Radiation-induced synthesis of poly(vinylpyrrolidone) nanogel

Studies of the radiation-induced synthesis of poly(vinylpyrrolidone) (PVP) nanogels, intended to provide a basis for obtaining intra-molecular cross-linked products, which are more useful in drug delivery, show that a sharp change in the controlling mechanism from inter-molecular to intra-molecular cross-linking occurs above a threshold temperature around 50 °C-55 °C, even though the rate of inter-molecular cross-linking is enhanced as the temperature is raised. When aqueous solutions of PVP are irradiated, the activation energy of the decay of the PVP· radical is observed to rise sharply above this threshold temperature. This can be attributed to the collapse of the polymer chains, which occurs at temperatures above approximately 55 °C and leads to a reduction of the R_h of the irradiated polymer molecules at 77 °C to (44 ± 3) % of that of PVP molecules that were not irradiated at 20 °C, as shown by the results of AFFFF measurements. The abrupt transition to a mechanism controlled by intra-molecular cross-linking is due to the thermal collapse of the polymer structure. This accounts for the observation that activation energy is higher within the temperature range above 55 °C. Higher pulse repetition rates during electron irradiation also promote intra-molecular cross-linking.     

Stimuli responsive gels based on interpenetrating network of chitosan and poly(vinylpyrrolidone)

New spherically shaped crosslinked IPN hydrogels based on chitosan and poly(vinylpyrrolidone) were prepared. The IPN hydrogels were synthesized in two steps: (1) chitosan (CHT) crosslinked beads were obtained by reaction of chitosan with ethyleneglycol diglycidyl ether (EGDE); (2) absorption of a suitable amount of a solution of vinylpyrrolidone (VP) monomer from the porous CHT beads followed to VP polymerization and crosslinking inside the network. Sequential IPN's at different composition were obtained: they reversibly swell in water at various pH and show sensitive volumetric behaviour.     

Calorimetric determination of the enthalpy change for the binding of methyl orange to poly(vinylpyrrolidone) in aqueous solution

Thermodynamic parameters have been determined for the interaction of methyl orange and poly(vinylpyrrolidone) in aqueous solutions containing tris, tris and hydrochloric acid, or water only. Enthalpy changes were determined by use of a flow microcalorimeter. Free energy changes were calculated from the results of equilbrium dialysis studies. The results are interpreted in terms of the behaviour of poly(vinylpyrrolidone) in these systems. Analysis of data shows that the hydrophobic interactions in the systems are in the order: tris > wateronly > tris-HC1.     

Complexation of poly(vinylpyrrolidone) and gelatin with some transition metal chlorides in aqueous solution

Complexation of poly(vinylpyrrolidone) and gelatin with certain metal chlorides (HgCl₂, CdCl₂, CoCl₂, and ZnCl₂) have been investigated by viscosimetric and spectrophotometric techniques in aqueous solutions. While the change in intrinsic viscosity, [η], of poly(vinylpyrrolidone) has shown a discontinuity with a concentration of metal chlorides, gelatin showed a steady decrease with increasing metal chloride concentration. The decreasing order of effectiveness of cations in complex formation is Hg²⁺ > Cd²⁺ > Co²⁺ > Zn²⁺ for poly(vinylpyrrolidone) and Zn²⁺ > Co²⁺ > Cd²⁺ > Hg²⁺ for gelatin solutions. It has been suggested that the poly(vinylpyrrolidone)/metal cation interaction is a charge-controlled reaction, and gelatin/metal cation is a covalent coordination in character. A similar metal cation effect has been observed for poly(vinylpyrrolidone) by UV-VIS spectrophotometry. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 891–895, 1998     

Self diffusion of small molecules in aqueous solution of poly(vinylpyrrolidone)

The self-diffusion coefficients of small penetrants were measured in aqueous solutions at varying concentrations of poly(vinylpyrrolidone). Measurements have been performed using the n.m.r. pulsed-gradient spin-echo (PGSE) technique and the classical gradient diffusion (CGD) method, modified for ternary systems. A good agreement was found between the two, confirming the validity of the latter. The results have been quantitatively analysed by a free-volume approach adapted for diffusion of a solute in moderately concentrated polymer solutions. From this model a linear relationship is predicted between ln $\text{D}\text{D}{}_{\mathrm{<mtext>o</mtext>}}$ and ?^?1, the reciprocal volume fraction of solvent, which was also found experimentally for all diffusants studied. An enhanced concentration dependence of penetrant diffusion with increasing size of the diffusing molecules was observed. These findings are in agreement with predictions from the free-volume theory.     

