Interaction of dextran sulfates with positively and negatively charged silver bromide hydrosols

Summary The effects of dextran sulfates of different molecular weights and charge densities on the stability of positively and negatively charged silver bromide solsin statu nascendi have been studied by means of light scattering.The plots of scattering intensities of a positively charged sol against the concentration of the added dextran sulfates show one pronounced maximum, the position which is independent on the molecular weight of the polyelectrolyte used. The maximum shifts to lower polyion concentrations with dilution of the sol.The effect of polyanions on the stability of silver bromide sols of the same sign of charge were investigated as a function of molecular weight of the polymers, the sol concentration, the charge and the concentration of counterions, and the addition of methanol. Destabilization only occurred if sufficient amount of indifferent electrolyte was present in the system. However, the concentration of counterions necessary to produce a flocculation maximum was lower in the presence of the polyelectrolytes than in their absence. The results obtained were compared with the data on sols containing nonionic dextrans reported earlier.

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Zusammenfassung Der Einfluß der Dextransulfate von verschiedenen Molekulargewichten und Ladungsdichten auf die Stabilität der positiv und negativ geladenen Silberbromid-Solein statu nascendi wurden durch Lichtstreuung untersucht. Wenn die Intensitäten der Lichtstreuung eines positiv geladenen Silberbromid-Sols gegen die Konzentration der zugesetzten DextranSulfate aufgetragen werden, tritt ein ausgeprägtes Maximum auf, dessen Lage von dem Molekulargewicht des angewandten Polyelektrolyten unabhängig ist. Bei Verdünnung des Sols wird das Maximum zur niedrigeren Konzentration des Polyanions verschoben.Der Einfluß der Polyanionen auf die Stabilität der Silberbromid-Sole mit gleichem Ladungsvorzeichen wurde in Abhängigkeit von dem Molekulargewicht des zugesetzten Dextransulfats, der Solkonzentration, der Ladung und Konzentration der Gegenionen und dem Zusatz von Methylalkohol untersucht. Destabilisierung wird nur in Anwesenheit einer genügenden Menge von Neutralelektrolyten in den untersuchten Systemen beobachtet. Die Konzentration der Gegenionen, die ein Flockungsmaximum verursachen, ist immer niedriger als die kritische Koagulationsmenge derselben Ionen für das gleiche Sol in Abwesenheit von Makroionen. Die Resultate wurden mit den Wechselwirkungen der Silberbromid-Sole mit nichtionogenen Dextranen verglichen, und der Mechanismus der Flockung durch Polyelektrolyte wurde diskutiert.

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5 figures and 1 table

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Supported by the NSF Grant GP 42331 X.

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A part of the Ph.D. Thesis by David Lindsay.     

Quantitative analysis of the low molecular weight serum proteome using 18O stable isotope labeling in a lung tumor xenograft mouse model

With advancements in the analytical technologies and methodologies in proteomics, there is great interest in biomarker discovery in biofluids such as serum and plasma. Current hypotheses suggest that the low molecular weight (LMW) serum proteome possesses an archive of clipped and cleaved protein fragments that may provide insight into disease development. Though these biofluids represent attractive samples from which new and more accurate disease biomarkers may be found, the intrinsic person-to-person variability in these samples complicates their discovery. Mice are one of the most extensively used animal models for studying human disease because they represent a highly controllable experimental model system. In this study, the LMW serum proteome was compared between xenografted tumor-bearing mice and control mice by differential labeling utilizing trypsin-mediated incorporation of the stable isotope of oxygen, 18O. The digestates were combined, fractionated by strong cation exchange chromatography, and analyzed by nanoflow reversed-phase liquid chromatography coupled online with tandem mass spectrometry, resulting in the identification of 6003 proteins identified by at least a single, fully tryptic peptide. Almost 1650 proteins were identified and quantitated by two or more fully tryptic peptides. The methodology adopted in this work provides the means for future quantitative measurements in comparative animal models of disease and in human disease cohorts.     

An analysis of the complex molecular orbitals method

Numerical results for the ground state of the HN ₂ ⁺ and HCO⁺ molecular ions at their near equilibrium geometry, obtained by the complex molecular orbitals (CMO) method in the extended basis set, are reported. The CMO wavefunction of the HN ₂ ⁺ ion is compared with the CI wavefunction obtained in the same basis set. This reveals the nature of approximations inherent in the CMO method. A peculiar feature of the occupation numbers of the CMO natural orbitals is also explained.Alexander von Humboldt Fellow. On leave from the Institute Rudjer Bokovi, Zagreb, Croatia, Yugoslavia.     

