Physicochemical and biological characterization of a xanthan gum-polyvinylpyrrolidone hydrogel obtained by gamma irradiation.

Xanthan gum (XG) and polyvinylpyrrolidone (PVP) are two polymers with low toxicity, high biocompatibility, biodegradability, and high hydrophilicity, making them promising candidates for multiple medical aspects. The present work aimed to synthesize a hydrogel from a mixture of XG and PVP and crosslinked by gamma irradiation. We assessed the hydrogel through a series of physicochemical (FT-IR, TGA, SEM, and percentage of swelling) and biological (stability of the hydrogel in cell culture medium) methods that allowed to determine its applicability. The structural evaluation by infrared spectrum demonstrated that a crosslinked hydrogel was obtained from the combination of polymers. The calorimetric test and swelling percentage confirmed the formation of the bonds responsible for the crosslinked structure. The calorimetric test evidenced that the hydrogel was resistant to decomposition in contrast to non- irradiated material. The determination of the swelling degree showed constant behavior over time, indicating a structure resistant to hydrolysis. This phenomenon also occurred during the test of stability in a cell culture medium. Additionally, microscopic analysis of the sample revealed an amorphous matrix with the presence of porosity. Thus, the findings reveal the synthesis of a novel material that has desirable attributes for its potential application in pharmaceutical and biomedical areas.

Effect of gamma sterilization on the properties of microneedle array transdermal patch system.

Soluble microneedles (MNs) of four different hydrophilic polymers namely sodium carboxymethyl cellulose (CMC), polyvinylpyrrolidone (PVP) K30, PVP K90 and sodium hyaluronate (HU) were fabricated by mold casting technique. When exposed to gamma radiation, a dose of 25 kilogray (kGy) was found to render the microneedle (MN) sterile. However, CMC was found to form MNs with poor mechanical properties, whereas PVP K30 MNs were drastically deformed upon exposure to applied dose as observed in bright field microscopy. Scanning electron microscopy (SEM) revealed that morphology of PVP K90 and HU MNs were not significantly affected at the applied dose. The appearances of characteristic peaks of irradiated MNs of PVP K90 and HU in Fourier-transform infrared spectra suggested structural integrity of the polymers on irradiation. Differential scanning calorimetry (DSC) indicated gamma irradiation failed to alter the glass transition temperature and thus mechanical properties of PVP K90 MNs. However, DSC and Powder X-ray Diffraction (PXRD) conclusively indicated that the degree in crystallinity of HU was substantially reduced on irradiation. In vitro dissolution profiles of sterile PVP K90 and HU MNs were similar to un-irradiated MNs with a similarity factor (f2) of 64 and 54, respectively. In vivo dissolution studies in human subjects indicated that sterile MNs of PVP K90 and HU exhibited dissolution of 78.45 ± 1.09 and 78.57 ± 0.70%, respectively, after 20 min. The studies suggested that PVP K90 and HU could be suitable polymers to fabricate soluble MNs as the structural, morphological, microstructural and dissolution properties remained unaltered post γ sterilization.

Convection-Induced vs. Microwave Radiation-Induced in situ Drug Amorphization.

The aim of the study was to investigate the suitability of a convection oven to induce in situ amorphization. The study was conducted using microwave radiation-induced in situ amorphization as reference, as it has recently been shown to enable the preparation of a fully (100%) amorphous solid dispersion of celecoxib (CCX) in polyvinylpyrrolidone (PVP) after 10 min of continuous microwaving. For comparison, the experimental setup of the microwave-induced method was mimicked for the convection-induced method. Compacts containing crystalline CCX and PVP were prepared and either pre-conditioned at 75% relative humidity or kept dry to investigate the effect of sorbed water on the amorphization kinetics. Subsequently, the compacts were heated for 5, 10, 15, 20, or 30 min in the convection oven at 100 °C. The degree of amorphization of CCX in the compacts was subsequently quantified using transmission Raman spectroscopy. Using the convection oven, the maximum degree of amorphization achieved was 96.1% ± 2.1% (n = 3) for the conditioned compacts after 30 min of heating and 14.3% ± 1.4% (n = 3) for the dry compacts after 20 min of heating, respectively. Based on the results from the convection and the microwave oven, it was found that the sorbed water acts as a plasticizer in the conditioned compacts (i.e., increasing molecular mobility), which is advantageous for in situ amorphization in both methods. Since the underlying mechanism of heating between the convection oven and microwave oven differs, it was found that convection-induced in situ amorphization is inferior to microwave radiation-induced in situ amorphization in terms of amorphization kinetics with the present experimental setup.

