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Phase-transition polymers show changes in response to external stimuli, such as pH, temperature, light, metabolite, and electric current. Based on the stimuli-induced phase transition, many applications have been developed to improve drug delivery. This paper summarizes various phase-transition polymers and their applications relevant to modulated-drug delivery.
A new thermotropic phase transition, at -30 degrees C and atmospheric pressure, was found to occur in the gel phase of aqueous DPPC dispersions. The Raman spectral changes at this phase transition are similar to those observed in the gel phase of DMPC dispersions at -60 degrees C. The thermotropic phase transition at -30 degrees C is equivalent to the barotropic GII to GIII phase transition observed in DPPC at 1.7 kbar and 30 degrees C. It is shown that the rate of the large angle interchain reorientational fluctuations decreases gradually with decreasing temperature, and that the orientationally disordered acyl chain structure of the GII phase is extended into the GIII phase of DPPC. The interchain interaction, arising from the damping of the reorientational fluctuations, increases with decreasing temperature in the GII gel phase as well as in the GIII gel phase.
We have examined the calorimetric behavior of large liposomes consisting of symmetric saturated chain phosphatidylcholines. Most notably, for systems made in solutions containing solute (e.g., NaCl, glucose, etc.) there was an additional major endotherm just below the main phase transition temperature. The new endotherm was found to represent a population of lipid whose main phase transition was shifted to lower temperature due to an induced osmotic stress across the membrane. Absent for isoosmotic systems, the osmotic stress was created when the liposome internal volume decreased, a consequence of the Lbeta' (gel) to Pbeta' (rippled) phase transition. That is, rippling of the membrane caused vesicle volume to decrease (> or = 28%) and because the free flow of water outward was restricted by solute, an osmotic gradient was created where none had existed before. The distribution of enthalpy between the new shifted Tm and the expected Tm correlated with the percent of lipid in the outer bilayer and it was concluded that only the outer bilayer sensed the induced stress. Internalized liposome structures were shielded, thus explaining the persistence of the expected Tm in preparations made in solute. The shift in Tm (deltaTm) was discrete and linearly dependent upon lipid chain length for the PC series di-17:0 (deltaTm approximately 1.4 degrees C) through di-20:0 (deltaTm approximately 0.6 degrees C), suggesting a structural change (i.e., lipid packing/orientation) was involved. Although freeze-fracture electron microscopy of stressed and unstressed bilayers revealed no differences in ripple periodicity there were differences in surface features and in vesicle shape. The fact that this phenomenon has gone unnoticed for MLVs is probably due to the fact that these systems are known to exclude solute and thus exist under osmotic compression.
The main phase transition of phospholipid bilayers is a property expressed by the order-disorder conformational change of the lipid tails. Nevertheless, with ionizable phospholipids, changes in the surface charge have large effects on the membrane properties. The free energy of a charged phospholipid membrane depends on the degree of ionization, area per phospholipid molecule, and the temperature. Here, the effect of surface electrostatic charges on the temperature and the enthalpy of the main phase transition of dimyristoylphosphatidic acid vesicle membranes is analyzed. A simple equation is presented that describes the relationship among the surface charge density, the phase-transition temperature, the surface area ratio between solid and liquid membranes, and the excess enthalpy. The theory indicated that the pH-induced shift in the excess enthalpy is attributable to the change in the surface area ratio between the solid and liquid membranes.
