Transport properties of water in hydroxypropyl methylcellulose

The relation between the self-diffusion coefficient, D_self, of water and the free volume hole size, V_h, has been investigated in a hydroxypropyl methylcellulose (HPMC)-water system in the water content range 0.08-0.36 w/w, at room temperature. Furthermore, the thermal properties of the water in the HPMC-water system, as measured with differential scanning calorimetry (DSC) and the tensile storage, E′, and tensile loss, E″, moduli, of the HPMC-water systems, as determined with dynamic mechanical analysis (DMA), have been probed. Pulsed-field gradient nuclear magnetic resonance (PFG NMR) was used to measure the D_self of water and positron annihilation lifetime spectroscopy (PALS) was used to measure the ortho-Positronium (o-Ps) lifetime in the HPMC-water system. The glass transition temperature of the HPMC was found to be reduced by the water to room temperature in the water content range 0.10-0.15 w/w. The relation between ln D_self of water and the inverse free volume hole size of the HPMC-water system was non-linear. Furthermore, the PALS measurements showed that molecular water co-existed with water clusters in the HPMC-water system.     

Cephalexin synthesis using immobilizedXanthomonas citri cells

For continuous production of cephalexin, whole cells ofXanthomonas citri were immobilized by entrapment in polyacrylamide gel and kappa-carrageenan gel. It wasfound that cells immobilized with kappa-carrageenan showed better thermal stability compared to those immobilized by polyacrylamide gel. The cells immobilized with kappa-carrageenan were treated with glutaraldehyde and hexamethylenediamine to prevent gel destruction during prolonged operation. By immobilizing intact cells, the optimal temperature for the synthetic enzyme reaction shifted higher by 8°C and the optimal pH became broader around 6.2 In continuous operation, the immobilized cells retained better operational stability at 25 than at 37°C, and also showed maximal conversion up to 83% at 25°C.     

Wetting behavior of mixtures of water and nonionic polyoxyethylene alcohol

Five binary water + C4Ej mixtures, water + n-C4E0, water + 2-C4E0, water + iso-C4E0, water + n-C4E1, and water + iso-C4E1, were chosen to perform the surface/interfacial tension measurements over the experimental temperature range from 10 to 85 degrees C at the normal pressure by using a homemade pendent drop/bubble tensiometer. The symbol CiEj is the abbreviation of a nonionic polyoxyethylene alcohol CiH(2i+1)(OCH2CH2)jOH. The wetting behavior of the CiEj-rich phase at the interface separating gas and the aqueous phase is systematically examined according to the wetting coefficient resulting from the experimental data of surface/interfacial tensions measurements. For those systems with a lower critical solution temperature, for example, water + n-C6E2, water + n-C4E1, and water + iso-C4E1, a wetting transition from partial wetting to nonwetting is always observed when the system is brought to close to its lower critical solution temperature. On the other hand, to start with a partial wetting CiEj-rich phase, a wetting transition from partial wetting to complete wetting is always observed when the system is driven to approach its upper critical solution temperature. The effect of hydrophobicity of CiEj on the wetting behavior of the CiEj-rich phase at the interface separating gas and the aqueous phase was carefully investigated by using five sets of mixtures: (1) water + n-C4E0, water + n-C5E0, and water + n-C6E0; (2) water + 2-C4E0 and water + 2-C5E0; (3) water + 2-C4E0 and water + n-C4E0; (4) water + n-C4E1, water + n-C5E1, and water + n-C6E1; (5) water + n-C4E0 and water + n-C4E1. The CiEj-rich phase would tend to drive away from complete wetting (or nonwetting) to partial wetting with an increase in the hydrophobicity of CiEj in the binary water + CiEj system. All the wetting behavior observed in the water + CiEj mixtures is consistent with the prediction of the critical point wetting theory of Cahn.     

Phase diagram of electrostricted H2O at surfaces of electrodes at 273-373 K: electric critical point of water.