Carbon dot cross-linked polyvinylpyrrolidone hybrid hydrogel for simultaneous dye adsorption, photodegradation and bacterial elimination from waste water.

The creation of a polymeric hydrogel from polyvinylpyrrolidone (PVP) cross-linked by Carbon Quantum Dots (CD) for the adsorption and photocatalytic degradation of both cationic and anionic dyes. PVP, an important biocompatible constituent and often surplus in cosmetic industry, was carboxylated through NaOH refluxing and covalently conjugated to surface amine functionality of CD derived from lemon juice and Cysteamine. The hybrid hydrogel was obtained from PVP-CD covalent conjugate by careful manipulation of pH and found to possess better rheological properties than only carboxylate-PVP. The monolayer physisorption of the dyes on the hydrogel was affected by hydrogen bonding, dispersion or inductive effect, and π-π interaction with the polymer backbone as well as the CD that followed pseudo-second-order kinetics. Degradation of the adsorbed dyes was instated by the unique Reactive Oxygen Species (ROS) generating ability of the CD embedded in the hydrogel matrix upon exposure to sunlight, the mechanism of which is also unveiled. The same CD-induced ROS was found to effectively annihilate both gram-positive and gram-negative bacteria in real polluted water in less than 10 min of photoexcitation of the hydrogel. The hydrogel was restored by mild acid wash that is able to perform dye adsorption and photo-degradation upto four cycles.

Quantification of microwave-induced amorphization of celecoxib in PVP tablets using transmission Raman spectroscopy.

In this study, the influence of drug load on the microwave-induced amorphization of celecoxib (CCX) in polyvinylpyrrolidone (PVP) tablets was investigated using quantitative transmission Raman spectroscopy. A design of experiments (DoE) setup was applied for developing the quantitative model using two factors: drug load (10, 30, and 50% w/w) and amorphous fraction (0, 25, 50, 75 and 100%). The data was modeled using partial least-squares (PLS) regression and resulted in a robust model with a root mean-square error of prediction of 2.5%. The PLS model was used to study the amorphization kinetics of CCX-PVP tablets with different drug content (10, 20, 30, 40 and 50% w/w). For this purpose, transition Raman spectra were collected in 60 s intervals over a total microwave time of 10 min with an energy input of 1000 W. Using the quantitative model it was possible to measure the amorphous fraction of the tablets and follow the amorphization as a function of microwaving time. The relative amorphous fraction of CCX increased with increasing microwaving time and decreasing drug load, hence 90 ±â€¯7% of the drug was amorphized in the tablets with 10% drug load whereas only 31 ±â€¯7% of the drug was amorphized in the 50% CCX tablets. It is suggested that the degree of amorphization depends on drug loading. The likelihood of drug particles being in direct contact with the polymer PVP is a requirement for the dissolution of the drug into the polymer upon microwaving, and this is reduced with increasing drug load. This was further supported by polarized light microscopy that revealed evidence of crystalline particles and clusters in all the microwaved tablets.

Highly dynamic PVP-coated silver nanoparticles in aquatic environments: chemical and morphology change induced by oxidation of Ag(0) and reduction of Ag(+).