The proteolipid apoprotein from bovine white matter has been reported to increase the phase transition temperature of dimyristoyl phosphatidylcholine, in contrast to a proteolipid apoprotein fraction from human myelin, called lipophilin, which decreases the enthalpy without altering the phase transition temperature. Since these results lead to different conclusions concerning the structure and amount of boundary lipid surrounding these proteins, the effects of the two proteins on the phase transition of dimyristoyl phosphatidylcholine were compared. Neither protein has any effect on the phase transition temperature, regardless of the method of delipidation of the protein, the amount of residual lipid, the method of incorporation into vesicles, or heating rates used for differential scanning calorimetry. However, a higher melting component was observed when decomposition of the lipid to lysophosphatidylcholine had occurred. Addition of as little as 6% of the decomposition products of dimyristoyl phosphatidylcholine, lysodimyristoyl phosphatidylcholine and myristic acid, is enough to produce a higher-temperature peak. The intensity of this peak increases with increasing protein concentration similar to the reported result on the bovine white matter proteolipid. The question as to whether the protein-induced decrease in enthalpy is due to boundary lipid or entrapment of lipid in protein aggregates was also addressed by studying the appearance of the intramembranous protein particles by freeze-fracture electron microscopy at temperatures above and below the phase transition and between the premelt and main transitions. The protein is randomly dispersed above the phase transition. At low concentrations, below the phase transition, it clusters, forming particle-free and particle-rich areas, but does not aggregate. At higher concentrations it is randomly dispersed below the premelt and main transition but is clustered between the premelt and main transition. Since the protein is more randomly dispersed above the transition than below, the reduction in enthalpy of the freezing transition was compared to that of the melting transition and was found to be identical, suggesting that the withdrawal of lipid from the phase transition is probably not due to lipid entrapment but due to the formation of a boundary lipid interface between the protein and the bulk lipid.
The phase transition of dimyristoylphosphatidylglycerol (DMPG) bilayers has been studied by measurements of light scattering under high electric field pulses. Midpoints of phase transitions have been identified by a clear discontinuity of field induced relaxation amplitudes. We show that the phase transition of DMPG suspensions in monovalent salt is virtually independent of the electric field strength up to approx. 35 kV/cm. A shift of the lipid phase by electric field pulses has been observed, however, for DMPG suspensions in the presence of Ca2+ ions. DMPG suspensions exhibit a jump of the phase transition temperature from 17 degrees C at Ca/DMPG molar ratios r less than 1/7 to 32 degrees C at r greater than 1/7. Field pulses of 60 to 100 microseconds applied to DMPG suspensions with Ca2+ at r greater than 1/7 induce discontinuities of relaxation amplitudes in the temperature range 15 to 22 degrees C in addition to the 'standard' one at 32 degrees C, when the electric field strength is above 15 kV/cm. These results indicate that electric field pulses induce a transition from the phase formed at 'high' Ca(2+)- to the one formed at 'low' Ca(2+)-ion concentrations. Our results are consistent with a dissociation field effect on Ca(2+)-lipid complexes which drives the phase transition.
Quantum phase transitions in mesoscopic systems are studied. It is shown that the main features of phase transitions, defined for infinite number of particles, N--> infinity, persist even for moderate N approximately 10. A Landau analysis of first order transitions is done and a "critical" exponent at the spinodal point is defined. Two order parameters are introduced to distinguish first from second order transitions. Applications to atomic nuclei, molecules, atomic clusters, and finite polymers are mentioned. Experimental evidence in atomic nuclei is presented.
Crystals of phase II K2Cr2O7, potassium dichromate, space group P1 , grown from aqueous solution undergo a first-order transition to phase I, space group reportedly P21/n, at a phase-transition temperature, TPT, of 544 (2) K on first heating; the corresponding transition on cooling is at 502 (2) K. The endotherm on subsequent heatings occurs reproducibly at TPT = 531 (2) K. Mass loss between ca 531 and 544 K, identified as included water, is rapid and continues more slowly to higher temperatures for a total loss of ca 0.20%. The higher TPT on first heating is associated with the increasing pressure of superheated water occupying inclusion defects. The latent diagonal glide plane in phase II allows the structure of phase I to be inferred. The triclinic structure at 296 K has been independently redetermined. Normal probability analysis shows high consistency between the resulting and previous atomic coordinates, but with uncertainties reduced by a factor of ca 2. The earlier uncertainties are systematically underestimated by a comparable factor. The structure of phase IIb, space group A2/a on transposing axes, was determined at ca 300 K by Krivovichev et al. [Acta Cryst. (2000), C56, 629-630]. The first-order transition between phases I and II arises from the ca 60 degrees relative rotation of terminal O atoms in each tetrahedron as the n glide plane is gained or lost. A transition between phases IIb and I, also of first order, is likely but not between phases II and IIb. An intermediate phase may exist between phases IIb and I.
