Properties of cholesteryl esters in pure and mixed monolayers

The surface properties of cholesteryl palmitate, stearate, linoleate, linolenate, arachidonate, and acetate were investigated. Long-chain esters were not surface-active and force-area (pi-A) isotherms were not obtained. Unsaturated cholesteryl esters were oxidized at the air-water interface and these oxidized lipids gave expanded pi-A isotherms. Cholesteryl acetate had an equilibrium spreading pressure of 14.0 dynes/cm and formed a stable monolayer indistinguishable from cholesterol below that surface pressure. Cholesteryl linoleate formed mixed monolayers with surface-active lipids, and the amount of cholesteryl linoleate in the monolayer depended both on its solubility in the other lipid and on the surface pressure. Even at moderate surface pressures cholesteryl linoleate was extruded from the monolayer into a bulk phase. Cholesteryl acetate exhibited the well-known condensing effect of cholesterol in mixed monolayers with egg lecithin.     

Predictive simulations of the structural and adsorptive properties for PIM-1 variations

Despite the sizeable and growing body of research on polymers of intrinsic microporosity (PIMs), a greater understanding of the relationship between the monomer, polymer–polymer and polymer–gas interaction is of significant interest. Methane (CH₄), carbon dioxide (CO₂), oxygen (O₂) and nitrogen (N₂) adsorption isotherms at 20°C and up to 20 bar obtained from grand canonical Monte Carlo simulations are presented for PIM-1, PIM-1c, PIM-1n and PIM-1f. The new proposed structure, PIM-1f, is presented and characterised by geometric accessible surface area, pore size distribution, radial distribution function, X-ray scattering and gas adsorption isotherms. PIM-1f increased the geometric surface area when compared with PIM-1; however, the higher system density in combination with the lack of strong adsorption sites yielded the least effective adsorbent for the gases analysed in this study. The gas solubility and ideal solubility selectivity values are also presented and compared with available experimental data for all gases and several gas mixtures illustrating that PIM-1c is the most effective functionality studied for adsorbing these four gases. The conclusions made here are projected to facilitate the design of a material that combines the higher surface area of PIM-1f with the high adsorption capacity of PIM-1c, which will improve the performance of future PIMs.     

Effect of water activity on enzyme hydration and enzyme reaction rate in organic solvents

The effects of water on enzyme (protein) hydration and catalytic efficiency of enzyme molecules in organic solvents have been analyzed in terms of the thermodynamic activity of water, which has been estimated by the NRTL or UNIFAC equations. When the amount of water bound to the enzyme was plotted as a function of water activity, the water adsorption isotherms obtained from the water-solvent liquid mixtures were similar to the reported water-vapor adsorption isotherms of proteins. The water adsorption of proteins from the organic media was not significantly dependent on the properties of the solvents or the nature of the proteins. It is also shown that there is a linear relationship between the logarithm of the enzyme reaction rate and water activity. However, the dependence of the enzyme reaction rate on water activity was found to be different depending on the properties of the solvent. The relationship between water activity and other solvent parameters such as solvent hydrophobicity and the solubility of water in the solvent is also discussed.     

Combining synthetic and analytical strategies for preparative HPLC enantioseparation of monastrol racemic mixture

Large-scale resolution of racemic monastrol has been carried out by normal-phase mode HPLC on an amylose-based chiral stationary phase. Because monastrol solubility, in media of proper compositions for normal-mode HPLC separations (in terms of retention factors and selectivity), was significantly low and impractical for preparative scopes, racemic monastrol was transformed into the corresponding O-tert-butyldimethylsilyl derivative. The tert-butyldimethylsilyl group was chosen as a suitable derivatizing agent because it induced approximatively a six-times higher solubility and allowed for an almost quantitative recovery of pure monastrol from the derivatization-deprotection sequence. The competitive isotherms of the O-tert-butyldimethylsilyl compounds, measured through frontal analysis, were fitted to competitive Langmuir and four-parameter bi-Langmuir models. The equilibrium dispersive model of chromatography was used for modeling the nonlinear separation of the racemate and to optimize the experimental conditions for collection of highly concentrated fractions of pure (R,S)-O-tert-butyldimethylsilyl compounds, from which significant amounts of the corresponding enantiomers of monastrol (about 100 mg of each enantiomer with 30 runs on an analytical-scale column) were obtained by quantitative back-derivatization.     

