Sol-gel transition temperature of PLGA-g-PEG aqueous solutions

Aqueous solutions of poly(DL-lactic acid-co-glycolic acid)-g-poly(ethylene glycol) copolymers exhibited sol-to-gel transition with increasing temperature. Further increase in temperature makes the system flow and form a sol phase again. Subcutaneous injection of a copolymer aqueous solution (0.5 mL) resulted in a formation of a hydrogel depot by temperature-sensitive sol-to-gel transition in a rat model. The reliable determination and control of sol-to-gel transition temperatures are the most important issues for this kind of sol-gel reversible hydrogel. The sol-to-gel transition temperature determined by the test tube inverting method, falling ball method, and dynamic mechanical analysis coincided within 1-2 degrees C. Fine tuning of the sol-to-gel transition temperature was achieved by varying the ionic strength of the polymer solutions and by mixing two polymer aqueous solutions with different sol-to-gel transition temperatures. The sol-to-gel transition temperature of polymer mixture aqueous solutions was well described by an empirical equation of miscible blends, indicating miscibility of the two polymer systems in water on the molecular level.     

Effect of temperature on argyrophil impregnation: development of a high temperature rapid argyrophil procedure

Our studies on the effects of temperature on the demonstration of neurosecretory granules using argyrophil stains indicate an inverse relationship between the time needed for staining and temperature of the silver and reducing solutions. Careful monitoring of the temperature of silver solutions during the Grimelius procedure and its modifications show long incubation times serve in large part only to bring the solutions to reaction temperature. Tissue sections added when this temperature has been reached will stain with the same intensity as sections impregnated for the entire incubation period. We have modified the argyrophil procedure so that double-impregnation with solutions preheated to 60-70 C and development in Bodian's reducer prepared with preheated water rapidly demonstrates secretory granules. Our method does not require a microwave oven and much shorter incubation periods are required than with usual procedures. It is not necessary to incubate sections in hot solutions for extended periods of time, which can lead to detachment of sections, nonspecific staining and decomposition of the silver solution. Rinsing after impregnation and before development greatly increases contrast of argyrophil cells by reducing background staining. Our procedure results in more reliable staining of argyrophil and argentaffin cells and takes only ten minutes.     

Effect of Temperature on Argyrophil Impregnation: Development of A High Temperature Rapid Argyrophil Procedure

Out studies on the effects of temperature on the demonstration of neurosecretory granules using argyrophil stains indicate an inverse relationship between the time needed for staining and temperature of the silver and reducing solutions. Careful monitoring of the temperature of silver solutions during the Grimelius procedure and its modifications show long incubation times serve in large part only to bring the solutions to reaction temperature. Tissue sections added when this temperature has been reached will stain with the same intensity as sections impregnated for the entire incubation period. We have modified the argyrophil procedure so that double-impregnation with solutions preheated to 60-70 C and development in Bodian's reducer prepared with preheated water rapidly demonstrates secretory granules. Our method does not require a microwave oven and much shorter incubation periods are required than with usual procedures. It is not necessary to incubate sections in hot solutions for extended periods of time, which can lead to detachment of sections, nonspecific staining and decomposition of the silver solution. Rinsing after impregnation and before development greatly increases contrast of argyrophil cells by reducing background staining. Our procedure results in more reliable staining of argyrophil and argentaffin cells and takes only ten minutes.     

Study of the stability of promethazine enantiomers by liquid chromatography using a vancomycin-bonded chiral stationary phase

