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Mobility in thin polymer films ranging from local segmental motion, Rouse modes to whole chain motion: a coupling model consideration.

Large increases of mobility of local segmental relaxation observed in polymer films as the film thickness is decreased, as evidenced by decreases of the glass temperature, are not found for relaxation mechanisms that have longer length scales including the Rouse relaxation modes and the diffusion of entire polymer chains. We show that the coupling model predictions, when extended to consider polymer thin films, are consistent with a large increase of the mobility of the local segmental motions and the lack of such a change for the Rouse modes and the diffusion of entire polymer chains. There are two effects that can reduce the coupling parameter of the local segmental relaxation in thin films. One is the chain orientation that is induced parallel to the surface when the film thickness h becomes smaller than the end-to-end distance of the chains and the other is a finite-size effect when h is no longer large compared to the cooperative length scale. Extremely thin ( approximately 1.5 nm) films obtained by intercalating a polymer into layered silicates have thickness significantly less than the cooperative length scale near the bulk polymer glass transition temperature. As a result, the coupling parameter of the local segmental relaxation in such thin films is reduced almost to zero. With this plausible assumption, we show the coupling model can explain quantitatively the large decrease of the local segmental relaxation time found experimentally.

Journal Article↗

Oxidation of a glucose polymer during exercise: comparison with glucose and fructose.

The purpose of this study was to compare the oxidation of 13C-labeled glucose, fructose, and glucose polymer ingested (1.33 g.kg-1 in 19 ml.kg-1 water) during cycle exercise (120 min, 53 +/- 2% maximal O2 uptake) in six healthy male subjects. Oxidation of exogenous glucose and glucose polymer (72 +/- 15 and 65 +/- 18%, respectively, of the 98.9 +/- 4.7 g ingested) was similar and significantly greater than exogenous fructose oxidation (54 +/- 13%). A transient rise in plasma glucose concentration was observed with glucose ingestion only. However, plasma insulin levels were similar with glucose and glucose polymer ingestions and significantly higher than with water or fructose ingestion. Plasma free fatty acid and glycerol responses to exercise were blunted with carbohydrate ingestion. However, fat utilization was not significantly different with water (82 +/- 14 g), glucose (60 +/- 3 g), fructose (59 +/- 11 g), or glucose polymer ingestion (60 +/- 8 g). Endogenous carbohydrate utilization was significantly lower with glucose (184 +/- 22 g), glucose polymer (187 +/- 31 g), and fructose (211 +/- 18 g) than with water (239 +/- 30 g) ingestion. Plasma volume slightly increased with water ingestion (7.4 +/- 4.5%), but the decrease was similar with glucose (-7.6 +/- 5.1%) and glucose polymer (-8.2 +/- 4.6%), suggesting that the rate of water delivery to plasma was similar with the two carbohydrates.(ABSTRACT TRUNCATED AT 250 WORDS)

Adult↗

Rapid and efficient vascular transport of arginine polymers inhibits myointimal hyperplasia.

BACKGROUND: We recently discovered that short polymers of arginine efficiently translocate across the cytoplasmic membrane independent of the basic amino acid transporter. We evaluated the kinetics and biological effects of heptamers of L-arginine and D-arginine (L-R7 and D-R7, respectively) in vascular cells. We assessed the effects of these peptides on the NO synthesis pathway and vascular cell proliferation. METHODS AND RESULTS: Human umbilical vein endothelial cell and rabbit vascular segments were incubated in medium containing biotin-labeled L-R7 or D-R7. Both polymers rapidly translocated through the vessel wall and into the vascular cells in a dose- and time-dependent fashion. At a dose of 10 micromol/L for 30 minutes, 100% of the endothelial cells showed evidence of cytoplasmic and nuclear localization of the peptides. To evaluate the biological effects of the polymer translocation on myointimal formation, rabbit jugular vein segments were incubated with polymers (10 micromol/L, 30 minutes) or vehicle before arterial interposition grafting. Planimetric measurement 28 days after surgery revealed that L-R7 and D-R7 substantially reduced myointimal formation compared with the control condition (intima/media ratio: control 1. 50.5, L-R7 0.40.2, and D-R7 0.80.2; P:<0.05). Furthermore, basal nitrate and nitrite production from L-R7-treated grafts was significantly higher than that from both control and D-R7-treated veins. Studies in vitro of cultured vascular smooth muscle cells revealed that both polymers also exhibit an NO-independent inhibition of vascular smooth muscle cell proliferation. CONCLUSIONS: Short polymers of arginine have the unique ability of vascular cell translocation, and they also have direct biological effects. These attributes are potentially useful in treating myointimal hyperplasia.

