Synthesis and characterization of poly(vinyl pyrrolidone)-capped bismuth nanospheres

Poly(vinyl pyrrolidone)-capped bismuth nanospheres were synthesized by a simple and convenient wet chemical method. In the process, bismuth nitrate was reduced by ethylene glycol in the presence of poly(vinyl pyrrolidone) (PVP) at 185 °C in air. PVP was used as a protecting agent to prevent oxidation of the sperical bismuth particles. PVP molecules were absorbed on the surface of bismuth nanospheres through the interaction of O–Bi bond which was confirmed by Fourier transform infrared (FT-IR) measurement. The thermal analysis shows the samples contained about 73 wt.% metallic bismuth. The optical absorption spectrum of poly(vinyl pyrrolidone)-capped bismuth nanosphere shows a strong absorption band at 275 nm.     

Interaction of collagen and poly(vinyl pyrrolidone) in blends

The interaction between collagen and poly(vinyl pyrrolidone) (PVP) in blends has been studied by viscometry, differential scanning calorimetry (DSC) and by Fourier transform infrared spectroscopy (FTIR). It was found that the amide A and amide I bands position in FTIR spectra of collagen were shifted after blending with PVP to higher wavenumbers. DSC measurements showed different melting temperature, glass transition temperature and enthalpy for the blends and for the single components. Viscosity measurements showed interaction between collagen and PVP also in a dilute water solution.The results have shown, that the interactions between collagen and PVP exist due to the strong interactions between the synthetic and biological component, mainly by hydrogen bonds. These interactions caused that collagen and PVP are miscible at molecular level. The blending of collagen with PVP may give the possibility of producing new materials for potential biomedical applications.     

Rheological behaviour of irradiated wound dressing poly(vinyl pyrrolidone) hydrogels

The use of hydrogels as biomaterials has increased lately. Poly(vinyl pyrrolidone) (PVP) is an example of polymer hydrogels applied for the synthesis of hydrogel to be used in different biomedical applications. This paper describes a study on rheological properties of PVP hydrogels obtained by gamma radiation techniques. PVP hydrogels were obtained by gamma radiation of PVP water solutions with different radiation doses. It was studied the influence of additives such as poly(ethylene glycol) (PEG), poly(ethylene oxide) (PEO) and glycerol on the rheological behaviour of the gel. The rheological behaviour of hydrogel samples was characterized by measuring the shear storage modulus (G′) under dynamic shear loading. Besides this, sterility and cytotoxicity tests were performed. The study on rheological behaviour of hydrogels showed that G′ of PVP gels change according to the additive used. Glycerol increases the fluidity of the gel. The influence of PEG depends on the amount and on its molecular mass. The increase on PEG amount and molecular mass cause a decrease of G′ and an increase in the crosslinking density of PVP hydrogel network. The use of high molecular weight PEO allows the increase of the elasticity of the PVP gels.     

Benzylic and pyridinium head groups controlled surfactant-polymer aggregates of mixed cationic micelles and anionic polyelectrolytes

The oppositely charged electrostatic interactions between cationic single and mixed micelles of benzyldimethylhexadecylammonium chloride (BHDACl), hexadecylpyridinium bromide (HPyBr), hexadecylpyridinium chloride (HPyCl), and their mixtures with anionic polyelectrolytes, namely carboxymethylcellulose sodium salt (CMC) and polystyrene sulfonate sodium salt (PSS) were studied with the help of conductivity (), viscosity (), turbidity (), and NMR studies. showed single aggregation process, which was represented by apparent critical micelle concentration, acmc, of each surfactant in aqueous polyelectrolyte solution. Both and demonstrated strong electrostriction effects in the case of BHDACl-polyelectrolyte systems due to weak electrostatic interactions in view of steric hindrances created by benzylic group of BHDACl. ¹H NMR results showed that the head group proton resonances of BHDACl upon incorporation of HPyBr or HPyCl in the presence of CMC or PSS remained identical to that in pure water, which demonstrated very weak interactions between BHDACl and polyelectrolytes. A less shielding of pyridinium head group protons by BHDACl in the presence of polyelectrolytes in comparison to that in pure water indicated favorable electrostatic interactions between pyridinium head groups and anionic polyelectrolytes. HPyBr in comparison to HPyCl showed stronger interactions with polyelectrolytes.     

