroxylamino derivatives, is the same as the expected metabolites.     

Lobocyclamides A-C,lipopeptides from a cryptic cyanobacterial mat containing Lyngbya confervoides

The structures of lipopeptides lobocyclamides A (1), B (2), and C (3) were solved using a combination of mass spectrometry, 2D NMR spectroscopy, and degradative analysis. Lobocyclamides B and C are the first peptides reported with the unusual amino acid 4-hydroxythreonine and also incorporate the rare homologous long-chain beta-amino acids 3-aminooctanoic acid and 3-aminodecanoic acid, respectively. The absolute configurations of the amino acid residues in each compound were assigned, after acid hydrolysis, by either direct chiral HPLC comparison with authentic standards or by prior derivatization by Marfey's method and reversed-phase HPLC. Both compounds exhibited moderate antifungal activity against a panel of Candida spp., including two fluconazole-resistant strains. When tested as a mixture, lobocyclamides A and B displayed synergistic in vitro antifungal activity, a phenomenon noted earlier for the related peptides laxaphycins A and B.     

Determination of mono-ortho substituted chlorobiphenyls by multidimensional gas chromatography and their contribution to TCDD equivalents

The mono-ortho chlorobiphenyls (CBs) 60, 74, 114, 123, 157, 167 and 189 were determined in Aroclor mixtures and aquatic organisms by multidimensional gas chromatography with electron capture detection (MDGC/ECD), using a combination of an Ultra 2 and an FFAP column. MDGC/ECD is recommended as the most suitable technique for direct determination of these CBs, without a liquid chromatographic (LC) pre-separation of mono-ortho CBs from the other CBs. Dependent, to some extent, on the stationary phase used, single-column determinations of these CBs easily yield too high results due to the presence of interferences. The contribution of the mono-ortho CBs studied to the total 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents (TEQs) from CBs in fish is highly dependent on the toxic equivalency factors (TEFs) used and varies between 0.02 and 22%. This contribution is mainly due to CBs 74, 114, 157 and 167 which may easily be determined by taking three heart-cuts and combining them into one MDGC/ECD run. The analytical error is negligible compared with the huge uncertainty of the TEFs. A need for more precise TEFs is emphasized.