Three chiral stationary phases based on macrocyclic antibiotics (teicoplanin, vancomycin and ristocetin A) have been tested for chiral separations of promethazine. The vancomycin phase permits the best, baseline enantioseparation of promethazine, with a mobile phase of a 80:20 (v/v) mixture of methanol with a 1% aqueous triethylamine acetate buffer of pH 4.1 and with the analysis time not exceeding 15 min. The limits of detection amount to 27.5 and 31.0 ng/ml for the earlier and later eluting enantiomers, respectively. This separation system, that also permits a sufficient resolution between the promethazine enantiomers and their degradation products, has further been used for the monitoring of the effects of light, temperature and the promethazine concentration in solution on the stability of methanolic promethazine solutions over a period of 19 days. It has been found that the stability of more concentrated solutions is primarily affected by the temperature, whereas the effects of the temperature and light are comparable with more dilute solutions. After 19 days, a solution of 0.5 mg/ml promethazine stored in darkness at a low temperature still contained 84.0% of the original amount of the enantiomers; this value was 89.6% for a solution with the ten times lower promethazine concentration. If the solutions were stored in darkness but at laboratory temperature, the respective values decreased to 38.1 and 62.6% and for the solutions exposed to light at laboratory temperature they decreased even more to 36.7 and 52.6% of the initial promethazine amount.     

Benchmark solution for the prediction of temperature distributions during radiofrequency ablation of cardiac tissue

Several studies on radiofrequency (RF) ablation are aimed at accurately predicting tissue temperature distributions by numerical solution of the bioheat equation. This paper describes the development of a solution that can serve as a benchmark for subsequent numerical solutions. The solution was obtained using integral transforms and evaluated using a C program. Temperature profiles were generated at various times and for different convection coefficients. In addition, a numerical model was developed using the same assumptions made in obtaining the benchmark solution. Comparison of surface and axial temperature profiles shows that the two solutions match very closely, cross validating the numerical methods used in evaluating both solutions.     

STUDIES ON THE FORMATION AND IONIZATION OF THE COMPOUNDS OF CASEIN WITH ALKALI : II. THE CONDUCTIVITIES OF ALKALI CASEINATE SOLUTIONS.

1. The results of conductivity experiments with alkali caseinate solutions are given and a graphical method of extrapolation, which gives a straight line, is described. The results of the conductivity experiments are shown to be in accord with the results of the previous transference experiments. 2. The change of conductivity of the alkali caseinate solutions with temperature is shown to follow a straight line relationship. 3. The high value of the mobility which was obtained for the casein ion and the high temperature gradient are discussed in relation to McBain''s theory of colloidal electrolytes.     

Critical helix content in gelatin gels

Aqueous gelatin solutions of different concentrations have been investigated at various quench temperatures by viscosity measurements to determine the gel times and by optical rotation measurements to derive the evolution of the helix content by reference to native collagen. As a result, it appears that the gelation of the different aqueous gelatin solutions tested takes place at a common helix concentration independent of the initial gelatin concentration and quench temperature. Further, for each concentration, the dependence of gel time as a function of quench temperature has revealed the existence of two domains: a higher temperature domain where gel times increase strongly with quench temperature and a lower temperature domain where gel times are short and only slightly dependent on quench temperature.     

Hydroxyl-proton resonance shifts for a range of aqueous sugar solutions

At low temperature and in a narrow pH-range, the hydroxyl-proton resonance spectra of a range of mono-, di- and oligo-saccharides in dilute aqueous solutions have been resolved. The signals rapidly broaden on raising the temperature and on changing the pH of the solutions. Optimum conditions for obtaining maximum resolution are described and attempts are made to assign the resonances to specific hydroxyl groups. In all cases the resonances for the anomeric hydroxyl-proton occurred at lowest field and the pH value for optimum resolution of these resonances was always lower than that for the other hydroxyl resonances.     

In vitro and in vivo release of albumin using a biodegradable MPEG-PCL diblock copolymer as an in situ gel-forming carrier

