Gelatin‐carbohydrate phase‐separated hydrogels as bioactive carriers in vaginal delivery: Preparation and physical characterizations

The current study focuses on the alteration of properties of the gelatin hydrogels using polysaccharides (e.g., maltodextrin, dextran, and sodium carboxymethyl cellulose) for probable use in vaginal delivery of antimicrobials. The hydrogels were prepared by varying the proportions of gelatin and polysaccharides and were characterized by microscopy, mechanical testing, and impedance spectroscopy. Metronidazole (MZ), drug of choice for the treatment of bacterial vaginosis, was incorporated within the hydrogels. In vitro release studies of MZ from the hydrogels was studied in‐depth using modified Franz's diffusion cell. Antimicrobial efficiency of the MZ‐loaded hydrogels was tested against E. coli and B. subtilis. The results suggested that the incorporation of polysaccharides resulted in the phase‐separated hydrogels. The properties of the hydrogels was found be suitable for vaginal delivery. The drug release and antimicrobial efficiency from the hydrogels suggested that the developed hydrogels may be used for the delivery of antimicrobials in the vaginal lumen. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40445.     

Development and characterization of gelatin‐based hydrogels,emulsion hydrogels,and bigels: A comparative study

This study was designed to examine the physicochemical and electrical properties of gelatin‐based hydrogels, emulgels, and bigels. The chemical studies suggested an increase in hydrogen bonding in the emulgel and bigel when sesame oil (SO; representative vegetable oil) and SO organogel (OG; representative OG) were incorporated within the gelatin matrix. The emulgel and bigel showed better mechanical properties and higher electrical impedances compared to the hydrogel. The hydrogel showed similar swelling at pH 1.2 and 7.2. The swelling of the emulgel and bigel was higher at pH 7.2. The formulations were found to be highly hemocompatible; this indicated their biocompatible nature. Ciprofloxacin, a model antimicrobial drug, was incorporated within the formulations. The release of the drug was found to be diffusion‐mediated. The antimicrobial efficiency of all of the drug‐loaded formulations was found to be equivalent. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41502.     

Preparation and characterization of poly(D,L‐lactic‐co‐glycolic acid) nanoparticles containing 3‐(benzoxazol‐2‐yl)‐7‐(N,N‐diethyl amino)chromen‐2‐one

Nanoparticles (NPs) of poly(D,L ‐lactic‐co‐glycolic acid) containing the compound 3‐(benzoxazol‐2‐yl)‐7‐(N,N‐diethyl amino)chromen‐2‐one (C2) were prepared by the solvent‐evaporation technique with a mean loading efficiency of 74.0 ± 3.0%. Size distribution studies, done with dynamic light scattering and scanning electron microscopy, revealed that these particles were spherical in shape, with a mean diameter of 253 nm, a low polydispersity, and a tendency toward aggregation; the last was confirmed by the low ζ potential. A low release profile was observed for C2 when the NPs were dispersed in Hank's buffer (pH = 7.4); this was related to the low porosity of the NPs and the extremely low diffusivity of C2 in water. Differential scanning calorimetry data presented a glass‐transition temperature depression caused by an increase in the NP molecular mobility after the incorporation of C2. Spectroscopic and photophysical data exploring the capabilities of C2 as a fluorescent probe suggested a high microviscosity for the environment in which the probe was allocated, which was most likely due to strong polar interactions involving ester groups from the polymer and the diethylamino moiety from C2. The cellular toxicity and uptake of C2 and NP–C2 systems were evaluated with B16‐F10 murine cells, which showed that C2 (in solution or encapsulated) was nontoxic and able to be located inside the neoplasic cells. Besides, the encapsulation method was capable of maintaining the drug's properties and improved the drug delivery to the target cell. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Acrylic bone cements modified with poly(ethylene glycol)‐based biocompatible phase‐change materials

The high polymerization temperature of acrylic bone cements used in hip replacement implantation may cause thermal necrosis of surrounding tissues. In order to reduce the polymerization temperature, acrylic bone cement has been modified with a biocompatible polymeric phase‐change material (PCM) based on poly(ethylene glycol) (PEG) of different molecular weights and stabilized with potato starch. Structural and morphological studies were performed, and the thermal and mechanical properties were investigated. The incorporation of PEG‐based PCM led to a decrease in the polymerization temperature of bone cement from 70 °C for unmodified cement to 58 °C for modified cement. Modified cement materials were stable in incubation tests, although acoustic analysis data revealed a decrease in propagation speed after incubation, which indicates formation of material defects (pores, cracks, voids, etc.) due to water activity. However, in the regeneration process, these defects can be filled by freshly grown bone tissue leading to better incorporation of bone cement replacements into tissue. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43898.     