Animals↗

Inhibition of experimental vasospasm in rats with the periadventitial administration of ibuprofen using controlled-release polymers.

BACKGROUND AND PURPOSE: The chronic phase of vasospasm after an aneurysmal subarachnoid hemorrhage may be mediated in part by early leukocyte-endothelial cell interactions. Ibuprofen is an anti-inflammatory agent that inhibits expression of certain cell adhesion molecules and therefore disrupts leukocyte-endothelial cell interactions. Its systemic administration, however, has dose-limiting side effects. We evaluated the effect of the periadventitial delivery of ibuprofen using controlled-release polymers in the rat femoral artery model of chronic posthemorrhagic vasospasm. METHODS: Before the animal studies, the release pharmacokinetics of the ibuprofen-loaded ethylene-vinyl acetate polymers were determined in vitro. Subsequently, the femoral arteries (n=266) of Fischer 344 rats (n=133) were enclosed in latex pouches bilaterally. In the toxicity study (n=15 rats), the animals were randomized into 5 dose groups in which 0%-, 10%-, 20%-, 30%-, or 50%-loaded ibuprofen polymers were evaluated. In the efficacy study, the animals were randomized into 5 time groups in which 50%-loaded ibuprofen polymers were inserted at 0 (n=58 rats), 6 (n=16), 12 (n=13), 24 (n=11), or 48 hours (n=12) after blood injection into the pouch. The rats were killed 12 days after blood exposure, at the time of maximal vasospasm in this model. Vasospasm was expressed as percent lumen patency. To evaluate the effect of ibuprofen on leukocyte migration, 8 rats were randomized into 2 groups. Macrophages and granulocytes were stained by immunohistochemistry with the use of a mouse OX-41 monoclonal antibody and counted in the periadventitial space 24 hours after blood exposure. RESULTS: In vitro pharmacokinetics showed that the 50%-loaded ibuprofen polymer released its total drug load over a 12-day period. In the toxicity study, a nonsignificant arterial vasodilatation with ibuprofen treatment was seen at higher doses, and no deleterious effects were noted on the vessel wall histologically. In the efficacy study, ibuprofen treatment resulted in significant vasospasm inhibition when treatment was initiated at 0 hour (73.7+/-4.9% versus 94.5+/-3.3% [mean+/-SEM percent lumen patency]; P<0.001) and 6 hours (69.2+/-5.7% versus 98.0+/-3.9%; P=0. 002) after blood exposure, but not at 12, 24, or 48 hours. Leukocyte immunohistochemistry showed that ibuprofen treatment resulted in significantly lower periadventitial macrophage and granulocyte counts of 25.0+/-3.9 cells per high-powered field compared with counts of 140.5+/-18.2 cells per high-powered field in the untreated vessels (P<0.001). CONCLUSIONS: The periadventitial, controlled release of ibuprofen from surgically implanted polymers significantly inhibits chronic posthemorrhagic vasospasm in this model when treatment is initiated within 6 hours of blood exposure. Vasospasm inhibition with ibuprofen correlates with a significant decrease in the number of macrophages and granulocytes in the periadventitial space. This study supports the hypothesis that inflammation mediates in part the chronic phase of posthemorrhagic vasospasm and suggests a potential alternative treatment for this condition.

Animals↗

Self-association and micelle formation of biodegradable poly(ethylene glycol)-poly(L-lactic acid) amphiphilic di-block co-polymers.