The equation of state of an open system containing water in an electric field of strength E greater than 108 V m-1 leads to a phase diagram with two-phase and single-phase regions in the Pi,E,T coordinates (=electrostriction pressure). The phases differ by their degree of orientation of H2O molecules in the field. The phase transition is discontinuous with respect to E. The calculation shows that the discontinuity vanishes at the critical point: Pi(c) approximately 0.2 GPa, Ec approximately 109 V m-1 and below 313 K. The thermal effect of the transition is calculated and compared with an experiment at the Hg/aqueous electrolyte interface found in the literature.     

The rheological study of the interaction between alkali metal ions and kappa-carrageenan gels

The rheological change in kappa-carrageenan and agarose gels immersed in alkali metal salt solution was studied by the measurement of longitudinal vibrations. The storage modulus of kappa-carrageenan gel increased remarkably by the immersion, while that of agarose gel did not change so much. The reason of this change in kappa-carrageenan was ascribed to the shielding effect of the electrostatic repulsion of sulfate groups by alkali metal ions. As a result of the shielding, the helical structure was thought to become the densely packed state. The difference of the action between the two groups (Li⁺, Na⁺) and (K⁺, Cs⁺) was discussed from the viewpoint that these ions are either structure makers or breakers for the structure of water.     

Dynamic mechanical analysis

Using dynamic mechanical analysis (DMA) we have studied thermal degradation for a system containing a diglycidyl ether of bisphenol A (DGEBA) and 1,3-bisaminomethylcylohexane (1,3-BAC). The changes of dynamic mechanical properties during thermal degradation indicated a shift of the glass transition temperature (T _g) to higher temperatures and a decrease in the peak value of the dynamic loss factor (tan δ) with an increasing of aging time. The value of dynamic storage modulus (E′) at the rubbery state showed an increase with aging time, whiteE′ at the glassy state only underwent a moderate change with increased thermal degradation. From these results it can be argued that thermal degradation during the stage prior to the onset of the severe degradation involves structural changes in the epoxy system, as further crosslinking and loss of dangling chains in the crosslinked network.     

Beiträge zur Chemie der Pyrrolpigmente, 28. Mitt.: Die thermische Stabilität der geometrischen Isomeren von Bilatrienen-abc

In the equilibrium between the two diastereomeric (Z, Z, Z) and (E, Z, Z) forms of aetiobiliverdine-IV- the former is preferred by about 20kJ/mol. For the thermal isomerization a barrier of 108kJ/mol has to be surmounted—as measured for the latter isomer. A value of 12.4 for the logarithm of the preexponential factor leads to a polar singlet mechanism, which was deduced previously for pyrromethenones and arylmethylenepyrrolinones, but a much more positive activation entropy for the verdinoid system indicates a pronounced delocalisation of charge over the entire conjugated system in the corresponding transition state.

27. Mitt.:H. Falk, K. Grubmayr undF. Neufingerl, Mh. Chem.110, 1027 (1979).     

Thermal diffusion behavior of nonionic surfactants in water

We studied the thermal diffusion behavior of hexaethylene glycol monododecyl ether (C12E6) in water by means of thermal diffusion forced Rayleigh scattering (TDFRS) and determined Soret coefficients, thermal diffusion coefficients, and diffusion constants at different temperatures and concentrations. At low surfactant concentrations, the measured Soret coefficient is positive, which implies that surfactant micelles move toward the cold region in a temperature gradient. For C12E6/water at a high surfactant concentration of w1 = 90 wt % and a temperature of T = 25 degrees C, however, a negative Soret coefficient S(T) was observed. Because the concentration part of the TDFRS diffraction signal for binary systems is expected to consist of a single mode, we were surprised to find a second, slow mode for C12E6/water system in a certain temperature and concentration range. To clarify the origin of this second mode, we investigated also, tetraethylene glycol monohexyl ether (C6E4), tetraethylene glycol monooctyl ether (C8E4), pentaethylene glycol monododecyl ether (C12E5), and octaethylene glycol monohexadecyl ether (C16E8) and compared the results with the previous results for octaethylene glycol monodecyl ether (C10E8). Except for C6E4 and C10E8, a second slow mode was observed in all systems usually for state points close to the phase boundary. The diffusion coefficient and Soret coefficient derived from the fast mode can be identified as the typical mutual diffusion and Soret coefficients of the micellar solutions and compare well with the independently determined diffusion coefficients in a dynamic light scattering experiment. Experiments with added salt show that the slow mode is suppressed by the addition of w(NaCl) = 0.02 mol/L sodium chloride. This suggests that the slow mode is related to the small amount of absorbing ionic dye, less than 10(-5) by weight, which is added in TDFRS experiments to create a temperature grating. The origin of the slow mode of the TDFRS signal will be tentatively interpreted in terms of a ternary mixture of neutral micelles, dye-charged micelles, and water.     