Design and construction of an quasi-adiabatic dissolution calorimeter with a novel dosing apparatus and a low heat capacity

A quasi-adiabatic calorimeter for determining the molar solution enthalpies (Δ_sol H) of non-volatile solids was constructed. The design of the instrument was adjusted to allow the determination of solution enthalpies of small amounts of solids. For that purpose, the novel apparatus for sample dosage with virtually negligible “blank heat” was built. The rather low heat capacity of the calorimeter was achieved by reducing the volume of the reaction cell (20 mL), the dosing unit, and electric elements (the thermistor and the heater). Good thermal isolation of the reaction cell from the surroundings was accomplished by placing the cell into an evacuated polypropylene vessel. A computer program for processing the calorimetric data according to modified Regnault–Pfaundler method was written. The performance of the calorimeter was tested by determining the heats of the reactions serving as thermochemical standards at 25 °C (the dissolution of KCl and NaCl in water and the dissolution of tris(hydroxymethyl)-aminomethane in 0.1 mol dm^?3 HCl(aq)). The obtained data were in very good agreement with the literature values.     

Solvophobically Driven Complexation of Adamantyl Mannoside with β-Cyclodextrin in Water and Structured Organic Solvents

The effects of solvent and temperature on the complexation of adamantyl mannoside with β-cyclodextrin and 6-O-monotosyl-6-deoxy-β-cyclodextrin were explored experimentally and by means of molecular dynamics simulations. Efficient binding was observed only in hydrogen-bonded solvents, which indicated solvophobically driven complexation. The stability of the inclusion complex was considerably higher in aqueous media. A pronounced temperature dependence of Δ_rH^○ and Δ_rS^○, resulting in perfect enthalpy–entropy compensation, was observed in water. The complexation thermodynamics was in line with classical rationale for the hydrophobic effect at lower temperatures and the nonclassical explanation at higher temperatures. This finding linked cyclodextrin complexation thermodynamics with insights regarding the effect of temperature on the hydration water structure. The complexation enthalpies and entropies were weakly dependent on temperature in organic media. The signs of Δ_rH^○ and Δ_rS^○ were in accordance with the nonclassical hydrophobic (solvophobic) effect. The structures of the optimized product corresponded to those deduced spectroscopically, and the calculated and experimentally obtained values of Δ_rG^○ were in very good agreement. This investigation clearly demonstrated that solvophobically driven formation of cyclodextrin complexes could be anticipated in structured solvents in general. However, unlike in water, adamantane and the host cavity behaved solely as structure breakers in the organic media explored so far.     

Circulating Levels of Dephosphorylated-Uncarboxylated Matrix Gla Protein in Patients with Acute Coronary Syndrome

Vascular calcification contributes to the pathogenesis of coronary artery disease while matrix Gla protein (MGP) was recently identified as a potent inhibitor of vascular calcification. MGP fractions, such as dephosphorylated-uncarboxylated MGP (dp-ucMGP), lack post-translational modifications and are less efficient in vascular calcification inhibition. We sought to compare dp-ucMGP levels between patients with acute coronary syndrome (ACS), stratified by ST-elevation myocardial infarction (STEMI) and non-ST-elevation myocardial infarction (NSTEMI) status. Physical examination and clinical data, along with plasma dp-ucMGP levels, were obtained from 90 consecutive ACS patients. We observed that levels of dp-ucMGP were significantly higher in patients with NSTEMI compared to STEMI patients (1063.4 ± 518.6 vs. 742.7 ± 166.6 pmol/L, p < 0.001). NSTEMI status and positive family history of cardiovascular diseases were only independent predictors of the highest tertile of dp-ucMGP levels. Among those with NSTEMI, patients at a high risk of in-hospital mortality (adjudicated by GRACE score) had significantly higher levels of dp-ucMGP compared to non-high-risk patients (1417.8 ± 956.8 vs. 984.6 ± 335.0 pmol/L, p = 0.030). Altogether, our findings suggest that higher dp-ucMGP levels likely reflect higher calcification burden in ACS patients and might aid in the identification of NSTEMI patients at increased risk of in-hospital mortality. Furthermore, observed dp-ucMGP levels might reflect differences in atherosclerotic plaque pathobiology between patients with STEMI and NSTEMI.     

Gas chromatographic determination of two isosorbide mononitrates in plasma

A GC/EC method has been developed for the determination of 2-isosorbide mononitrate (2-ISMN) and 5-isosorbide mononitrate (5-ISMN) in blood plasma. The procedure is based on extraction of ammonium sulfate-treated plasma with ether followed by a cleanup via n-heptane/methanol partitioning. After conversion to t-butyldimethylsilyl ethers, the ISMNs are chromatographed on a 3% OV-17 column. Absolute recoveries of 76.7 and 84.8% were achieved for 2-ISMN and 5-ISMN, respectively. Using o-nitrobenzyl alcohol as an internal standard, relative standard deviations of 4.8 to 6.1% were observed over the concentration ranges of 10 to 100 ng/ml for 2-ISMN and 250 to 1500 ng/ml for 5-ISMN.     

On Hadamard Inequality for Log-Concave Functions

Some improvements and generalizations of Finks results about Hadamards inequality for log-concave functions are given.AMS Subject Classification: 26D07, 26D15, 26A51.