Di-block co-polymers of poly(ethylene glycol)-poly(L-lactic acid) (PEG-PLLA) were prepared by ring-opening polymerization, and their self-association and micelle formation were investigated. The block co-polymers have the same block length of the hydrophilic PEG segment (Mn = 2000), but different chain lengths of the hydrophobic PLLA segment (Mn = 700, 1000 and 1300, respectively). The di-block co-polymers synthesized were characterized by GPC, 1H-NMR, TGA and DSC. The critical micelle concentration (CMC) of the PEG-PLLA micelles was determined at various temperatures (5-45 degrees C) using a dye absorption technique involving fluorescence spectrophotometry with pyrene as a probe to monitor the change in the polarity of the microenvironment in the micelle. An increase in the molecular weight of the hydrophobic block decreases the CMC. The partition coefficients of pyrene between the micellar and aqueous phases range from 0.68 x 10(4 )to 1.76 x 10(4), depending on the PLLA content in the block co-polymers. An Arrhenius plot of ln(CMC) versus 1/T exhibited an almost constant CMC at low temperatures (<35 degrees C), followed by an increase of the CMC at higher temperatures (>35 degrees C). The increase of the CMC with temperature indicates the increase of the mobility of the hydrophobic PLLA core. These results were confirmed by 1H-NMR measurements. The micelle size and size distribution were determined by dynamic light scattering (DLS), and were in the range of 78-92 nm. A spherical micelle shape was confirmed by transmission electron microscopy. These results indicate that the CMC and the thermal characteristics of the core-forming segment of the block co-polymer play an important role in the properties of the polymer micelles used for drug delivery.

Biodegradation, Environmental↗

Calculation of solvation interaction energies for protein adsorption on polymer surfaces.

Of the interactions that govern protein adsorption on polymer surfaces, solvation interactions (repulsive hydration and attractive hydrophobic interactions) are thought to be among the most important. The solvation interactions in protein adsorption, however, have not been dealt with in theoretical calculation of the adsorption energy owing to the difficulties in modelling such interactions. We have evaluated the solvation interaction energies using the fragment constant method of calculating the partition coefficients of amino acids. The fundamental assumption of this approach is that the partition coefficients of amino acids between water and organic solvent phases are related to the free energies of transfer from bulk water to the polymer surface. The X-ray crystallographic protein structures of lysozyme, trypsin, immunoglobulin Fab, and hemoglobin from the Brookhaven Protein Data Bank were used. The model polymer surfaces were polystyrene, polypropylene, polyethylene, poly(hydroxyethyl methacrylate) [poly(HEMA)], and poly(vinyl alcohol). All possible adsorption orientations of the proteins were simulated to study the effect of protein orientation on the solvation interactions. Protein adsorption on either hydrophobic or hydrophilic polymer surfaces was examined by considering the sum of solvation and other interaction energies. The results showed that the contribution of the solvation interaction to the total protein adsorption energy was significant. The average solvation interaction energy ranged from -259.1 to -74.1 kJ/mol for the four proteins on the hydrophobic polymer surfaces, such as polystyrene, polypropylene, and polyethylene. On the other hand, the average solvation interaction energies on hydrophilic surfaces such as poly(HEMA) and poly(vinyl alcohol) were larger than zero. This indicates that repulsive hydration interactions are in effect for protein adsorption on hydrophilic polymer surfaces. The total interaction energies of the proteins with hydrophobic surfaces were always lower than those with more hydrophilic surfaces. This trend is in agreement with the experimental observations in the literature. This study suggests that consideration of the solvation interaction energies is necessary for accurate calculation of the protein adsorption energies.

Adsorption↗

A new hydrophilic polymer for biomaterial coatings with low protein adsorption.