A DSC Study of Thermal Transitions of Apple Systems at Several Water Contents

The dependence of phase transitions in apple systems at several different water contents has been studied by using differential scanning calorimetry (DSC). The pre-cooled samples with high water fractions show a small but distinct thermal effect at low temperature before the final melting of the ice. The samples with low water content show a second order type transition, characterised by a temperature which increases with decreasing water content. The temperature/composition behaviour is reported in the form of the so-called 'supplemented' state diagram, including the solid/liquid coexistence boundaries and the extrapolated glass transition curve. This diagram contributes towards understanding the transformations encountered during the temperature process of partially dried samples of apple. An interpretation is presented about the existence of phase-segregated regions, which could give the observed thermal effects at low temperatures. This revised version was published online in July 2006 with corrections to the Cover Date.     

The pressure- and temperature-induced wetting transitions in the binary water + ethylene glycol monoisobutyl ether mixture

A homemade pendent drop/bubble tensiometer is applied to perform the surface/interfacial tension measurements for the binary water + ethylene glycol monoisobutyl ether (iso-C4E1) mixture over the temperature range from 25 to 150 degrees C and over the pressure range up to 100 bar. The symbol C(i)E(j) is the abbreviation of a nonionic polyoxyethylene alcohol C(i)H(2i+1)(OCH2CH2)(j)OH. The wetting behavior of the iso-C4E1-rich phase at the surface of the aqueous phase is systematically examined according to the wetting coefficient determined from the experimental results of surface/interfacial tensions. It is found that the iso-C4E1-rich phase exhibits a sequence of wetting transitions, nonwetting --> partial wetting --> complete wetting, at the water surface in the water + iso-C4E1 system along with increasing temperature. On the other hand, the iso-C4E1-rich phase undergoes a wetting transition from partial wetting to nonwetting at the surface of the aqueous phase by increasing the system pressure at a fixed temperature near the lower critical solution temperature (LCST) of the closed-loop miscibility gap in the water + iso-C4E1 system.     

Design of a rate- and time-programming drug release device using a hydrogel: pulsatile drug release from kappa-carrageenan hydrogel device by surface erosion of the hydrogel

We have found that a repetitive pulsatile drug release with a certain time interval is observed from a monolithic hydrogel device by surface erosion of the hydrogel. As a model system of pulsatile drug release, dibucaine hydrochloride and kappa-carrageenan hydrogel were chosen as a drug and a device, respectively. Electrostatic interactions between dibucaine hydrochloride and kappa-carrageenan polymer segments are strong, since dibucaine hydrochloride is positively charged and each disaccharide repeating unit of kappa-carrageenan chains has one sulfate group. Dibucaine hydrochloride was loaded into the hydrogel by immersing dry kappa-carrageenan hydrogel disks in a dibucaine hydrochloride solution for 24 h. The pulsed release of dibucaine hydrochloride from the device was observed every 50 min between 30 and 250 min after the release starts. The weight of kappa-carrageenan hydrogel decreases in an oscillatory manner with time in distilled water. The oscillatory changes observed in the hydrogel weight in distilled water are considered to be caused by influx and efflux of water molecules into and from the surface and core of the hydrogel and by polymer liberation from the hydrogel. This phenomenon was well explained by our kinetic model [Colloids and Surfaces B 8 (1996) 93-100]. The time interval between pulses observed in drug release coincides with that observed in the oscillatory weight change of the hydrogel. From these, it was concluded that the pulsatile release of dibucaine hydrochloride from the device was caused by the pulsatile liberation of swollen kappa-carrageenan hydrogel from the surface of the device.     