We introduce a simple growth model for a driven interface in random media, exhibiting a smoothing (roughening) transition as well as a pinning-depinning transition in a nonequilibrium (1+1)-dimensional system. At both transition points, the scaling exponents belong to the directed percolation universality class. The rough interface at the pinning-depinning transition point belongs to the quenched Kardar-Parisi-Zhang universality class. The two transitions are second order phase transitions. We also introduce a modified growth model exhibiting the pinning-depinning transition. In the modified model, the pinning-depinning transition is a first order phase transition in the directed percolation universality class.
The kinetics of the phase transition between the (2 x 2) and (p x square root[3])-Bi structures on Au(111) was investigated using electrochemical methods and time-resolved surface X-ray diffraction. The temporal changes in the current value and the diffracted X-ray intensity that originated from the (2 x 2)-Bi overlayer were monitored during the phase transitions at various over-potentials. The phase transition models and kinetics parameters were deduced from each of the current and X-ray intensity transient curves. We also carried out comparative studies of the phase transition from the structural and electrochemical points of view. For the (p x square root[3]) --> (2 x 2) phase transition, the phase transition models determined by the X-ray and electrochemical measurements were a surface-diffusion controlled instantaneous nucleation-growth process and a Langmuir process, respectively. For the reverse transition, the phase transition models determined by X-ray and electrochemical measurements were a Langmuir adsorption process and a surface diffusion controlled nucleation-growth process, respectively. Our results revealed that the current transient curve does not always reflect the phase transition model in both cases and suggest that a structural analysis is fundamental in the phase transition studies. The disagreements between the phase transition models and their mechanisms are discussed.
Phase transitions in bilayers and monolayers of various synthetic phospholipids with different chain lengths as well as different polar head groups were studied by differential scanning calorimetry or with the film balance technique, respectively. With the film balance, area versus temperature curves (isobars) were recorded at different surface pressures. The monolayer phase transition from the fluid-condensed to the fluid-expanded phase is shifted towards higher temperature when the lateral pressure in the monolayer is increased. The temperature dependence of the equilibrium pressure as well as the magnitude of the area change at the transition depends only on the nature of the phospholipid head group and not on the chain length of the hydrocarbon chains of the lipid. Phospholipids with strong intermolecular attractive interactions between the head groups show low values for dpi/dTm and for the area change, deltaf, whereas phospholipids with negatively charged head groups without intermolecular attractive forces exhibit higher values for dpi/dTm and deltaf. The shift of the monolayer phase transition temperature when increasing the chain length of the lipid is almost identical to the shift in Tm observed for the bilayer system of the same phospholipids. A comparison of monolayer and bilayer systems on the basis of the absolute value of the molecular area of the phospholipid in the bilayer gel phase and the change in area at the bilayer and monolayer transition leads to the following conclusions. The behaviour of the bilayer system is very similar to that of the respective monolayer system at a lateral pressure of approx. 30 dyne/cm, because at this pressure the absolute area and the area change in both systems are the same. Further support for this conclusion comes from the experimental finding that a lateral pressure of 30 dyne/cm the shift in Tm due to the increase in charge when the methyl ester of phosphatidic acid is investigated is the same for the bilayer and the monolayer system.
The influence of the addition of Ca2+ on the phase behaviour of vesicles, composed of dipalmitoylphosphatidylcholine (DPPC) and dimyristoylphosphatidic acid (DMPA) in a ratio of 4 to 1, has been investigated by means of turbidity measurements. As expected one single phase transition for the mixed phospholipids was observed in the absence of Ca2+. Passing through the temperature range of this transition after the addition of Ca2+, conditions appeared to favor fusion of the vesicles. A possible reason for this is that during the transition Ca2+ may permeate through the vesicle membranes and gain access to the inside DMPA binding sites. Therefore it is not unambiguously possible to determine phase transition temperatures from the turbidity changes that occur under these conditions. However, when within the temperature range of the phase transition of the mixed phospholipids the influence of Ca2+ addition to the vesicles was recorded isothermally, at each temperature separately, the final plot of turbidity versus temperature turned out to be far less confused by fusion events and adopted the form of two separate phase transitions. The temperatures at which these two transitions occur closely resemble the phase transition temperatures that may be observed in the absence of Ca2+ for DMPA and DPPC alone, 39 degrees C and 43 degrees C respectively. The results of this study suggest that when Ca2+ has only access to the outside of the vesicle membranes it may segregate the neutral and the acidic phospholipids into separate domains, both domains adopting their proper phase condition at the actual temperature.(ABSTRACT TRUNCATED AT 250 WORDS)
Highly correlated electronic systems--such as transition-metal oxides that are doped Mott insulators--are complex systems which exhibit puzzling phenomena, including high-temperature superconductivity and colossal magnetoresistivity. Recent studies suggest that in such systems collective electronic phenomena are important, arising from long-range Coulomb interactions and magnetic effects. The qualitative behaviour of these systems is strongly dependent on charge filling (the level of doping) and the lattice constant. Here we report a time-efficient and systematic experimental approach for studying the phase diagrams of condensed-matter systems. It involves the continuous mapping of the physical properties of epitaxial thin films of perovskite manganites (a class of doped Mott insulator) as their composition is varied. We discover evidence that suggests the presence of phase boundaries of electronic origin at room temperature.