BIOPOL polyurethane polymers, an extension of the HYPOL Polymer series of foamable hydrophilic polymers, have been developed which exhibit improved performance for selected biomedical applications. Members of the BIOPOL polyurethane polymer series, with molecular weights in the range of 7000 to 30,000, are larger molecules than HYPOL polymers (MW less than 3000) and produce hydrogels, rather than foams, when mixed with water. The prototype material in this series, BIOPOL XP-5, is a liquid prepolymer which chain extends in water and forms a hydrogel which can contain greater than 85% water. The time required for polymerization with water was dependent on the prepolymer: water ratio. This prepolymer was coated onto silica and medical grade tubing and then cured in place with water to form a stable coating which was resistant to non-specific protein binding. In addition, soluble, isocyanate-free forms of the prepolymer were tested for toxicity and shown to produce no adverse effects when injected intravenously into mice or when applied to a chicken chorioallantoic membrane. BIOPOL polymers can be useful in applications where protein adsorption is an undesirable event.

Adsorption↗

Biospecific polymers: recognition of phosphorylated polystyrene derivatives by anti-DNA antibodies.

The recognition of DNA-like phosphorylated polymers by anti-DNA antibodies from the plasma of systemic lupus erythematosus patients was evidenced a few years ago by our research group. However, the radioimmunological Farr assay used for the assessment of anti-DNA antibodies adsorption was not sensitive enough to give accurate results, particularly in the case of weak levels of antibodies. An alternative method based on the use of radiolabelled species was set up in order to check the validity of previous results. Polystyrene resins with different levels in phosphate groups substitution were assessed with regard to their interactions with anti-DNA antibodies. Results show that the anti-DNA antibodies affinity is dependent on the composition of the polymers and reaches a maximum for a composition of 17.5-22.5 mol of phosphorus per 100 mol of monomeric units. This composition corresponds to the DNA-like polymer previously described. A computer-assisted method was used in order to have an insight into the structure of the active sites responsible for the DNA-like behaviour of this polymer. Numerical simulations of the phosphorylation reaction were performed using a Monte Carlo method, taking the structure predictions and the environment of the phosphorylated units into account. A number of thus generated virtual polymers correlated with the experimental results of the adsorption of anti-DNA antibodies. The chemical structure of the active site was determined by computations introducing selected hypotheses on the structure of the phosphorylated units. Moreover, since the number of active sites is directly related to the number of adsorbed anti-DNA antibodies in the experimental results, the most probable structure of the active sites is proposed and compared to a fragment of DNA. Conclusions are that the distances between the phosphate groups in the active sites of the DNA-like polymer and in the DNA fragment are similar. Optimal conditions for the purification of SLE sera by highly specific liquid chromatography using phosphorylated polystyrene resins of precise compositions as stationary phases can thus be envisaged, as well as a new method for the detection of anti-DNA antibodies.

Adsorption↗

Platelet adhesion on the gradient surfaces grafted with phospholipid polymer.

We have synthesized omega-methacryloyloxyalkyl phosphorylcholine (MAPC) polymers as new blood-compatible materials, with attention to the surface structure of the biomembrane and investigated their blood compatibility. The blood compatibility observed on the MAPC polymers is due to their strong affinity to phospholipids. When the blood comes in contact with the MAPC polymer, phospholipids in the plasma preferentially adsorb on the surface, compared with the plasma proteins or cells. The adsorbed phospholipids construct a biomembrane-like structure on the MAPC polymer surface. The MAPC polymers then have an excellent blood compatibility. In this study, we prepared a gradient poly(MAPC)-grafted polyethylene (PE) surface using a corona discharge treatment method to clarify the effect of the chemical structure of the MAPC unit on the blood compatibility of the MAPC polymers. The surface composition of MAPC and the hydrophilicity on the poly(MAPC)-grafted PE surface were determined by X-ray photoelectron spectroscopic (XPS) analysis and contact angle measurement with water, respectively. The phosphorus/carbon (P/C) ratio determined by the XPS analysis increased, but the water contact angle decreased with increasing corona irradiation energy. These results indicated that the surface density of the MAPC unit was increased. More than 2.5 cm from the starting point of the corona irradiation, the P/C ratio and water contact angle of the surface achieved a constant level. Thus, the surface was completely covered with the grafted poly(MAPC) chain. The effect of the methylene chain length of the MAPC unit on surface properties was also observed. The phospholipid polar group of the MAPC unit was effectively exposed on the surface as the chain length became longer. Moreover, the hydrophobicity of the surface was increased with the increase in the methylene chain length of the MAPC unit. The number of platelets adhering to the poly(MAPC)-grafted PE surface was reduced from the same point where the P/C ratio became constant.