Preparation and characterization of novel oxidized cellulose acetate methyl esters

In this paper, we report the preparation of oxidized cellulose acetate methyl esters (OCAM) from OCA (OC14A: carboxylic acid content 10.6% (w/w), degree of acetyl group substitution: 1.89; OC21A: carboxylic acid content 15.7% (w/w), degree of acetyl group substitution: 1.70) by treatment with methanol at room temperature using 4-dimethylaminopyridine (DMAP) as a catalyst and dicyclohexylcarbodiimide (DCC) as a coupling agent. The new polymers were characterized by Fourier-transform infrared (FT-IR) and (1)H and (13)C nuclear magnetic resonance spectroscopies, carboxylic acid content determination, moisture sorption isotherms, intrinsic viscosity, and powder X-ray diffractometry. The new polymers are amorphous powders. It is practically insoluble in water but show solubility in a range of organic solvents.     

The binding isotherms for the interaction of 5-doxyl stearic acid with bovine and human albumin.

Binding isotherms for the interaction of 5-doxyl stearic acid with bovine and human albumin are reported. The critical micelle concentration (CMC) and the limiting solubility of 5-doxyl stearic acid were determined using the electron spin resonance (ESR)-spin label method. The CMC and the limiting solubility of this spin-label stearic acid in saline-phosphate buffer are 3.5 x 10(-5) M and 2 x 10(-4) M, respectively. We found no ESR line width evidence for pre-association of the spin-label stearate below the CMC. Maximum binding of the spin-label stearate to both bovine and human albumin occurs before micelle formation. The binding isotherm for spin-label stearic acid interaction with bovine albumin is in agreement with data obtained by others using [1-(14)C]stearic acid. For human albumin, comparison is difficult since previous data obtained with [1-(14)C]stearic acid vary widely. Comparison of the ESR 2T(||) values (the splitting between low and high field extremes, a measure of the degree of immobilization of protein-bound spin-label stearate) for bovine and human albumin indicates a greater immobilization of the spin-label molecules bound to human albumin. The binding data indicate that complexes are formed with bound spin-label stearate/albumin ratios of at least 18. The computed equilibrium constants for both bovine and human albumin indicate that the first seven spin-label molecules are tightly bound, log K > 5.0. The species predicted to form in solution by these equilibrium constants are reported.     

Interactions of free and immobilized myelin basic protein with anionic detergents

The interaction of free and immobilized myelin basic protein (MBP) with sodium deoxycholate (DOC) and sodium dodecyl sulfate (NaDodSO4) was studied under a variety of conditions. Free MBP formed insoluble complexes with both detergents. Analysis of the insoluble complexes revealed that the molar ratio of detergent/MBP in the precipitate increased in a systematic fashion with increasing detergent concentration until the complex became soluble. At pH 4.8, equilibrium dialysis studies indicated that approximately 15 mol of NaDodSO4 could bind to the protein without precipitation occurring. Regardless of the surfactant, however, minimum protein solubility occurred when the net charge on the protein-detergent complex was between +18 and -9. Complete equilibrium binding isotherms of both detergents to the protein were obtained by using MBP immobilized on agarose. The bulk of the binding of both detergents was highly cooperative and occurred at or above the critical micelle concentration. At I = 0.1, saturation levels of 2.09 +/- 0.15 g of NaDodSO4/g of protein and 1.03 /+- 0.40 g of DOC/g of protein were obtained. Below pH 7.0 the NaDodSO4 binding isotherms revealed an additional cooperative transition corresponding to the binding of 15-20 mol of NaDodSO4/mol of protein. Affinity chromatography studies indicated that, in the presence of NaDodSO4 (but not in its absence), [125I]MBP interacted with agarose-immobilized histone, lysozyme, and MBP but did not interact with ovalbumin-agarose. These data support a model in which the detergent cross-links and causes precipitation of MBP-anionic detergent complexes. Cross-linking may occur through hydrophobic interaction between detergents electrostatically bound to different MBP molecules.     