An MPEG-PCL diblock copolymer was synthesized as an in situ gel carrier, and its phase transition behavior in aqueous solutions was examined. For comparison, aqueous solutions of Pluronic F-127, a widely used injectable gel-forming solution, were also studied. Both MPEG-PCL copolymer and Pluronic aqueous solutions were sols at room temperature. As the temperature was increased above room temperature, the diblock copolymer and Pluronic solutions underwent a sol-to-gel phase transition, which manifested as an increase in viscosity indicative of the formation of a gel. All of the copolymer solutions became gels at body temperature, although the gel viscosity increased with the increasing concentration of the MPEG-PCL diblock copolymer in the solution. In in vitro experiments, in which the gels were exposed to PBS, the MPEG-PCL gels maintained their structural integrity for more than 28 days, whereas the Pluronic gel disappeared within 2 days. The same results were observed when the polymer solutions were subcutaneously injected into rats. The MPEG-PCL gels maintained their structural integrity longer than 30 days, while the Pluronic gel could not be observed after 2 days. The ability of the gels as drug carriers was studied by measuring the release of fluorescein isothiocyanate-labeled bovine serum albumin (BSA-FITC) from MPEG-PCL diblock copolymer gels in vitro as well as in vivo. In vitro, BSA release was sustained above 20 days, with a greater release at lower diblock copolymer concentration; by contrast, Pluronic gels exhibited almost complete release of BSA-FITC within 1 day. When the BSA-FITC-loaded diblock copolymer and Pluronic solutions were subcutaneously injected into rats, they immediately transformed into a gel. In vivo, sustained release of BSA-FITC over 30 days was observed from the MPEG-PCL gel, whereas BSA-FITC release from the Pluronic gel ceased within 3 days. Collectively, the present findings show that MPEG-PCL diblock copolymer solutions are thermo-responsive and maintain their structural integrity under physiological conditions, indicating that they are suitable for use as injectable drug carriers.     

Motion of the lengthened zwitterionic head groups of C16-lecithin analogues in aqueous solutions as studied by dielectric relaxation measurements

Phosphatidyl choline analogues with increased phosphate-trimethylammonium distance were synthesized and aqueous solutions of these bilayer forming phospholipids were prepared. Dielectric spectra of the solutions were measured at several temperatures around the crystalline/liquid-crystalline phase transition temperature of the samples. The observed data are treated in terms of a Debye relaxation function and also of a relaxation function based on a theoretical model of the aqueous solutions of multibilayer vesicles. As a noteworthy result, a pronounced cooperativity effect in the diffusive motions of the zwitterionic head groups emerges. The degree of cooperativity depends on the radius of curvature of the multibilayer vesicles and also on the length of the phospholipid zwitterions. The values for the mobility of the trimethylammonium group are of the same order of magnitude as those for the mobility of whole phospholipid molecules in its lateral diffusive motion. Indications for a phase transition at a temperature above the main transition temperature are found with solutions of C_16⁻ lecithin analogues with 9 and 10 methylene groups between the phosphate and the trimethylammonium group.     

Low Temperature Absorption Spectra of Chlorophyll a in Polar and Nonpolar Solvents

Absorption spectra of chlorophyll a were measured in polar and non-polar solvents, as a function of temperature from 298 degrees to 77 degrees K. Both dilute and concentrated solutions were examined. In both types of solvents at room temperature, the absorption spectra of concentrated solutions differ from dilute ones in that the half width of the main red absorption band is greater, and all bands are shifted to longer wavelengths. These differences are largely due to the presence of dimers when the pigment concentration is high. In dilute ethanol solutions, where the chlorophyll is unassociated, cooling causes a red shift in all bands which is due to the increased polarity of the solvent at low temperature. On cooling at high concentrations in ethanol and EPA, a new band appears near 700 nm. This band is attributed to dimers present prior to cooling, but absorbing at shorter wavelengths at room temperature. In nonpolar solvents, a band near 700 nm appears at the solvent freezing point. In these solvents, the "700" nm absorption is attributed to dimers, and/or small polymers, partly formed by cooling. A change in aggregate geometry when the solvent becomes viscous or frozen can account for the appearance of this "700" nm absorption band at low temperature, in polar and nonpolar media.     