Influence of temperature and alkyl chain length on phase behavior in Langmuir monolayers of some oxyethylenated nonionic surfactants

We study the surface phase behavior in Langmuir monolayers of a series of nonionic surfactants of the general formula CnE1 with n=14, 16, and 18 by film balance and Brewster angle microscopy (BAM) over a wide range of temperatures. A cusp point followed by a pronounced plateau region in the pressure-area (pi-A) isotherms indicates a first-order phase transition in the coexisting state between a lower density liquid expanded (LE) phase and a higher density liquid condensed (LC) phase at the air-water interface. The formation of bright two-dimensional (2D) LC domains in a dark background visualized by BAM further confirms this observation. In addition to the cusp point at the onset of the LE-LC coexistence state, another cusp point followed by a small plateau is observed for the C14E1 and C18E1 monolayers, indicating a second phase transition between two condensed phases of different compressibility and tilt orientation of the molecules. This unusual two-step phase transition is explained by the Ostwald step rule. The C16E1 and C18E1 monolayers show a kink in their respective isotherms, after which the surface pressure increases steeply with only a little decrease in the molecular area, suggesting that the molecules undergo a transition from a tilted to an almost vertical orientation with respect to the water surface. The thermodynamic parameters for the condensation of the molecules in the LE-LC coexistence state were calculated by employing the 2D Clapeyron equation. The temperature coefficient of the critical surface pressure dpi(c)/dT values shows a decreasing trend from C14E1 to C18E1, suggesting that the condensation process becomes less and less prone to thermal perturbation as the chain length increases. For all the amphiphiles, the DeltaH values are found to be negative, suggesting an exothermic nature of condensation. The negative DeltaS values obtained from the relation DeltaH/T probably come from the restriction on the rotational and translational motion of the molecules constrained in a confined area in the LE-LC transition region.     

Effect of sol-gel transition on shear-induced drop deformation in aqueous mixtures of gellan and kappa-carrageenan

In this work, we present an experimental methodology to investigate the dynamics under shear flow of a drop that is gelling as a consequence of a temperature quench. The experiments were carried out on the system water/gellan/kappa-carrageenan in the biphasic region of the phase diagram, the gellan-rich phase being used as the dispersed phase. Gelation was brought about by lowering the temperature during flow after steady state drop deformation had been reached. Simple shear flow was applied by using a parallel plate apparatus equipped with optical microscopy and image analysis, which made it possible to monitor drop shape evolution before, during, and after gelation. The onset of gelation trapped drop deformation, thus producing anisotropic particles. The fingerprint of gelation was the simultaneous tumbling of the drops, which rotated as rigid ellipsoids under the action of shear flow. Interfacial tension between the two equilibrium phases was determined at different times during the temperature quench by analyzing drop retraction upon cessation of flow. Up to gelation, no significant change was observed in the measured values.     

Thermal analysis of protein–metallic ion systems

Advanced thermal analysis methods, such as temperature modulated DSC (differential scanning calorimetry) and quasi-isothermal TMDSC were used to analyze the protein–metallic ion interactions in silk fibroin proteins. The precise heat capacities were measured and theoretically predicted in this study. To remove bound water and simplify the system, a thermal cycling treatment through both standard DSC and TMDSC was used to detect the underlying heat capacity and reveal the phase transitions of the silk–metallic salts system. Results show that K⁺ metallic salts play the role of plasticizer in silk fibroin proteins, which reduces the glass transition (T_g) of the pure silk protein and negatively affects its structural thermal stability. On the other hand, Ca²⁺ metallic salts act as an anti-plasticizer, and increase the glass transition and the thermal stability of the silk protein structure. This indicates that the thermal analysis methods offer a new pathway to study protein–metallic ion systems, yielding very fruitful information for the study of protein structures in the future.     