Animals↗

Biochemical characterization of ADP-ribose polymer metabolism in SLE.

The metabolism of poly(ADP-ribose) in peripheral blood mononuclear (PBM) cells was studied in 13 patients with systemic lupus erythematosus (SLE) and in 12 age and sex matched controls. Poly(ADP-ribose) polymerase activity was measured as the net accumulation of ADP-ribose polymers during the conversion of 32P-NAD to poly(ADP-ribose) in PBM cells in vitro. The control population showed a mean activity of 418 +/- 91(s.d.)pmol ADP-ribose/10 min/10(6) cells. The SLE population was more heterogeneous and showed a lower mean of 225 +/- 147(s.d.)pmol ADP-ribose/10 min/10(6) cells. The mechanism of decreased ADP-ribose polymer accumulation was investigated. Measurements of turnover of the ADP-ribose polymers and its substrate, NAD+, showed that diminished ADP-ribose polymer accumulation in SLE subjects resulted from decreased poly(ADP-ribose) synthesis and not from altered rates of polymer turnover or NAD utilization. Western blot analyses of enzyme protein levels, kinetic studies of poly(ADP-ribose) polymerase activity and analyses of polymer size distribution suggested that the mechanisms of poly(ADP-ribose) synthesis in SLE cells is not altered but that the number of active poly(ADP-ribose) polymerase molecules is reduced.

Adult↗

Developments in the chemistry and biochemistry of pectic and hemicellulosic polymers.

Improved methods of isolation and analysis of cell walls from a range of plant tissues have shed new light on the structure of the constituent polymers, and have also helped to clarify some of the conflicting opinions on their mode of occurrence and association within the walls. The chemistry (and biochemistry) of pectic and hemicellulosic polymers in different types of plant organs is outlined, with particular emphasis on parenchymatous and immature tissues. The following aspects are discussed: the mode of occurrence of arabinans, galactans and arabinogalactans, and the possible association of some of them with proteins; the structural features of the esterified rhamnogalacturonans and associated neutral sugar residues in the pectic substances of middle lamellae and primary cell walls; the occurrence of acidic xylans, acidic arabinoxylans, and acidic arabinoxylans in association with other polymers in the cell walls of cambial, suspension-cultured and parenchymatous tissues of dicotyledons; evidence for the occurrence of small but significant amounts of xyloglucans in association with other polymers, and the occurrence of a range of xyloglucans in parenchymatous tissues; evidence for the occurrence of phenolic ester and phenolic cross-linkages between the cell wall polymers of parenchymatous tissues of both dicotyledons and monocotyledons, particularly the association of hydroxycinnamic acids with some pectic substances; the occurrence of proteoglycans and proteoglycan-polyphenol complexes and their relationship to the traditional hemicelluloses; and some aspects of the non-cellulosic polymers of non-endospermic and endospermic seeds.

Cell Wall↗

Fabrication and analysis of a low-loss in-fiber active polymer waveguide.

We present a method for fabricating an in-fiber electro-optic polymer waveguide within a D-shaped optical fiber. A combined process of selective chemical etching and spin coating creates a 2-cm in-fiber poly(methyl methacrylate)-DR1 dye polymer waveguide section with an overall insertion loss of micro 1.6 dB at 1550 nm. Numerical simulations show that, for in-fiber polymer waveguides to have low loss, the polymer layer's thickness must be kept below a certain value so that it will not support slab waveguide modes. Long transition regions between the unetched fiber and the polymer waveguide section also reduce loss. We analyze the efficiency of an in-fiber polymer waveguide by simulating its theoretical performance as an electro-optic modulator.

Journal Article↗

Size distribution of linear and helical polymers in actin solution analyzed by photon counting histogram.