Dielectric relaxation in lecithin/cholesterol/water-mixtures

The dielectric spectrum of aqueous solutions of dimyristoyl-l-3-phosphatidylcholine and dipalmitoyl-l-3-phosphatidylcholine with admixed cholesterol has been determined by means of a pulse reflection method which was used to measure the complex permittivity of the solutions as a function of frequency between 100 kHz and 50 MHz. Measurements have been performed at various concentrations of cholesterol in dependence of temperature around the crystal-line/liquid-crystalline phase transition temperature of the solutions.The measured dielectric spectra are treated in terms of a Debye-function. The dielectric relaxation strength and the relaxation time decrease distinctly with increasing cholesterol concentration. In addition, the data are treated on the basis of a theoretical solution model in order to allow for conclusions concerning the lecithin head group motion in the lipid bilayer surface. One important result is that increasing cholesterol concentration affects the interaction of the lecithin head groups and increases their mobility. These effects already occur at small concentrations of cholesterol.     

Water proton magnetic resonance studies of normal and sickle erythrocytes. Temperature and volume dependence.

The temperature and cell volume dependence of the NMR water proton line-width, spin-lattice, and spin-spin relaxation times have been studied for normal and sickle erythrocytes as well as hemoglobin A and hemoglobin S solutions. Upon deoxygenation, the spin-spin relaxation time (T2) decreases by a factor of 2 for sickle cells and hemoglobin S solutions but remains relatively constant for normal cells and hemoglobin A solutions. The spin-lattice relaxation time (T1) shows no significant change upon deoxygenation for normal or sickle packed red cells. Studies of the change in the NMR linewidth, T1 and T2 as the cell hydration is changed indicate that these parameters are affected only slightly by a 10-20% cell dehydration. This result suggests that the reported 10% cell dehydration observed with sickling is not important in the altered NMR properties. Low temperature studies of the linewidth and T1 for oxy and deoxy hemoglobin A and hemoglobin S solutions suggest that the "bound" water possesses similar properties for all four species. The low temperature linewidth ranges from about 250 Hz at -15 degrees C to 500 Hz at -36 degrees C and analysis of the NMR curves yield hydration values near 0.4 g water/g hemoglobin for all four species. The low temperature T1 data go through a minimum at -35 degrees C for measurements at 44.4 MHz and -50 degrees C for measurements at 17.1 MHz and are similar for oxy and deoxy hemoglobin A and hemoglobin S. These similarities in the low temperature NMR data for oxy and deoxy hemoglobin A and hemoglobin S suggest a hydrophobically driven sickling mechanism. The room temperature and low temperature relaxation time data for normal and sickle cells are interpreted in terms of a three-state model for intracellular water. In the context of this model the relaxation time data imply that type III, or irrotationally bound water, is altered during the sickling process.     

Vibrational Properties of Cyclodextrin�CWater Solutions Investigated by Low-Frequency Raman Scattering: Temperature and Concentration Effects

Depolarized low-frequency Raman spectra from several cyclodextrin–water solutions have been investigated as a function of both temperature and macrocycle concentration. The differences between the vibrational spectra of solutions and pure water have been discussed, focusing the attention on the modifications of the vibrational bands assigned to the H-bond bending and stretching intermolecular modes of water. These features are in turn related to the structural changes occurring in the H-bonded water molecules allowing us to evince a destructuring effect on the tetrahedral hydrogen bonding arrangements induced in solution by increasing temperature and solute concentration.     

Changes in the Mark–Houwink hydrodynamic volume of chitosan molecules in solutions of different organic acids, at different temperatures and ionic strengths

The objective of this study is to explore the cause(s) of changes in the hydrodynamic volume of chitosan molecules in solutions of different organic acids, at different temperatures and ionic strengths. Change in intrinsic viscosity is used as the parameter to elucidate the causes of changes in the hydrodynamic volume of chitosan molecules in these solutions. Results show that the intrinsic viscosity of chitosan decreases in acetic acid or in malic acid over storage time. These decreases are more pronounced in acetic acid solution than in malic acid solution, more significant in higher temperature than in lower temperature solutions, and greater in solutions without NaCl than in solutions containing higher NaCl. The decrease in intrinsic viscosity can perhaps be attributed to the compounded effects of compaction of the chitosan molecules and/or acidic degradation during storage.     