Effect of kappa-carrageenan on the properties of poly(N-vinyl pyrrolidone)/kappa-carrageenan blend hydrogel synthesized by γ-radiation technology

A series of hydrogels in the form of rods were prepared from kappa-carrageenan (KC) and poly (N-vinyl pyrrolidone) (PVP) by gamma radiation with ⁶⁰Co γ source at room temperature. The properties of the prepared hydrogels, such as the gel strength, gel fraction and swelling behavior were investigated. Incorporation of KC into the PVP/water system increased obviously the gel strength and equilibrium degree of swelling (EDS) of PVP hydrogel. The experimental analyses showed that the crosslinking reaction of PVP was quicker than the degradation of KC at a low dose (less than 30 kGy), and the degradation of KC was inhibited in the PVP/KC mixture system. So an interpenetrating polymer network (IPN) hydrogel composed of PVP (a chemical crosslinking network) and KC (a physical crosslinking network) was proposed here. The existence of different classes of water in this IPN system was shown by water melting curves using DCS.     

Thermal induced phase separation of E7/PMMA PDLC system

The phase behaviour of thermoplastic polymer-dispersed liquid crystal system is studied with particular emphasis on the various transitions that occur within the system. The extent of plasticization of the polymer(polymethyl methacrylate) by the low molecular weight liquid crystal(E7) along with the several transitions of theLC(Liquid Crystal) are determined by modulated DSC. Optical microscopy was used to construct the temperature versus composition phase diagram. Our study indicates the existence of a limiting temperature of 40°C around which the PMMA matrix turns glassy irrespective of the initial composition within the phase separated region, suggesting the intersection of the glass transition curve with the coexistence curve. A slight depression of theN-I(Nematic to Isotropic) transition of theLC is observed with increasing composition of PMMA whereas theS-M(Smectic to Nematic) transition and theT _g (Glass transition temperature) of theLC remain unaffected. The one phase mixture remains isotropic until phase separation at a lower temperature where theLC rich domains become nematic. The growth ofLC rich domains is studied as a function of temperature and time.     

Sol–gel transition of methylcellulose in phosphate buffer saline solutions

The effect of phosphate buffer saline (PBS) on the thermoreversible sol–gel transition of methylcellulose has been systematically investigated with turbidimetric, microcalorimetric, and rheological methods. In the presence of PBS, the cloud points in the sol–gel transition and the clear points in the gel–sol transition shift to lower temperatures with increasing PBS content. This salting-out effect is considered to be due to the competition between salts and methylcellulose for water molecules involved in the formation or destruction of cagelike water structures. The microcalorimetric studies prove that with increasing PBS content, the endothermic peak temperature decreases, whereas the enthalpy and entropy changes of the sol–gel transition increase. The rheological studies show that the addition of PBS favors the sol–gel transition, but the gel strength is almost independent of the PBS content, indicating an effect of adding salt equivalent to that of increasing the temperature. The results obtained from the rheological, microcalorimetric, and turbidimetric measurements are consistent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1849–1860, 2004     

Effusive molecular beam study of C2H6 dissociation on Pt(111)