The fast growing and abundant use of silver nanoparticles (AgNPs) in commercial products alerts us to be cautious of their unknown health and environmental risks. Because of the inherent redox instability of silver, AgNPs are highly dynamic in the aquatic system, and the cycle of chemical oxidation of AgNPs to release Ag(+) and reconstitution to form AgNPs is expected to occur in aquatic environments. This study investigated how inevitable environmentally relevant factors like sunlight, dissolved organic matter (DOM), pH, Ca(2+)/Mg(2+), Cl(-), and S(2-) individually or in combination affect the chemical transformation of AgNPs. It was demonstrated that simulated sunlight induced the aggregation of AgNPs, causing particle fusion or self-assembly to form larger structures and aggregates. Meanwhile, AgNPs were significantly stabilized by DOM, indicating that AgNPs may exist as single particles and be suspended in natural water for a long time or delivered far distances. Dissolution (ion release) kinetics of AgNPs in sunlit DOM-rich water showed that dissolved Ag concentration increased gradually first and then suddenly decreased with external light irradiation, along with the regeneration of new tiny AgNPs. pH variation and addition of Ca(2+) and Mg(2+) within environmental levels did not affect the tendency, showing that this phenomenon was general in real aquatic systems. Given that a great number of studies have proven the toxicity of dissolved Ag (commonly regarded as the source of AgNP toxicity) to many aquatic organisms, our finding that the effect of DOM and sunlight on AgNP dissolution can regulate AgNP toxicity under these conditions is important. The fact that the release of Ag(+) and regeneration of AgNPs could both happen in sunlit DOM-rich water implies that previous results of toxicity studies gained by focusing on the original nature of AgNPs should be reconsidered and highlights the necessity to monitor the fate and toxicity of AgNPs under more environmentally relevant conditions.

Poly(N-vinylpyrrolidone)-modified surfaces for biomedical applications.

Poly(N-vinylpyrrolidone) (PVP), an important water soluble synthetic polymer, has many desirable properties including low toxicity, chemical stability, and good biocompatibility. Since PVP is hemocompatible and physiologically inactive, it has been used as a blood plasma substitute. Surface modification with PVP has been investigated extensively over the past few years as a means of preventing nonspecific protein adsorption. PVP may therefore be seen as a promising antifouling surface modifier comparable to poly(ethylene glycol) (PEG). In this review, various approaches for the design and preparation of PVP-modified surfaces are summarized and potential biomedical applications of these PVP-modified materials are indicated. Finally, some perspectives on future research on PVP for surface modification are discussed.

[Stability of probucol-polyvinylpyrrolidone solid dispersion systems].

After solid dispersion systems of probucol-polyvinylpyrrolidone K30 (1 : 9 in weight ratio) were exposed to light (10000 lx) for 7 days, 84% of the probucol remained. Commercial probucol fine granules were thus fairly stable under light exposure. When solid dispersion systems were stored in heat-sealed packages at relative humidity (R.H.) of 75% and 92% for 30 days at 30°C, the weight of the samples increased by 22% and 43%, respectively. When these solid dispersion systems were dissolved in water, the probucol concentration decreased with the duration of storage. The crystalline nature of probucol in the solid dispersion systems could not be detected by powder X-ray diffraction or differential scanning calorimetry. After passing the dissolution medium through the membrane filter, retention time of the residue on the filter in the HPLC method corresponded to that of probucol. These results suggest that the partial crystallization of probucol in the solid dispersion systems may occur during storage under these conditions. Solid dispersion systems in heat-sealed packages were fairly stable when stored under room conditions or in light-resistant tightly sealed containers for 5 months.

Effect of molecular weight on the ultrasonic degradation of poly(vinyl-pyrrolidone).

The ultrasonic degradation of poly(vinyl-pyrrolidone) (PVP) of different initial molecular weights was studied at a fixed temperature. The effect of solution concentration on the rate of degradation was investigated. A method of viscometry was used to study the degradation behavior and kinetic model was developed to estimate the degradation rate constant. The results were indicated that the rate of ultrasonic degradation increased with increasing molecular weight. It was found that rate constant decreases as the concentration increases. The calculated rate constants correlated in terms of inverse concentration and relative viscosity of PVP solutions. This behavior in the rate of degradation was interpreted in terms of viscosity and concentration of polymer solution. With increasing solution concentration, viscosity increases and it causes a reduction in the cavitation efficiency thus, the rate of degradation will be decreased. The experimental results show that the viscosity of polymers decreased with ultrasonic irradiation time and approached a limiting value, below which no further degradation took place. This study confirms the general assumption that the shear forces generated by the rapid motion of the solvent following cavitational collapse are responsible for the breakage of the chemical bonds within the polymer. The effect of polymer concentration can be interpreted in terms of the increase in viscosity with concentration, causing the molecules to become less mobile in solution and the velocity gradients around the collapsing bubbles to, therefore, become smaller.

Oxidation of polyvinylpyrrolidone and an ethoxylate surfactant in phase-inversion wastewater.