Influence of alkoxyethanols on the mixed micelle formation by hexadecyltrimethylammonium bromide and tetradecyltrimethylammonium bromide surfactant mixtures

 The conductances of hexadecyltrimethylammonium bromide (HTAB) and tetradecyltrimethylammonium bromide (TTAB) mixtures over the entire mole fraction range of HTAB were measured in aqueous binary mixtures of ethylene glycol monomethyl ether, monoethyl ether, and monobutyl ether, and of diethylene glycol monomethyl ether and monoethyl ether containing 10–30 wt% additive in their respective binary mixtures at 30 °C. Each conductivity curve showed a single break over the whole mole fraction range of HTAB–TTAB mixtures. From the break in the conductivity curve, various micellar parameters were calculated and the results were discussed with respect to the alkoxyethanol's additive effect on the mixed micelle formation. The micellar parameters of HTAB, TTAB, and of their mixtures showed a strong dependence both on the amount as well as on the number of repeating units in the presence of ethylene glycol derivatives, whereas a significant dependence only on the amount of additive was observed in aqueous diethylene glycol derivatives. The results in the former case were attributed to the hydrophobic hydration of the mixed micelles by the ethylene glycol derivatives, which showed a large dependence on the increase in the alkyl chain length of the additive. The hydrophobic hydration was considerably reduced in the case of diethylene glycol derivatives owing to the presence of an extra ether oxygen. An evaluation of the nonideality in the HTAB–TTAB mixtures revealed that in spite of the strong hydrophobic hydration of the HTAB–TTAB mixtures by the alkoxyethanols, the mixed micelles remain almost free from the additive molecules. Received: 11 January 2000/Accepted: 14 April 2000     

Photochemical stability of poly(vinyl pyrrolidone) in the presence of collagen

The photochemical stability of poly(vinyl pyrrolidone) (PVP) in the presence of 1%, 3% and 5% of collagen has been studied by UV-vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), thermogravimetry analysis (TG) and derivative thermogravimetry (DTG). Surface properties have been studied by contact angle measurements. PVP samples and samples containing 1%, 3% and 5% of collagen were irradiated with UV light of wavelength λ = 254 nm in air for up to 24 h. The amount of gel created during UV irradiation was estimated.PVP in the presence of 1%, 3% and 5% of collagen is less stable both thermally and photochemically. Collagen enhances photochemical processes leading to crosslinking of PVP. The contact angle measurements and values of surface free energy showed that the wettability of PVP films was changed by the addition of collagen and by UV irradiation. The increase of polarity of samples indicates an efficient photooxidation on the surface upon UV irradiation.     

Electrospinning of poly(vinyl pyrrolidone)-iodine complex and poly(ethylene oxide)/poly(vinyl pyrrolidone)-iodine complex - a prospective route to antimicrobial wound dressing materials

New nanofibers containing poly(vinyl pyrrolidone)-iodine complex (PVP-iodine) were obtained by electrospinning in order to prepare materials suitable for wound dressings. Different approaches were used: a one-step method based on electrospinning of PVP-iodine or poly(ethylene oxide)/PVP-iodine solutions and a three-step method based on electrospinning of PVP or poly(ethylene oxide)/PVP mixed solutions followed by photo-mediated crosslinking of the obtained nanofibers and subsequent complexation with iodine. The average diameters of the fibers were in the range 150-470 nm depending on the composition and on the applied field strength (AFS) and increased with increasing the amount of PEO in the spinning solutions. Higher AFS resulted in greater fiber diameter and in size distribution broadening. Photo-mediated crosslinking in the presence of 4,4′-diazidostilbene-2,2′-disulfonic acid disodium salt successfully stabilized the electrospun PVP and PEO/PVP nanofibers against water and water vapor.     

Effect of temperature on the intrinsic viscosity of poly(ethylene glycol)/poly(vinyl pyrrolidone) blends in aqueous solutions

In this work the intrinsic viscosity of poly(ethylene glycol)/poly(vinyl pyrrolidone) blends in aqueous solutions were measured at 283.1–313.1 K. The expansion factor of polymer chain was calculated by use of the intrinsic viscosities data. The thermodynamic parameters of polymer solution (the entropy of dilution parameter, the heat of dilution parameter, theta temperature, polymer–solvent interaction parameter and second osmotic virial coefficient) were evaluated by temperature dependence of polymer chain expansion factor. The obtained thermodynamic parameters indicate that quality of water was decreased for solutions of poly(ethylene oxide), poly(vinyl pyrrolidone) and poly(ethylene oxide)/poly(vinyl pyrrolidone) blends by increasing temperature. Compatibility of poly(ethylene oxide)/poly(vinyl pyrrolidone) blends were explained in terms of difference between experimental and ideal intrinsic viscosity and solvent–polymer interaction parameter. The results indicate that the poly(ethylene glycol)/poly(vinyl pyrrolidone) blends were incompatible.     