Characterization of thin layer drying of Spirulina platensis utilizing perpendicular air flow

Spirulina is the most extensively used microalgae for animal and human nutrition mostly because of its high protein content, 60-65% on a dry weight basis. The drying is the most expensive operation. The aim of the study was to characterize drying of Spirulina platensis in thin layer. A Statistical model was applied to analyze the effects of independent variables (air temperature and loads of solids in the tray) on the response of solubility in acid medium. The analysis of phycocyanin content was determined at the best drying condition. The Spirulina isotherm data were adjusted through Guggenheim, Anderson and de Boer (GAB) and Brunauer, Emmett and Teller (BET) correlations. The nonlinear regression analysis of isotherms data showed that the GAB equation more effective adjusted the experimental data (R(2)>99% and E%<10%). Drying curves of Spirulina showed only a decreasing rate-drying period. The material load and the interaction between the air temperature and material load were significant effects (P0.05), and the best results of solubility in acid medium ( approximately 79%) occurred at 60 degrees C and 4 kg/m(2). In under these conditions the phycocyanin content was determined to be 12.6% of dried Spirulina.     

Comparing experimental and simulated pressure-area isotherms for DPPC

Although pressure-area isotherms are commonly measured for lipid monolayers, it is not always appreciated how much they can vary depending on experimental factors. Here, we compare experimental and simulated pressure-area isotherms for dipalmitoylphosphatidylcholine (DPPC) at temperatures ranging between 293.15 K and 323.15 K, and explore possible factors influencing the shape and position of the isotherms. Molecular dynamics simulations of DPPC monolayers using both coarse-grained (CG) and atomistic models yield results that are in rough agreement with some of the experimental isotherms, but with a steeper slope in the liquid-condensed region than seen experimentally and shifted to larger areas. The CG lipid model gives predictions that are very close to those of atomistic simulations, while greatly improving computational efficiency. There is much more variation among experimental isotherms than between isotherms obtained from CG simulations and from the most refined simulation available. Both atomistic and CG simulations yield liquid-condensed and liquid-expanded phase area compressibility moduli that are significantly larger than those typically measured experimentally, but compare well with some experimental values obtained under rapid compression.     

Synthesis of MCC–PEG Conjugate and Its Evaluation as a Superdisintegrant

PEGylated conjugate of microcrystalline cellulose (MCC) was synthesized by reacting MCC with polyethylene glycol (PEG) 200 in the presence of catalyst at elevated temperature. Conjugation between MCC and PEG was confirmed by FT-IR and ¹H NMR studies. The conjugate showed 61% PEG content increase in molecular weight determined by mass spectroscopy. PEGylation did not improve solubility of cellulose significantly. The physico-chemical properties of conjugate were compared against MCC. This conjugate was evaluated for water vapor uptake isotherms, maximum water saturation, water penetration rate, disintegration time, superdisintegration power, and dissolution study. After comparing its results with that of commercial superdisintegrants, it can be concluded that MCC–PEG conjugate can prove to be a good superdisintegrant.     

Optically detected magnetic resonance of tryptophan residues in Escherichia coli ssb gene product and E. coli plasmid-encoded single-stranded DNA-binding proteins and their complexes with poly(deoxythymidylic) acid