In this paper, components of an industrial wastewater that cause operational problems during biological treatment were oxidized by UV light and hydrogen peroxide (UV/H202). Preoxidation of wastewater was shown to remove polyvinylpyrrolidone (PVP) and ethoxylate surfactant and increase overall biodegradability. Several UV intensities and hydrogen peroxide concentrations were tested to find optimal conditions for the complete depolymerization of PVP in a synthetic wastewater composed of high concentrations of hydroxyl radical scavengers. To compare treatment options, absorption isotherms for PVP on granular activated carbon (GAC) in water and in the synthetic phase-inversion wastewater matrix were determined. The data were extrapolated to estimate the cost of using UV/H2O2, GAC, or off-site treatment. It was found that UV/H2O2 pretreatment was economically viable. Incomplete oxidation of an ethoxylate surfactant increased foaming tendency and foam stability; however, extended oxidation (> 90 minutes) destroyed the foam.

Femtosecond laser direct writing of metallic microstructures by photoreduction of silver nitrate in a polymer matrix.

Continuous silver microstructures were produced by three-dimensional (3-D) direct laser writing using a femtosecond-pulsed laser beam with polyvinylpyrrolidone (PVP) films containing silver ions. The lines drawn by scanning a tightly focused laser beam ranged from 200 nm to 1.7 microm. Using a sample solution of high density of silver nitrate, a continuous silver line with a resistivity of 3.48 x 10(-7) ohms m was produced. Not only 3-D microstructures such as pyramidal models but also hybrid microstructures comprising polymer and silver lines were demonstrated. The 3-D direct laser writing of metallic microstructures has potential for application to 3-D electrical wiring of electronic devices and MEMS devices.

Photopolymerization and shrinkage kinetics of in situ crosslinkable N-vinyl-pyrrolidone/poly(epsilon-caprolactone fumarate) networks.

Biodegradable, injectable and in situ photocrosslinkable macromers based on fumaric acid and polycaprolactone (PCLF) were prepared and characterized by FTIR, 1HNMR, and 13CNMR spectroscopy. The multifunctional macromers dissolved in N-vinyl pyrollidone (NVP) were photopolymerized by visible light irradiation in the presence of camphorquinone as photoinitiator. The photocrosslinking reaction was monitored by measuring shrinkage strain and shrinkage strain rate. The degree of photopolymerization reaction i.e. degree of conversion (DC%) was traced using FTIR spectroscopy. A three level factorial design was developed to study the effects of initiator concentration, NVP concentration, and molecular weight of PCLF upon photocrosslinking characteristics including degree of conversion and shrinkage strain. Results revealed that although neat PCLF was photopolymerized, but it was putty like after 220 seconds of irradiation and showed a very low degree of conversion (29%). Adding about 20% NVP caused a dramatic increase in its degree of conversion (63.33%). Increasing NVP up to 50% resulted in a decrease in DC% because of lower reactivity of NVP and leaving more unreacted NVP monomers. Sol fraction studies supported these results indicating that at higher NVP concentration, most of NVP and PCLF have not undergone the crosslinking reaction, leading to 55% decrease in DC%. Shrinkage strain measurement also confirmed the FTIR results.

Studies on PVP hydrogel-supported luminol chemiluminescence: 1. Kinetic and mechanistic aspects using multivariate factorial analysis.

The chemiluminescent oxidation of luminol by hydrogen peroxide in the presence of hemin is revisited in an UV-C cross-linked PVP hydrogel. Chemiluminescence properties such as initial light intensity (I(0)), area of emission (S) and observed rate constants (k(obs)) are studied, varying the concentration of all reactants using a multivariate factorial approach.

Viscoelasticity of radiation-formed PVA/PVP hydrogel.