The effect of three anions, Cl-, Br- and I-, on the phase transitions of dipalxnitoylphosphatidyicholine (DPPC) was measured. Main phase transition was modestly affected by these anions in the salt concentration range 0.2 M. For Cl- and Br- the temperature of main phase transition was lower (by about 0.5 degrees C), its half-width modestly larger and enthalpy practically unchanged, all three parameters were altered to a much larger deuce. Main phase transition temperature was 1.5 degrees C lower and the peak hall-width significantly smaller. These changes were not accompanied by any alteration in main phase transition enthalpy. Iodide shifted the pretransition temperature toward lower values and increased its half-width to such an extent that at concentrations above 100 mM it was practically undetectable. Besides cations, the presence of anions also has a distinct effect on lipid bilayer interface properties.
The relation between thermodynamic phase transitions in classical systems and topology changes in their configuration space is discussed for a one-dimensional, analytically tractable solid-on-solid model. The topology of a certain family of submanifolds of configuration space is investigated, corroborating the hypothesis that, in general, a change of the topology within this family is a necessary condition in order to observe a phase transition. Considering two slightly differing versions of this solid-on-solid model, one showing a phase transition in the thermodynamic limit and the other not, we find that the difference in the quality or strength of this topology change appears to be insignificant. This example indicates the unattainability of a condition of exclusively topological nature which is sufficient to guarantee the occurrence of a phase transition in systems with nonconfining potentials.
The superconducting phase transition in heavy fermion CeCoIn5 (T(c)=2.3 K in zero field) becomes first order when the magnetic field H parallel [001] is greater than 4.7 T, and the transition temperature is below T0 approximately 0.31T(c). The change from second order at lower fields is reflected in strong sharpening of both specific heat and thermal expansion anomalies associated with the phase transition, a strong magnetocaloric effect, and a steplike change in the sample volume. This effect is due to Pauli limiting in a type-II superconductor, and was predicted theoretically in the mid-1960s.
Transitions between dynamically stable activity patterns imposed on an associative neural network are shown to be induced by self-organized infinitesimal changes in synaptic connection strength and to be a kind of phase transition. A key event for the neural process of information processing in a population coding scheme is transition between the activity patterns encoding usual entities. We propose that the infinitesimal and short-term synaptic changes based on the Hebbian learning rule are the driving force for the transition. The phase transition between the following two dynamical stable states is studied in detail, the state where the firing pattern is changed temporally so as to itinerate among several patterns and the state where the firing pattern is fixed to one of several patterns. The phase transition from the pattern itinerant state to a pattern fixed state may be induced by the Hebbian learning process under a weak input relevant to the fixed pattern. The reverse transition may be induced by the Hebbian unlearning process without input. The former transition is considered as recognition of the input stimulus, while the latter is considered as clearing of the used input data to get ready for new input. To ensure that information processing based on the phase transition can be made by the infinitesimal and short-term synaptic changes, it is absolutely necessary that the network always stays near the critical state corresponding to the phase transition point.
The phase transition of dipalmitoyl lecithin, measured by thermal analysis, was eliminated by the plant sterol, sitosterol, and by the derivatives steryl glucoside and acylated steryl glucoside, which were isolated from soybean lipids.When digitonin was added to dipalmitoyl lecithin-sterol mixtures, in amounts equimolar to sterol, the phase transition of the phospholipid was revealed presumably because of the formation of a sterol complex. When digitonin in molar excess of sterol was added, the endothermic peak disappeared again.