Improvement of Permeability of Poly(vinyl alcohol) Hydrogel by Using Poly(ethylene glycol) as Porogen

The porous structure of PVA hydrogel achieved with varying content and varying molecular weight of PEG was investigated. It was found that with increasing content or molecular weight of PEG, the diffusion coefficient D _e and UV transmission of ink solution increased, indicating that the permeability and mass transfer capability of the gel beads were enhanced. The swelling rate constant k and equilibrium swelling rate of the gel were significantly improved by addition of PEG, and many pores formed inside the gel to provide channels for microbial metabolites. With increasing molecular weight of PEG, the size of pores became increasingly large.     

Adsorption behavior of poly(vinylpyrrolidone) toward fuller's earth suspensions

The adsorption of poly(vinylpyrrolidone) (PVP) onto Fuller's earth surface was studied at fixed pH (4.2) and room temperature (27 ± 0.2°C). The kinetics of the adsorption process was monitored and various adsorption and kinetic parameters such as the adsorption coefficient, the rate constants for adsorption and desorption, the diffusion constant, and the penetration constant were evaluated. The effects of various experimental factors such as the pH and the presence of inorganic and organic anions or aliphatic alcohols were also studied on the adsorbed amounts of PVP. The role of temperature was also investigated and various thermodynamic parameters such as the standard Gibb's free energy, enthalpy, and entropy were also evaluated. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2122–2133, 2000     

聚乙二醇增塑聚乳酸的等温结晶动力学研究

采用DSC方法对聚乙二醇(PEG)增塑聚乳酸的等温结晶动力学进行了研究。结果表明,PEG的加入提高了聚乳酸的结晶速度,在相同结晶温度下,随着PEG摩尔质量的增大,结晶速率增大,结晶活化能先减小后增大。不同摩尔质量PEG增塑PLA的结晶成核机理和生长方式一样。     

Poly(hydroxyethyl acrylate-co-coumaryl acrylate) as a photo-responsive amphiphile

Poly(hydroxyethyl acrylate-co-coumaryl acrylate)s P(HEA-CA)s were prepared as a photo-responsive amphiphile by a free radical polymerization. Their CA residues were readily dimerized under UV light irradiation (365 nm, 400 W). Their interfacial activity increased in proportional to the CA content. P(HEA-CA)s were self-assembled into microspheres in aqueous phase due to their amphiphilicity which were confirmed by TEM. And the mean diameter was higher with higher CA content. In addition, P(HEA-CA)s could emulsify mineral oil in distilled water. The emulsions prepared with higher CA content were more stable in terms of the droplet size change. They could be destabilized by UV light irradiation.     

Application of Poly(butylenes 2-methylsuccinate) as Migration Resistant Plasticizer for Poly(vinyl chloride)

The bio-based and biodegradable polyester poly(butylenes 2-methylsuccinate) (PBM) was successfully used as a polymeric plasticizer to modify poly(vinyl chloride) (PVC) in this work. The tensile properties, plasticization efficiency estimated by the lowered glass transition temperature and the enhanced elongation at break of the PVC/PBM blends and the migration stability of the PBM were investigated. It was indicated that the migration-resistant property of PVC plasticized with PBM was greatly superior to that with dioctyl phthalate (DOP). Furthermore, the tensile properties were comparable to that of PVC/DOP, indicating that the environmentally friendly PBM can be used as an alternative plasticizer to remove the potential health risks from migrating phthalates during applications.     

Properties of aqueous salt solutions of poly(vinylpyrrolidone). II. Polymer dimensions and thermodynamic quantities

The unperturbed dimensions and thermodynamic parameters of poly(vinylpyrrolidone) (PVP) have been studied in aqueous salt solutions, e.g. phosphates, mono- and dihydrogen phosphates, carbonates, sulphates of sodium and potassium. Values of K₀ ( = [η]_ΘM^-1/2, where [η]_Θ is intrinsic viscosity at the theta temperature and M is molecular weight) with M_w = 78 000 g mol^-1 were found to range from 4·63×10^-4 to 5·56×10^-4 dl g^-1, and root-mean-square end-to-end distances, 〈r²〉₀^1/2, ranging from 1·61×10^-6 to 1·68×10^-6cm were evaluated. Values of the characteristic ratio, C_n, the steric parameter, σ, and the enthalpy and the entropy of dilution parameters, χ_H and χ_S, have also been calculated, and the interaction parameter was found to be χ-0·5<-0·001 for aqueous salt solutions of PVP. ©1997 SCI     