Chemical treatment of membranes of a polymer blend: Mechanism of the reaction of hypochlorite with poly(vinyl pyrrolidone)

Sodium hypochlorite solutions are used to treat membranes prepared from a polymeric blend containing poly(vinyl pyrrolidone) (PVP) to increase their water permeability. Sodium hypochlorite affects the membrane material in such a way that PVP is selectively removed from the membrane matrix. The mechanism of the reaction between hypochlorite and PVP is investigated by several chemical analysis techniques of the reaction products. Strong indications are found that the reaction involves chain scission of PVP according to a radical mechanism. © 1995 John Wiley & Sons, Inc.     

A novel route to substituted poly(vinyl pyrrolidone)s via simple functionalization of 1-vinyl-2-pyrrolidone in the 3-position by ring-opening reactions

A general synthetic approach is described that allows to obtain novel 1-vinyl-2-pyrrolidone (VP) derivatives with different kinds of functional groups in its 3-position in a one-pot reaction. The strategy used to achieve this goal is the reaction of the carboxamide anion of 1-vinyl-2-pyrrolidone with cyclic precursors of these functionalities. While the driving force for the reactions of three-membered rings is their high annular tension, it is shown here that larger heterocycles can be opened with good yield when additional electron-withdrawing groups are present in the ring. This leads to VP with longer spacer groups between the functionality and the future polymeric main chain. Furthermore, the high versatility of this procedure is demonstrated by the preparation, for the first time, of VP modified with amine or sulfonic functionalities that allow to prepare the corresponding aminated and sulfonated PVPs.     

High-performances membranes for pervaporation I. Poly(vinyl alcohol)–poly(N-vinyl pyrrolidone) blends

Dense membranes were prepared from poly(vinyl alcohol)–poly(N-vinyl pyrrolidone) (PVA–PVP) blends of different compositions and studied in swelling and dehydration by pervaporation of three organic solvents contaminated by 5 wt% water. The swelling generally increases with the PVP content. No extraction occurs in water–tetrahydrofuran (THF) and water–methyl ethyl ketone (MEK) mixtures. In ethanol containing 10 wt% of water, there is no extraction for blends containing less than 40 wt% PVP and an increasing extraction beyond this PVP content. The pervaporation flux of the water–ethanol mixture increases drastically at the same threshold whereas the water permselectivity falls to a low level. The values of the diffusion and permeability coefficients determined from transient permeation of the test water–ethanol mixture exhibit a similar sudden increase at the same PVP content threshold. This singular behavior of the blend membranes is interpreted by a strong affinity of the PVP component to ethanol, combined with a disappearance of crystallites in the blend at this threshold. Consequently the amorphous membrane can swell freely according to the affinity of the PVP component, leading to the observed behavior.     

聚乙烯醇/聚乙烯吡咯烷酮碱性复合膜的制备及其性能

通过在不同浓度KOH溶液中进行掺杂,制备出了聚乙烯醇/聚乙烯吡咯烷酮(PVA/PVP)碱性聚合物电解质膜.详尽考察了膜的组成、微观结构、热稳定性、离子电导率和甲醇吸收率.结果表明,PVA与PVP两者具有较好的相容性,当m(PVA)∶m(PVP)=1∶0.5时,膜断面致密、均匀,未发生大尺度相分离.PVP的混入可以极大提高复合膜的电导率和热稳定性.当m(PVA)∶m(PVP)=1∶1时,复合膜的电导率可达2.01×10-3 S.cm-1.PVA/PVP/KOH膜的甲醇吸收率随温度的升高没有明显变化,100℃时其甲醇吸收率仅为同条件下Nafion 115膜的1/4.这表明该复合膜有望作为一种新型的碱性直接甲醇燃料电池用固体电解质膜且可提高膜的使用温度.     