Optically detected magnetic resonance (ODMR) spectroscopy has been applied to several single-stranded DNA-binding (SSB) proteins encoded by conjugative plasmids of enteric bacteria. Fluorimetric equilibrium binding isotherms confirm their preferential binding to single-stranded DNA and polynucleotides and reveal a limited protein solubility at low ionic strength. The plasmid SSB-like proteins show the highest affinity for polydeoxythymidylic acid; these complexes are the least sensitive to disruption by salt. ODMR data on these complexes suggest the existence of stacking interactions between tryptophan residue(s) and thymine bases, as evidenced by spectral red shifts of the tryptophan phosphorescence 0,0 band, reduction of the magnitude of D zero field splitting parameter, and a dramatic reversal of the polarity of the ODMR signals. Wavelength-selected ODMR results point to the existence of two distinct tryptophan sites in these complexes. The triplet state properties of the red-shifted site are drastically altered by its interaction with the thymine bases. The chromosomal Escherichia coli SSB protein-poly(dT) complex shows an additional tryptophan site with zero field splitting parameters similar to those of the free protein. This site can be attributed to Trp-135, which is missing in each of the other plasmid SSB proteins, suggesting that this particular residue is not involved in the interaction with polynucleotides.     

Adsorption of horseradish peroxidase, ovomucoid and anti-immunoglobulin to colloidal gold for the indirect detection of concanavalin A, wheat germ agglutinin and goat anti-human immunoglobulin G on cell surfaces at the electron microscopic level: a new method, theory and application.

A method is described for the adsorption of selected macromolecules to colloidal gold which is then used as an electron dense marker for the indirect detection of specific cell surface molecules. Membrane bound concanavalin A, which binds specific sugars on horseradish peroxidase, and wheat germ agglutinin, which binds specific sugars on ovomucoid are detected indirectly with gold labeled horseradish peroxidase and ovomucoid, respectively. Goat anti-human IgM on blood lymphocytes is detected with gold labeled rabbit anti-goat IgG. In the preparation of colloidal gold labeled proteins, the problems of flocculation of colloidal gold by proteins and nonadsorption of proteins to colloidal gold, are solved through a combination of concentration of protein and pH variable adsorption isotherms, which allows one to determine the conditions for adsorption of proteins to colloidal gold. Adsorption is pH dependent, the pH conditions correlating with the isoelectric point(s) of the major protein fraction(s); adsorption is influenced by interfacial tension, solubility and by the electrical charge on the molecules. Colloidal gold is inexpensive and preparation of a useful label is rapid, reproducible and the results easily quantitated from electron micrographs.     

黄芩苷溶解性能的测定与表征

目的：充分了解黄芩苷的溶解性质,为黄芩苷类制剂的研究设计提供依据。方法：采用HPLC法测定黄芩苷在各溶媒中的溶解度,考察温度、pH值、表面活性剂等对其溶解度的影响,利用溶度参数理论探讨其溶解性能理论及表征其溶解性能。结果：黄芩苷在水中属几乎不溶的范畴;溶解度随着温度升高和pH值的增加而升高,溶解过程是吸热的,溶解度与温度的关系方程线性关系良好,可用于预测黄芩苷在设定温度下的溶解度;吐温80可提高黄芩苷的增溶度;黄芩苷在各溶媒中的溶解度大小与利用溶度参数表征黄芩苷溶解性能的结果吻合。结论：黄芩苷水溶性差、脂溶性均较差,可通过升温、调节pH值及加表面活性剂改变黄芩苷的溶解性质,可利用溶度参数理论对黄芩苷的溶解性能进行表征。     