Surfactant-polymer interactions: Mixed micelles of hexadecylpyridinium bromide and trimethyltetradecylammonium bromide in aqueous poly(vinylpyrrolidone) solution

The conductance of hexadecylpyridinium bromide (HPyBr) and trimethyltetradecylammonium bromide (TTAB) mixtures over the entire mole fraction range of HPyBr (α_HPyBr) was measured in aqueous poly(vinylpyrrolidone) (PVP) solution containing 1, 5, and 10 wt% PVP at 30°C. Each conductivity curve showed two breaks corresponding to two aggregations throughout the whole mole fraction range of HPyBr and TTAB mixtures except for pure TTAB for which a single break corresponding to the conventional critical micelle concentration was observed. The two aggregation processes in the presence of low amounts of PVP were mostly similar to those in pure water, however, 10 wt% PVP shifted the break, corresponding to the second aggregation, toward the higher value. This was attributed to HPyBr/PVP interactions, which were also evident from the appearance of a second break in the conductivity (κ) plot of pure HPyBr in aqueous 10 wt% PVP. From conductivity data, various micellar parameters in the presence of PVP were determined and discussed from the standpoint of micelle-polymer interactions. The mixing behavior of HPyBr and TTAB corresponding to the first break in the presence of PVP was ideal for the most part and identical to that in pure water.     

聚酰胺胺(PAMAM)树形分子用作乳化炸药的稳定剂

用PAMAM树形分子作稳定剂制成了一种新型的乳化炸药,并用高低温循环及室温贮存的电导率测试、扫描电镜等技术对其稳定性作了表征.结果表明,用PAMAM稳定后的乳化炸药具有很好的稳定性,对该乳化炸药的爆速测试结果表明,添加PAMAM后的乳化炸药的爆速反而增加.同时,对此乳化炸药的稳定机理作了初步探讨.     

Poly(o-toluidine) as the matrix for incorporation of palladium species from PdCl2 aqueous solutions

Reactivity of poly(o-toluidine) in the emeraldine base form (POT) and protonated with HCl (POT/HCl) in PdCl₂ aqueous solutions of various HCl concentrations has been studied. Using elemental analysis, FTIR, UV–Vis, XPS and EXAFS spectroscopies as well as XRD and SEM it has been established that POT/HCl is more reactive than POT. The course of reactions is influenced by the type of the PdCl₂ solution. Thus, protonation of POT with incorporation of palladium (II) chloro–and/or aquachloro–and/or chlorohydroxycomplexes counterions is the main process occurring in the PdCl₂ solutions of higher HCl concentration. A redox reaction resulting in the oxidation of the polymer chain with simultaneous formation of metallic palladium takes place in the PdCl₂ solution of lower HCl concentration. POT/HCl shows enhanced reducing properties with respect to POT. Lowering of the protonation level (i.e. some deprotonation) of POT/HCl has been also observed. Coordination of palladium (II) ions by nitrogen atoms of the polymer chain can be also postulated.     

聚乙二醇改性聚乳酸及其在药物载体中的应用

综述了聚乙二醇改性聚乳酸及其端基化的制备方法,介绍了聚乙二醇-聚乳酸嵌段共聚物作为药物载体的研究进展,并对今后的研究进行了展望.     

Behaviour of poly(N-vinylcaprolactam) macromolecules in the presence of organic compounds in aqueous solution

Dynamic light scattering measurements have been performed for aqueous solutions of thermosensitive linear poly(N-vinylcaprolactam) (PVCa) macromolecules in the presence of NaCl and different water soluble amphiphilic organic compounds: pyrogallol (neutral amphiphilic compound), cetylpyridinium chloride (cationic surfactant) and sodium dodecylsulfate (anionic surfactant). A decrease in the macromolecular hydrodynamic diameter is observed upon addition of ionic surfactants (SDS, CPC) at low surfactant concentrations. This trend changes to an increase in the macromolecular hydrodynamic diameter at high surfactant concentration at temperatures below the temperature of polymer aggregation. This effect is in contrast with the behaviour of the systems of PVCa–non-ionic organic compounds (pyrogallol) and NaCl where we always observed the weak monotonic decrease of the hydrodynamic diameter with the increase in the concentration of organic compound, NaCl.

The behaviour of ternary systems PVCa macromolecules–ionic surfactant–pyrogallol and PVCa macromolecules–ionic surfactant–NaCl was studied. The addition of pyrogallol leads to the suppression of the intermacromolecular aggregation induced by temperature increase that is still observed at low surfactant concentrations and to the decrease of macromolecular hydrodynamic diameter. Also, the addition of NaCl to the PVCa/ionic surfactant systems results in the increase of the macromolecular hydrodynamic diameter. It is speculated that these results are due to the suppression of the cross-linking role of surfactant aggregates upon the addition of NaCl and pyrogallol.     