The dissociative sticking coefficient for C2H6 on Pt(111) has been measured as a function of both gas temperature (Tg) and surface temperature (Ts) using effusive molecular beam and angle-integrated ambient gas dosing methods. A microcanonical unimolecular rate theory (MURT) model of the reactive system is used to extract transition state properties from the data as well as to compare our data directly with supersonic molecular beam and thermal equilibrium sticking measurements. We report for the first time the threshold energy for dissociation, E0 = 26.5 +/- 3 kJ mol(-1). This value is only weakly dependent on the other two parameters of the model. A strong surface temperature dependence in the initial sticking coefficient is observed; however, the relatively weak dependence on gas temperature indicates some combination of the following (i) not all molecular excitations are contributing equally to the enhancement of sticking, (ii) that strong entropic effects in the dissociative transition state are leading to unusually high vibrational frequencies in the transition state, and (iii) energy transfer from gas-phase rovibrational modes to the surface is surprisingly efficient. In other words, it appears that vibrational mode-specific behavior and/or molecular rotations may play stronger roles in the dissociative adsorption of C2H6 than they do for CH4. The MURT with an optimized parameter set provides for a predictive understanding of the kinetics of this C-H bond activation reaction, that is, it allows us to predict the dissociative sticking coefficient of C2H6 on Pt(111) for any combination of Ts and Tg even if the two are not equal to one another.     

Influence of kappa-carrageenan gel structures on the diffusion of probe molecules determined by transmission electron microscopy and NMR diffusometry

The influence of the microstructures of different kappa-carrageenan gels on the self-diffusion behavior of poly(ethylene glycol) (PEG) has been determined by nuclear magnetic resonance (NMR) diffusometry and transmission electron microscopy (TEM). It was found that the diffusion behavior was determined mainly by the void size, which in turn was defined by the state of aggregation of the kappa-carrageenan. The kappa-carrageenan concentration was held constant at 1 w/w%, and the aggregation was controlled by the amount of potassium and/or sodium chloride and, for samples containing potassium, also by the cooling rate. Gels containing potassium formed microstructures where kappa-carrageenan strands are rather evenly distributed over the image size, while sodium gels formed dense biopolymer clusters interspersed with large openings. In a gel with small void sizes, relatively slow diffusion was found for all PEG sizes investigated. Extended studies of the self-diffusion behavior of the 634 g mol(-)(1) PEG showed that there is a strong time dependence in the measured PEG diffusion. An asymptotic lower time limit of the diffusion coefficient was found in all gels when the diffusion observation time was increased. According to the ratio, D/D(0), where D(0) is the diffusion coefficient in D(2)O and D is the diffusion coefficient in the gels, the gels could be divided into three classes: small, medium, and large voids. For quenched kappa-carrageenan solutions with salt concentrations of 20 mM K(+), 100 mM K(+), or 20 mM K(+)/200 mM Na(+) as well as slowly cooled solutions with only 20 mM K(+), D/D(0) ratios between 0.18 and 0.29 were obtained. By quenching a kappa-carrageenan solution with 100 mM K(+), the D/D(0) was 0.5, while D/D(0) ratios between 0.9 and 1 were obtained in a quenched solution with 250 mM Na(+) and slowly cooled samples with 20 mM K(+)/200 mM Na(+) or 250 mM Na(+).     

Studies on the mechanisms of gelation of kappa-carrageenan and agarose

It has been established that hydrogen bonds control both gelation and helix formation completely in the case of agarose and partially in the case of kappa-carrageenan, the major role belonging in the latter case to the interactions of a polysaccharide with metal ions. Na⁺ and K⁺ ions form contact ion pairs with sulphate groups of kappa-carrageenan. It is supposed that an increase in the number of contact ion pairs together with association of macromolecules having unordered conformation, a decrease in the second virial coefficient, and a decrease in the refraction index increment (i.e., an increase in the solvation degree of dissolved particles) is a necessary condition for forming the kappa-carrageenan gel netwórk. A sufficient condition of kappa-carrageenan gelation is the intermolecular coordination binding of ions such as K⁺ ions, promoting gelation. The coil-to-helix transition of the polysaccharide is controlled by shielding the charge of kappa-carrageenan-sulphate groups. Hydrophobic interactions proved to be unessential for gelation of either agarose or kappa-carrageenan.