The use of model-fitting in the interpretation of 'dual' uptake isotherms

Abstract. Published data of the concentration dependence of the uptake rate (uptake isotherms) of K⁺ Na⁺, Cl^?, SO2^?₄, and L-lysine in barley roots, and glucose and 3-O-methylglucose in potato tuber tissue, were re-examined. In as much as these isotherms yield non-linear, concave upward Eadie-Hofstee plots, they might have been termed ‘dual’ isotherms. In addition, all these isotherms have been considered to display discontinuous transitions in gradient. The following models that yield continuous isotherms were fitted to the isotherms: (1) the sum of a Michaelis-Menten term and a linear term; (2) the sum of two Michaelis-Menten terms; (3) the sum of two Michaelis-Menten terms and a linear one. Goodness of fit was judged from: (i) the weighted mean square of deviates; (ii) the standard errors of the kinetic parameters; (iii) the algebraic significance of the terms; (iv) a Rankits plot of the residuals; (v) a Runs test on the residuals. For the precise and detailed isotherms of SO^2? uptake, only model (3) gave a fit that was satisfactory in all respects. There appeared to be no reason to consider these isotherms as multiphasic. The same conclusion was reached for the L-lysine uptake isotherms. For the other isotherms the results were less conclusive. Thai for K⁺ and Na+ could, at any rate, be described satisfactorily by a continuous model, the best fit being obtained with model (2). The uptake isotherms of Cl^? and 3-0-methylglucose could be best described by model (2), and that of glucose by model (3), only the result of the Runs test being unsatisfactory. It is concluded that there is hardly any evidence that the presumed ‘jumps’ or discontinuities or inflections in the gradient of uptake isotherms are not due to experimental error in the data. It is suggested that many uptake isotherms may be described by model (3), although the reason for this is still incompletely understood.     

A study on moisture isotherms of formulations: the Use of polynomial equations to predict the moisture isotherms of tablet products

The objectives of this study were to investigate the effects of manufacturing parameters on the moisture sorption isotherms of some tablet formulations and to predict the moisture isotherms of the final formulations using polynomial equations. Three tablet formulations including a placebo and 2 drug products were prepared through wet granulation, drying, compression, and coating processes. Equilibrium moisture content of excipients and granules at 25°C with different relative humidities were determined using a dynamic moisture sorption microbalance, while such data for tablets were determined using desiccators. Moisture sorption isotherms were expressed in polynomial equations. Excipient isotherms were used to predict the moisture sorption isotherms of the 3 tablet products. Results showed that different physical properties of granules and tablets, such as particle size distribution, density, and porosity resulting from different granulation and compression conditions did not have significant effect on the moisture isotherms of the materials. Changing coating materials from a powder mixture to a film also did not change the moisture sorption characteristics significantly. The predicted moisture sorption isotherms of the formulations agreed well with the experimental results. These results show that moisture isotherms of solid pharmaceutical products manufactured with conventional processes may be predicted using the isotherms of excipients, and polynomial equations may be used as a tool for the prediction of moisture isotherms.     

Mixed monolayers of straight-chain/branched-chain phospholipids. I. Mixed monolayers of distearoyl phosphatidylcholine and diisoeicosanoyl phosphatidylcholine

The temperature dependence of the force/area isotherms of monolayer of distearoyl phosphatidylcholine (DSPC), diisoeicosanoyl phosphatidylcholine (DIEPC) and a complete mixed compositional range of these two lecithins are reported. The isotherms for DSPC closely resemble those previously reported for dipalmitoyl phosphatidylcholine but are shifted to higher temperatures by 16 degrees C. The isotherms of DIEPC, an iso-branched lecithin, show differences from these obtained for similar straight-chain lecithins in that the full condensed isotherms are more expanded, the fully expanded isotherms are more condensed and therefore the liquid expanded (LE)/liquid condensed (LC) intermediate region is significantly reduced. This means that the condensed state is more disordered and the expanded state is less disordered than the corresponding states in straight-chain lecithins. Data for the mixed films are interpreted in terms of surface pressure/mole fraction phase diagrams and both energies and entropies of compression associated with the LE/LC transition. The phase diagrams at 34.1 degrees C, 35.8 degrees C and 38.5 degrees C are all of the negative azeotropic type with the surface pressure minimum point shifting with temperature. The thermodynamic analysis indicates that from 34.1 degrees C to 38.5 degrees C the driving force for mixing changes from the entropy to the energy of the transition. It would seem that at the lower temperature the packing of the distearoyl lecithin is perturbed by the diisoeicosanoyl lecithin, while at higher temperatures the very high entropy of pure or nearly pure diisoeicosanoyl lecithin results in other mixtures having less entropy than would be expected on an ideal mixing basis.     