Synthesis and Characterization of Poly(acrylic acid)/Poly(vinyl alcohol)-xanthan Gum Interpenetrating Network (IPN) Superabsorbent Polymeric Composites

Initially interpenetrating network (IPN) hydrogel was prepared by dispersing xanthan gum (XG) into poly(vinyl alcohol) (PVA) backbone in an aqueous medium. Polyacrylic acid (PAA)/Poly (vinyl alcohol)-Xanthan gum IPN superabsorbent composite were fabricated well by dispersing the prepared IPN hydrogel in acrylic acid and polymerized in a complete aqueous environment through chemical cross-linking method. These superabsorbent polymeric composites were analytically evaluated by scanning electron microscopy (SEM), Fourier Transform Infrared Spectra (FTIR), Thermal analysis (DSC) and X-ray diffraction (XRD) analysis. Simultaneously water absorbency, swelling kinetics and water retention abilities of this prepared superabsorbent polymeric composites were also investigated systematically.     

Poly(thienylenevinylene) prepared by ring-opening metathesis polymerization: Performance as a donor in bulk heterojunction organic photovoltaic devices

Poly(3,4-dioctylthienylenevinylene) (PDOTV) was synthesised by ring-opening metathesis polymerization (ROMP) with controlled molecular weight. PDOTV has been used to fabricate organic photovoltaic devices in combination with phenyl C₆₁-butyric acid methyl ester (PCBM) for the first time. The devices show power conversion efficiency up to 0.18%. Optimal device performance was found at a film thickness of 100 nm and a ratio of PCBM to PTV of 2:1. External quantum efficiency (EQE) measurements, transient absorption spectroscopy and morphology studies were carried out to establish factors governing photovoltaic performance. These results suggest that the efficiency values for the devices were limited by the hole mobility and unexpected phase separation within the blend. Nevertheless, the results show that ROMP is a viable, alternative, synthetic strategy for preparing PTV donors for use in bulk heterojunction OPVs.     

Poly(ethylene oxide)-poly(butadiene) interpenetrated networks as electroactive polymers for actuators: A molecular dynamics study

Molecular dynamics (MD) techniques have been used to study ionic transport and coordination stability in an interpenetrating polymer (IPN) network used as electrolyte for actuator devices. The system consisted of poly(ethylene oxide) (PEO) and poly(butadiene) (PB) in a 80/20% weight ratio at a total polymer of 32%, immersed into propylene carbonate (PC) solutions of LiClO₄. The system has been studied for five different concentrations of LiClO₄ in PC: 0.25, 0.5, 0.75, 1.0 and 1.25 M, and with applied external electric fields of 0, 1 and 5 MV/m. It is shown that the polymer matrix has little involvement in the movement of ions and solvent, but that the polymer arrangement is important for the solvent phase nano-structure, and thereby influences the mobility. The mobility of PC is higher than of the other species in the system, but the charged species display higher mobility under external field. The field threshold level for conductivity processes is between 1 and 5 MV/m. It is argued that ion pairing, phase separation and coordination stability are important for the overall dynamic properties.     

Pectin grafted poly(N‐vinylpyrrolidone): Optimization and in vitro controllable theophylline drug release

The present article describes preparation, optimization, and characterization of pectin grafted polyvinylpyrrolidone hydrogels followed by controllable theophylline drug release. The gels were prepared in the presence of N,N′–methylenebisacrylamide (MBAA) crosslinker and ceric ammonium nitrate (CAN) initiator under N₂ atmosphere. Optimum conditions, in terms of percent of grafting (%G), were determined as follows: Pectin = 1.0 g, [NVP] = 2.81 mM, [MBAA] = 0.65 mM, [CAN] = 0.073 mM, polymerization temperature = 30°C and time = 4.0 hrs. Hydrogels were characterized by FTIR, TGA, DSC, XRD, and SEM. In vitro controllable release of theophylline model drug was studied using different N‐vinylpyrrolidone monomer to MBAA crosslinker ratio (i.e., [NVP]/[MBAA] ratios) and different polymerization temperatures at two pH values, namely 5.5 and 7.4. The optimum conditions for colon‐targeted vehicles that could provide the least theophylline release at pH 5.5, and the most theophylline release at pH 7.4, were as follows: [NVP]/[MBAA] = 4.33, polymerization temperature = 10°C and %G = 62.2. Such promising hydrogel characteristics may play the key role in many future drug release implementations. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010