The dynamic rheological behaviour of gamma-irradiated 12.8 wt% poly(vinyl alcohol) (PVA), 12.8 wt% poly(vinyl pyrrolidone) (PVP), and a blend of 8 wt% PVA and 4.8 wt% PVP aqueous solutions have been studied pre- and post-gelation. The non-irradiated solutions displayed rheological behaviour typical of dilute to semi-dilute polymer solutions, with the complex viscosity being independent of the frequency and shear rate (i.e. Newtonian behaviour) over the range of frequencies tested and the loss modulus G"(omega) and storage modulus G'(omega) being nearly proportional to omega and omega2, respectively. After a set of doses of gamma-radiation, the magnitudes of the dynamic moduli G'(omega) and G"(omega) increased as the absorbed dose increased, with notable differences between the two homopolymers and the blend. The stages of gelation were effectively monitored by means of dynamic rheological measurements, allowing the possible mechanisms of network formation to be elucidated. The doses required for gelation of the PVA, PVP, and blend samples, determined on the basis of the Winter and Chambon criteria for gelation, were found to be 12 kGy for the 12.8 wt% PVA, 4 kGy for the 12.8 wt% PVP, and 5 kGy for the 8 wt% PVA/4.8 wt% PVP solutions. The unexpected lower gelation dose demonstrated by the blend sample, compared with predictions based on the blend composition, and the associated gelation mechanism are also discussed.

Microwave disinfection of denture base materials colonized with Candida albicans.

STATEMENT OF PROBLEM: Infection of denture materials with Candida albicans is common and contributes to denture stomatitis. PURPOSE: This 3-phase investigation examined: (1) the efficacy of microwave irradiation against C albicans colonized on 3 soft denture liners and 1 heat-polymerized denture base resin, and (2) the effect of this irradiation on the hardness of the materials tested. MATERIAL AND METHODS: In phase 1, an experimental protocol was developed. Sterilized specimens from 2 denture base soft liners and 1 heat-polymerized acrylic resin denture base material (n = 45 each) were inoculated with C albicans. Two thirds of the specimens were irradiated in a 60 Hz microwave oven for 5 minutes (dry). C albicans growth was then assessed with streaked blood agar plates and thioglycollate broth. One third of the specimens were not irradiated and served as controls. Pretest and posttest Shore A hardness values were obtained and compared. For phase 2, 15 specimens from each material group were subjected to irradiation (while immersed in water) for 5 minutes; and, 15 from each material were subjected to 10- and 15-minute irradiation (dry), with subsequent sterility and change in hardness assessments completed as described in phase 1. In phase 3, 15 specimens from each material group were subjected to repeated 5-minute irradiation cycles (while immersed in water), and changes in hardness were examined. RESULTS: Only the 5-minute irradiated specimens immersed in water were effectively sterilized, as verified by the thioglycollate assay. The effect of repeated 5-minute irradiation cycles resulted in a significant change in hardness of the PermaSoft specimens. CONCLUSIONS: Five-minute irradiation, while immersed in water, killed all C albicans present on the materials tested; and, repeated 5-minute irradiation significantly affected the hardness of only the PermaSoft material.

[Experimental studies of new Polish hydrogel dressing materials HDR]. / Badania doswiadczalne nowych polskich opatrunków hydrozelowych o symbolu HDR.

Recently the spectrum of dressings was enriched, incorporating the so-called hydrogel dressing, made by Geistlich Sons Ltd. and Byk Goldbin-Konstanz referred to as "Geliperm". In Poland, HDR hydrogel dressings' technology was launched by Institute of Radiative Technology, Lódz+ Polytechnic. This type of dressing is obtained by radiative cross-linking of hydrophilic polymers. The experimental studies of the new Polish hydrogel materials were accomplished at the Department of Experimental Surgery and Biomaterials Research, the Chair of traumatologic Surgery, Medical Academy of Wroclaw. These studies concerned three kinds of hydrogel dressings, different in composition and irradiation conditions. HDR-1 10% of polyvinylpyrrolidone+, 1.5% of agar, 1.5% of polyethylene glycol 300, irradiated with 30 kGy (gamma radiation of 60Co); HDR-1 with neomycin--formula as above plus neomycin sulfate (2.5%); HDR-2 6% of polyvinylpyrrolidone++, 1% of agar, 1.5% of polyethylene glycol 300, irradiated with 25-27 kGy (gamma radiation of 60Co). The usable properties of the HDR dressings approximate those of the West German products. Owing to the lab tests, biological and in vitro examinations we had performed, it was possible to state that aqueous extracts of the hydrogel dressings subjected to assessment did'nt exhibit hemolytical or toxic activities in cellular tests, at the same time lacking an irritating effect. They cause a minimal tissular reaction and accelerate the process of healing.