Interactions between metal chlorides and poly(vinyl pyrrolidone) in concentrated solutionsand solid‐state films

The rheological behavior of poly(vinyl pyrrolidone) (PVP)/N,N‐dimethylformamide (DMF) solutions containing metal chlorides (LiCl, CaCl₂, and CoCl₂) were investigated, and the results showed that the nature of the metal ions and their concentration had an obvious effect on the steady‐state rheological behavior of PVP–DMF solutions with different molecular weights. The apparent viscosity of the PVP–DMF solutions increased with an increasing metal‐ion concentration, and the viscosity increment was dependent on the metal‐ion variety_. For a CaCl₂‐containing PVP–DMF solution, for example, the critical shear rate at the onset of shear thinning became smaller with increasing CaCl₂ concentration. It was believed that multiple interactions among metal ions, carbonyl groups of PVP, and amide groups in DMF determined the solution properties of these complex fluids; therefore, ¹³C NMR spectroscopy was used to detect the interactions in systems of PVP–CaCl₂–DMF and PVP–LiCl–DMF solutions. NMR data showed that there were obvious interactions between the metal ions and the carbonyl groups of the PVP segments in the DMF solutions. Furthermore, IR spectra of the PVP/metal chloride composites demonstrated that the interaction between the metal ions and carbonyl groups in the PVP unit occurred and that the PVP chain underwent conformational variations with the metal‐ion concentration. DSC results indicated that the glass transition temperatures of the PVP/metal chloride composites increased with the addition of metal ions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1589–1598, 2007     

Novel antibacterial fibers of quaternized chitosan and poly(vinyl pyrrolidone) prepared by electrospinning

The preparation of continuous defect-free fibers from quaternized chitosan derivative (QCh) has been achieved by electrospinning of mixed aqueous solutions of QCh with poly(vinyl pyrrolidone) (PVP). The average fiber diameter significantly decreases from 2800 to 1500 nm on increasing the polyelectrolyte content. In order to impart to QCh/PVP electrospun fibers stability to water and water vapor, the fibers have been crosslinked by incorporation of photo-crosslinking additives into QCh/PVP spinning solutions and subsequent UV irradiation of the electrospun fibers. Photo-crosslinked QCh-containing electrospun mats show high antibacterial activity against the Gram-positive bacteria Staphylococcus aureus and Gram-negative bacteria Escherichia coli.     

Interactions of 3, 3.5, 4, and 4.5 generations of poly(amido amine) dendrimer with cationic surfactants

The conductivity (κ), turbidity (τ), NMR, and Krafft temperature (T _K) studies have been carried out for hexadecylpyridinium bromide (HPyBr), hexadecylpyridinium chloride (HPyCl), and hexadecyltrimethylammonium bromide (HTAB) in the presence of 3G, 3.5G, 4G, and 4.5G generations of poly(amido amine) dendrimers (PAMAM) in aqueous phase. The cmc of all present surfactants were evaluated from κ and τ measurements, both in the presence as well as in the absence of PAMAM. The cmc values decrease in the presence of PAMAM in comparison to that in pure water, especially in the presence of amine terminated PAMAM. Krafft temperature values of pure surfactants also decrease in the presence of various generations of PAMAM. A comparison of all present results from different techniques indicates that HPyBr interacts more strongly with all generations of PAMAM rather than HPyCl and HTAB.     

Interpolymer complexation and thermal behaviour of poly(styrene-co-maleic acid)/poly(vinyl pyrrolidone) mixtures

Polymer complexation between poly(styrene-co-maleic acid), (SMA28) and (SMA50) containing 28 and 50 mol% of maleic acid and poly(vinyl pyrrolidone) (PVP), has been investigated by differential scanning calorimeter (DSC), Fourier-transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). All results showed that the ideal complex composition of SMA28/PVP and SMA50/PVP leads, respectively, to 2:1 and 1:1 mole ratio of interacting components.For the investigated systems, the T_g versus composition curve does not follow any of the usual proposed models for polymer blends. Withal, a new model proposed by Cowie et al. is used to fit the T_g data and it is found to reproduce the experimental results more closely. According to n and q obtained values, it seems reasonable to conclude that the inter-associated hydrogen bonds dominate in SMA28/PVP (2:1) complexes. This effect is corroborated by the FTIR study as evidenced by the high displacement of the specific bands and ionic interactions have been clearly identified. Finally, a thermogravimetric study shows that ionic interactions increase the thermal stability of these complexes.     