Actin is a ubiquitous protein that is a major component of the cytoskeleton, playing an important role in muscle contraction and cell motility. At steady state, actin monomers and filaments (F-actin) coexist, and actin subunits continuously attach and detach at the filament ends. However, the size distribution of actin oligomers in F-actin solution has never been clarified. In this study, we investigated the size distribution of actin oligomers using photon-counting histograms. For this purpose, actin was labeled with a fluorescent dye, and the emitted photons were detected by confocal optics (the detection volume was of femtoliter (fL) order). Photon-counting histograms were analyzed to obtain the number distribution of actin oligomers in the detection area from their brightness, assuming that the brightness of an oligomer was proportional to the number of protomers. We found that the major populations at physiological ionic strength were 1-5mers. For data analysis, we successfully applied the theory of linear and helical aggregations of macromolecules. The model postulates three states of actin, i.e., monomers, linear polymers, and helical polymers. Here we obtained three parameters: the equilibrium constants for polymerization of linear polymers, K(l)=(5.2 +/- 1.1) x 10(6) M(-1), and helical polymers, K(h)=(1.6 +/- 0.5) x 10(7) M(-1); and the ratio of helical to linear trimers, gamma = (3.6 +/- 2.3) x 10(-2). The excess free energy of transforming a linear trimer to a helical trimer, which is assumed to be a nucleus for helical polymers, was calculated to be 2.0 kcal/mol. These analyses demonstrate that the oligomeric phase at steady state is predominantly composed of linear 1-5mers, and the transition from linear to helical polymers occurs on the level of 5-7mers.

Actins↗

Soft contact lens biomaterials from bioinspired phospholipid polymers.

Soft contact lens (SCL) biomaterials originated from the discovery of a poly(2-hydroxyethyl methacrylate) (poly[HEMA])-based hydrogel in 1960. Incorporation of hydrophilic polymers into poly(HEMA) hydrogels was performed in the 1970-1980s, which brought an increase in the equilibrium water content, leading to an enhancement of the oxygen permeability. Nowadays, the poly(HEMA)-based hydrogels have been applied in disposable SCL. At the same time, high oxygen-permeable silicone hydrogels were produced, which made it possible to continually wear SCL. Recently, numerous trials for improving the water wettability of silicone hydrogels have been performed. However, little attention has been paid to improving their anti-biofouling properties and biocompatibility. Since biomimetic phospholipid polymers possess excellent anti-biofouling properties and biocompatibility they have the potential to play a valuable role in the surface modification of the silicone hydrogel. The representative phospholipid polymers containing a 2-methacryloyloxyethyl phosphorylcholine (MPC) unit suppressed nonspecific protein adsorption, increased cell compatibility and contributed to blood compatible biomaterials. The MPC polymer coating on the silicone hydrogel improved its water wettability and biocompatibility, while maintaining high oxygen permeability compared with the original silicone hydrogel. Furthermore, the newly prepared phospholipid-type intermolecular crosslinker made it possible to synthesize a 100% phospholipid polymer hydrogel that can enhance the anti-biofouling properties and biocompatibility. In this review, the authors discuss how polymer hydrogels should be designed in order to obtain a biocompatible SCL and future perspectives.

Biocompatible Materials↗

Differences in pressure and temperature transitions of proteins and polymer gels.

Pressure-driven and temperature-driven transitions of two thermoresponsive polymers, poly(N-isopropylacrylamide) (pNIPAM) and poly(N-vinylisobutyramide) (pNVIBA)), in both a soluble linear polymer form and a cross-linked hydro-gel form, were examined by a dynamic light-scattering method and direct microscopic observation, respectively. Their behavior was compared with that of protein systems. Changes in some characteristic parameters in the time-intensity correlation functions of dynamic light-scattering measurement of aqueous solutions of pNIPAM at various pressures and temperatures showed no essential differences during temperature and pressure scanning and, as a whole, the motions of polymers in aqueous solutions were similar in two types of transitions until chain shrinkage occurred. The gels (cross-linked polymer gels) prepared from the thermoresponsive polymers also showed similar volume transitions responding to the pressure and temperature increase. In temperature transitions, however, gels showed drastic volume shrinkage with loss of transparency, while pressure-induced transition showed a slow recovery of transparency while keeping the size, after first transient drastic volume shrinkage with loss of transparency. At a temperature slightly higher than the transition under atmospheric temperature, so-called reentry of the volume change and recovery of the transparency were observed during the pressure-increasing process, which implies much smaller aggregation or non-aggregated collapsed polymer chains in the gel at higher pressures, indicating a certain mechanistic difference of the dehydration processes induced by temperature and pressure.