[Polymer materials for biomedical use obtained by radiation methods. III. Radiation cross-linking of acrylamide and N-vinylpyrrolidone]. / Materialy polimerowe do celów biomedycznych otrzymywane metodami radiacyjnymi. III. Sieciowanie radiacyjne akryloamidu i N-winylopirolidonu.

The course of the radiation formation of hydrogels in aqueous solutions of acrylamide and N-vinylpyrrolidone was investigated on the base of gel-sol analysis. Using relations from Inokuti's equation as a test of crosslinking mechanism it was pointed out that creation of gels takes place according to classical mechanism e.g. through four-functional joining points. In the systems containing oxygen gel formation results from simultaneous crosslinking and degradation. On the base of swelling measurements of gels (ROCH method) the yields of radiation processes were calculated. Using a method of pulse radiolysis the absorption spectra of macroradicals were recorded, their structures discussed and the rate constants of crosslinking estimated.

[Polymer materials for biomedical use obtained by radiation methods. IV. The therapeutic system for local release of prostaglandins]. / Materialy polimerowe do celów biomedycznych otrzymywane metodami radiacyjnymi. IV. System terapeutyczny dla lokalnego uwalniania prostaglandyn.

The suitability of a radiation crosslinked polyvinylpyrrolidone++ as a therapeutical system for local prostaglandin monitoring has been studied. The effect of the dose and dose rate of ionizing radiation and of the time of heating the matrix on the content of gel fraction and the degree of hydrogel swelling was determined. The dimensions of a polymer network as dependent on the parameters of the process were calculated. For a chosen way of obtaining the therapeutical system, the release of prostaglandin F2 alpha in vitro was also estimated.

PIP: N-Vinylpyrrolidone was used in glass vials for polymerization, and the therapeutical system was secured by means of 30-35 mm long columns of 8.5 mm diameter that ended in a tip of 12 mm diameter of one side. Inserts were placed into an external solution and fastened by silk threads that served the potential future purpose of removal from the neck of the uterus during the medically-indicated term of use. Cobalt-60, Polish-made BK-10,000 cobalt bombs, and Canadian-made Gammacell were placed in the irradiation chamber to provide irradiation. Prostaglandin F2-alpha (PGF2-alpha) (Enzaprost made in Hungary) was used as active substance. The preparation contained 5 mg PGF2-alpha and 40.8 mg of sodium octanate in 1 ml of aqueous solution. The degree of PGF2-alpha release from the inserts was demonstrated by spectrophotometry. The 3-phase process included polymerization of N-vinylpyrrolidone by irradiation and the network of derived polymers; the introduction of prostaglandins into the inserts that were formed; and sterilization irradiation. After the irradiation of the matrix by doses greater than 4.5 kGy (kilo Gray) the presence of monomers could not be determined by spectrophotometry. Nonsoluble forms appeared in the matrix only under a dose exceeding 10 kGy: gel (consisting of a spatial network of polyvinylpyrrolidone (PVP) chains) swelled in the solution without being dissolved. The proportion of sol and gel made up 1. Under 30 kGy dose the rapidity of nonsoluble fraction formation decreased significantly, thus further irradiation was ineffective. The PVP matrix obtained by irradiating the system with a 25 kGy dose contained about 70% nonsoluble fraction and about 30% sol. This meant that after 24 hours of extraction about 30% of the matrix was precipitated. The content of nonsoluble fraction increased for over 10 seconds during the 1st minute, and then stabilized at around 80%. A similar 10% increase of gel content could be obtained by an additional 15 kGy dose, but this would only prolong the process and add to the cost of producing inserts of a particular shape and size whose gel content fraction formation required about 30 minutes. Heating of the PvP inserts at 383 degrees Kelvin (K) after 25 kGy irradiation yielded a degree of 25 of equilibrium swelling (absorption of 25 times more water than their mass). It is sufficient to place the inserts in a 1 ml solution of PGF2-alpha solution for 1 hour in order to introduce 5 mg of it into them; but for deeper penetration 3 hours in required. After drying the finished inserts for 15 hours, in vitro experiments showed that 85% of PGF2-alpha was released into Ringer solution at 310 K after 3 hours. The above process is detailed in a patent application.