高稳定性化学交联聚乙烯醇/聚乙烯吡咯烷酮碱性固体电解质膜

碱性固体电解质膜的稳定性是影响其在电化学领域应用的一个重要因素.本文在前期研究工作的基础上,通过直接共混和化学交联修饰制备出了聚乙烯醇/聚乙烯吡咯烷酮(PVA/PVP)碱性聚合物电解质膜.采用傅里叶变换红外(FTIR)光谱、热重分析(TGA)、扫描电镜(SEM)和交流阻抗等方法详细考察了复合膜的分子结构、热稳定性、化学稳定性、氧化稳定性和尺寸稳定性.红外光谱结果表明,PVP成功地混入聚合物基体中,在1672cm-1处表现出来自于PVP第I带C襒O的强吸收峰.TGA结果表明,提高掺杂的KOH溶液浓度对PVA/PVP碱性膜的热稳定性没有明显影响.SEM分析结果表明,复合膜经高温、高浓度碱(80℃,10mol·L-1)处理后,其断面结构仍致密均匀,未出现类似小孔等膜降解情况,此时膜电导率(1.58×10-3S·cm-1)相比室温相同碱液时提高91.5%,表明PVA/PVP膜具有很好的耐碱化学稳定性.同时,PVA/PVP碱性膜表现出良好的抗氧化性,在60℃的3%和10%H2O2溶液中处理均没有观察到明显的质量损失,150h后仍能保持原膜质量的89%和85%.此外,由于膜内形成致密的内互交联网络结构,复合膜在水中800h之后也表现出很好的同向性和电导率稳定性.     

Intrinsic adhesion properties of poly(vinyl pyrrolidone) to pharmaceutical materials: humidity effect

Poly(vinyl pyrrolidone) (PVP) is widely used for bioengineering and pharmaceutical applications, and its adhesion characteristics are critical. When used as a binder in pharmaceutical granulation, it covers the resultant granules and governs their surface properties. The intrinsic adhesion forces of PVP toward common hydrophobic (magnesium stearate) and hydrophilic (lactose) pharmaceutical materials have been studied as a function of relative humidity (RH). The effect of RH on adhesion force was more significant for the PVP/hydrophilic material than the PVP/hydrophobic material. Adhesion was lowest between 20 and 40% RH, and it increased at RH above 40% and below 20%. This is likely to be due to the development of capillary and triboelectrification forces, respectively. In a nano-indentation experiment using a silicon tip at room temperature, the PVP surface underwent a glass transition at 70% RH. This result suggests that surface softening contributes to the increased PVP adhesion at RH above 70%. To adjust the adhesion properties of PVP, humidity control should be an essential part of research and development. Effect of humidity on the adhesion forces between PVP and lactose (LT) or magnesium stearate (MS).     

Synthesis of ion-free latex particles composed of polybutadiene and poly (vinyl pyrrolidone) as polymer electrolyte materials

The synthesis of polybutadiene (PB) by emulsion polymerization with use of poly (vinyl pyrrolidone) (PVP) stabilizer was investigated. The goal was to prepare flexible latex films that clearly retain particle morphology in the solid state after heat treatment and contain no ionic, hydroxyl, or (primary, secondary) amino groups. The latex particle core composed of PB was nonpolar and rubbery, while the particle shell composed of PVP was polar and glassy. Average particle diameter was measured by the dynamic light scattering technique, and particles were imaged by scanning and transmission electron microscopic analyses. Dialysis of the latices resulted in successful exchange of the dispersion medium without precipitation. © 1994 John Wiley & Sons, Inc.     

Mixed micelles of structurally related antidepressant drugs

 The composition of micelles in a binary mixture of the amphiphilic antidepressant drugs imipramine hydrochloride and clomipramine hydrochloride has been determined from an analysis of the variation of the critical micelle concentration from conductivity techniques as a function of solution composition. The equilibrium distribution of components between micelle and monomer phases was evaluated using a theoretical treatment based on excess thermo-dynamic quantities. The nonideality of mixing, expressed in terms of the interaction parameter β, was appreciable in systems containing low imipramine mole fractions, suggesting differences in the packing characteristics within micelles of these two drugs. Received: 7 July 1997 Accepted: 10 August 1997