Conductivity values of tissue culture medium from 20 degrees C to 40 degrees C

Few studies are available that relate conductivity and temperature in solutions commonly used in tissue culture media. The purpose of this paper is to provide equations relating conductivity and temperature (in the range 20 degrees C-40 degrees C) for five solutions: 0.9% saline, MEM (Minimum Essential Media), horse serum, MEM with 1% horse serum, and MEM with 10% horse serum.     

Dielectric changes in hyaluronate solutions at microwave frequencies as a function of concentration,system pH,and temperature

The dielectric response of human umbilical cord hyaluronic acid in various environments has been studied at microwave frquencies using a resonant microwave cavity as a probe. Both the real and imaginary parts of complex dielectric constant and the loss tangent for hyaluronate solutions are obtained by utilizing equations for perturbation of a resonant cavity. Dielectric changes at room temperature have been observed in aqueous solutions of hyaluronic acid as a function of concentration ranging from 0 to 350 mg/ml. The data indicate the existence of ordered phases in hyaluronate solutions at selective concentrations, that is, exhibiting lyotropic-type transitions. Hyaluronate solutions at 1.5 and 3 mg/ml concentrations have been studied at various pH in the range of 6–8 and at constant ionic strength 0.1. A temperature-dependent transition in hyaluronate solution of 120 mg/ml concentration has been observed at physiological temperature. It is shown that this temperature-dependent behavior can be related to the orientational polarizability term in the Debye theory of polar molecules in liquids.     

Rheology of concentrated isotropic and anisotropic xanthan solutions: 3. Temperature dependence

The oscillatory rheology of one rodlike and one semiflexible xanthan sample has been investigated as a function of temperature in the range of xanthan concentrations where the polymer forms a lyotropic liquid crystalline phase in aqueous NaCl solutions. Readily observed changes in the rheological observables at temperatures corresponding to phase boundaries permit construction of the biphasic chimney region of the temperature-composition phase diagram. The chimney region leans toward larger values of the polymer concentration with increasing temperature, presumably as a consequence of a reduction in the effective axial ratio of the helical polymer with increasing temperature. The results permit construction of plots of the rheological observables as a function of polymer concentration at temperatures T in the range 20 相似文献   

Molecular architecture influences the thermally induced aggregation behavior of elastin-like polypeptides

Elastin-like polypeptides are thermally responsive polymers that exhibit phase separation above a transition temperature. The effect of molecular architecture on the temperature responsive behavior of elastin-like polypeptide solutions was investigated by characterization of solutions of three-armed star polypeptides, linear polypeptides, and their mixtures. These biosynthesized polypeptides have precise lengths and amino acid sequences. Transition temperatures were measured as a function of molecular weight and solution concentration and compared to their linear counterparts. Like their linear counterparts, the transition temperature is linearly related to log concentration. A mathematical relationship was used to fit the transition temperature data of different polypeptide lengths to a volume-based concentration using the polymer coil volume. The results of this model suggest that the linear ELP is in a random coil conformation at the transition temperature while the three-armed ELP is in a compact extended coil conformation, consistent with different pathways for aggregation. Solutions containing both trimer and linear constructs have two transition temperatures, further supporting differing aggregation behaviors.     

Ice nucleation in solutions and freeze-avoiding insects-homogeneous or heterogeneous?

This article challenges the common view that solutions and cold-hardy freeze-avoiding insects always freeze by heterogeneous nucleation. Data are presented to show that the nucleation temperatures of a variety of solutions and freeze-avoiding insects are a function of the water volume as described by the data previously published by Bigg in 1953. The article also points out that the relationships between melting point depression and depression of nucleation temperature are different for samples undergoing homogeneous nucleation and those undergoing heterogeneous nucleation. Aqueous solutions and freeze-avoiding insects display a relationship like that of homogeneously nucleated samples. It is also argued that the identity of the "impurities" assumed to cause heterogeneous nucleation in aqueous solutions and insects is obscure and that the "impurities" have features which make their existence rather unlikely.