Acrylic Resins↗

Distribution analysis of epoxy groups in polymers by derivatization-electron probe X-ray microanalysis.

An analytical method, referred to as "derivatization-electron probe X-ray micro-analysis (XMA)", has been developed to determine the distribution of a small amount of the functional groups in a polymer. The suitable conditions for the derivatization reaction with epoxy groups, which contribute to the hardening reactions of polymers, were investigated. It was found that epoxy groups in polymers were derivatized selectively using gas-phase esterification with hydrochloric acid (HCI). The most suitable amount of HCl in a 50 ml vial was 300 microl. After setting a sample in the vessel without directly contacting the reagent, by reacting the reagent and the sample at 25 degrees C for 1 h, the highest reaction yield and selectivity were obtained. By derivatization-XMA using this reaction condition, the measurement of the distribution of epoxy groups in the polymer became feasible. Actual applications to a depth analysis of epoxy groups in the hardened acrylic coating and epoxy resin proved that this method is useful for the characterization of polymers and for the study of the hardening reaction of polymers.

Journal Article↗

Preparation and characterization of cyclodextrin polymer and its high-performance liquid-chromatography stationary phase.

Cyclodextrin (CD) polymers were synthesized from the reaction of native CDs with a hexamethylene diisocyanate (HDI) compound in a dried DMF solution. The obtained CD polymer contained a range of 8-14% N due to HDI by elemental analysis. The physical and chemical properties of the CD polymers were characterized by IR, solid state 13C NMR, TGA, and DSC, respectively. An HPLC column was prepared using the CD polymer with a carbamate linker by a slurry method. Separation of the phenol isomers was conducted using the CD polymer stationary phase and CD by HPLC. Furthermore, an inclusion complex of the phenol isomer was studied by FT-Raman spectroscopy. From the HPLC and FT-Raman results, inclusion phenomena of o-, m-, and p-nitrophenol onto CD and CD polymers were analyzed.

Calorimetry, Differential Scanning↗

Development of topically effective formulations of acetazolamide using HP-beta-CD-polymer co-complexes.

The myriad of side effects induced by acetazolamide (oral use), the introduction of newer topical carbonic anhydrase inhibitors (CAI's) and the advent of other antiglaucoma medications has led to a decreased interest in acetazolamide. The use of cyclodextrins to improve the solubility and bioavailability of poorly soluble drugs has however, rekindled an interest in acetazolamide (ACZ), because its poor solubility is one of the major factor responsible for its failure to show topical effectiveness. Since water soluble polymers have been reported to improve the complexing capabilities of beta-cyclodextrins, in the present study water soluble polymers like polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), hydroxypropymethylcellulose (HPMC) and the mucoadhesive polymer Carbopol 934P were incorporated into aqueous 10% w/v 2HP-beta-CD solution to improve the solubility of ACZ. The effect of these polymers on the corneal transport of 5 mg/ml (0.5% w/v) solution of ACZ in aqueous 10% 2HP-beta-CD was evaluated. The inclusion of these polymers significantly increased the solubility of ACZ from 3.43 mg/ml in aqueous 10% 2HP-beta-CD to 5.1 mg/ml (48.6%) in 0.05% PVP; 6.80 mg/ml (98.3%) in 0.05% PVA; and 6.74 mg/ml (96.5%) in 0.2% Carbopol 934P. From amongst the various polymers assessed in the study, PVA was deemed the best, based on the premise of better apparent permeability coefficient (P(app)) upon in vitro corneal permeation studies. Inspite of a large enhancement in solubility produced by Carbopol 934P, surprisingly, it could not efficiently increase the Papp.

2-Hydroxypropyl-beta-cyclodextrin↗