Adsorption of PAHs on the Sediments from the Yellow River Delta as a Function of Particle Size and Salinity

In a seawater environment, the particle size of sediment and salinity play an important role in the adsorption behaviors of polycyclic aromatic hydrocarbons (PAHs) on sediment. In this study, batch adsorption experiments were carried out with the sediments from the Yellow River Delta (YRD) to explore the effect of particle size and salinity on the adsorption behaviors of phenanthrene (Phe), fluoranthene (Fla), and pyrene (Pyr). Adsorption isotherms of PAHs on different-sized sediments can be described by a Freundlich model with the correlation coefficients ranging from 0.96 to 0.99. The adsorption capacity of PAHs was in reverse proportion to the particle size of the sediments and in direct proportion to salinity. The sediments with smaller particle size possessed higher content of aromatic and fat components, which had strong adsorption capacity toward PAHs. Salinity influenced the adsorption behaviors of PAHs by changing the solubility of PAHs and the physicochemical properties of the sediments. The salting-out constants of Phe, Fla, and Pyr were in the range of 0.292 to 0.296, 0.230 to 0.289, and 0.293 to 0.307 l/mol, respectively. These research findings are of importance to an assessment of the fate and transport of PAHs in seawater-sediment systems.     

The mode of action of N-(n-Dodecyl)diethanolamine with particular reference to the effect of protonation on uptake by Escherichia coli.

In a homologous series of N-(n-alkyl)diethanolamines antimicrobial activity was related to surface activity and increasing octanol-water partition coefficient. Maximum activity was exhibited by the dodecyl-, tetradecyl- and hexadecyl-derivatives. Dodecyldiethanolamine (DDE) displayed a broad spectrum of activity. Towards Escherichia coli NCIB8277, its bacteriostatic and bactericidal activity increased as the degree of protonation lessened, and may have been influenced by the formation of micelles. Uptake of DDE by washed suspensions of E. coli was more rapid and more extensive at pH 7.0 than pH 4.0. Within this pH range, bacterial uptake, the octanol-water partition coefficient (lipid solubility) and the proportion of unprotonated DDE all increased. Uptake isotherms at pH values in the range 4.0 to 8.0 are interpreted as signifying different uptake mechanisms for the protonated and unprotonated forms.     

Adsorption of allopurinol and ketotifen by chitosan

The experimental work of studying the adsorption of ketotifen and allopurinol by chitosan focused on determining the solubilities and the adsorption isotherms of the adsorbates employed in this study. The adsorption of the aforementioned compounds by chitosan was studied using the rotating bottle method. The concentrations, both before and after the attainment of equilibrium, were determined with the aid of a reversed-phase high-performance liquid chromatography column. The results of these studies demonstrated that ketotifen and allopurinol are both adsorbed by chitosan. The nonlinear Langmuir-like and the Freundlich models both were applied to the experimental data. The correlation coefficients obtained from the nonlinear Langmuir-like model were better than those obtained from Freundlich model, suggesting that allopurinol and ketotifen interacted with certain specific binding sites on the chitosan surface. The allopurinol adsorption experiments indicated that the particle size of chitosan and therefore the surface area can significantly affect the Langmuir capacity constant, while the affinity constants are statistically the same. As expected from the solubility studies, the ketotifen adsorption experiments at 2 different pHs (7 and 10) showed that the adsorption affinity at pH 10 was much higher than at pH 7. What was not expected was that the capacity constants were significantly different, suggesting that further studies are needed using common ion buffers and multicomponent adsorption for the proper mechanism to be determined.     

Relaxation in LE-LC transition of fatty acid monolayers

The break point observed on fatty acid isotherms corresponds to a transition between two two-dimensional phases, since it is clearly distinct from the collapse. But the transformation from the liquid expanded phase to the liquid condensed phase is slow and relaxations with characteristic times have been observed. Most of the isotherms published so far should be considered with caution since the barrier speed generally used is much greater than the relaxation rate we obtain. Hence, at least in the break point neighbourhood, they are not true equilibrium isotherms.