Synthesis and characterization of curable methacrylate‐based monomers

The synthesis of new methacrylate‐based, curable macromonomers, 4,4′‐bis[2‐hydroxy‐3‐aminopropylmethacrylate] diphenyl ether (BHAPE) and 4,4′‐bis[2‐hydroxy‐3‐aminopropylmethacrylate] diphenyl methane (BHAPM), is reported. BHAPE and BHAPM were prepared by the reaction of glycidyl methacrylate (GMA) with 4,4′‐diaminodiphenyl ether and 4,4′‐diaminodiphenyl methane, respectively. The progress of the reaction was monitored by thin‐layer chromatography (TLC), and the structure of the monomers was characterized by Fourier transform infrared (FTIR) and ¹H‐NMR spectroscopy. Thermal curing of the monomers was conducted in a differential scanning calorimeter (DSC) with peroxide as the initiator. Thermal curing of the monomers showed the highest rate at 100°C with the activation energy value in the range 80–90 kJ distilled/mol. The water absorption properties of the cured samples in water, acidic, and basic solutions were studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of the inclusion of PEG on the solid‐state properties and drug release from polylactic acid films and microcapsules

The use of poly(lactic acid) (PLA) for controlled drug delivery applications was limited by unfavorable physical properties such as hydrophobicity, high intrinsic crystallinity, low permeability, and high glass transition temperatures. This research used polyethylene glycols (PEGs) of varying molecular weights (300–18,500 g/mol) and concentrations (0–50% w/w) to modify the permeability, intrinsic crystallinity, glass transition temperature, residual solvent levels, and release of a model drug, 5‐flurouracil (5FU), from monolithic films and microcapsules fabricated with PLA. The films were fabricated by solvent casting from methylene chloride. The microcapsules were formed by a coacervation method by using a methylene chloride/hexane solvent/nonsolvent system. Compared to PLA films, all PLA : PEG films showed the following: (1) a glass transition temperature between 40 and 55°C, (2) 5–8% lower residual solvent levels, and (3) enhanced permeability to 5FU. These results suggested that the incorporation of PEG improves the physical properties of PLA films to enable fabrication of controlled release delivery systems. Similar to the films, incorporation of PEG also enhanced the permeability of PLA microcapsules to 5FU. However, high intrinsic crystallinity, dual endothermal character for PLA melting, and significant burst release of 5FU in PLA : PEG microcapsules may limit their development for controlled drug delivery applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2025–2030, 2004     

Synthesis,characterization, and curing of {2,6–bis‐[2‐(bis‐oxiranylmethyl‐amino)‐methylbenzyl]‐phenyl}‐bis‐oxiranylmethylamine (BPBOMA)

The curing behavior of epoxy resin prepared by reacting epichlorohydrin with amine functional aniline acetaldehyde condensate (AFAAC) was investigated using AFAAC as a curing agent. The epoxy resin, {2,6‐bis‐[2‐(bis‐oxiranylmethyl‐amino)‐methylbenzyl]‐phenyl}‐bis‐oxiranylmethylamine (BPBOMA), was characterized by FTIR and ¹H‐NMR spectroscopy, viscosity measurement, and determination of epoxy content. Analysis of the curing reaction was followed by differential scanning calorimetry (DSC) analysis. To investigate the curing kinetic with AFAAC, dynamic DSC scans were made at heating rates of 5, 10, 15, and 20°C/min. The activation energy and frequency factor of the AFAAC formulation were evaluated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3168–3174, 2006     

Investigation of thermally conducting phase‐change materials based on polyethylene/wax blends filled with copper particles

This article reports on the morphology, melting and crystallization behavior, thermal stability, tensile properties, and thermal conductivity of phase‐change materials (PCM) for thermal energy storage. These materials were based on a soft Fischer‐Tropsch paraffin wax (PCM) blended with low‐density polyethylene, linear low‐density polyethylene, and high‐density polyethylene. These immiscible blends were melt‐mixed with copper (Cu) microparticles (up to 15 vol %) to improve the thermal conductivity in the matrix material. The presence of the Cu microparticles in the PCMs did not significantly change the crystallization behavior, thermal stability, or tensile properties of the blend composites in comparison with the corresponding polyethylene/wax blends and polyethylene/Cu composites. The observed differences were related to the fact that the wax seemed to have a higher affinity for the Cu particles than any of the polyethylenes, and so it crystallized as a layer around the Cu particles. The thermal conductivity of the samples increased almost linearly with increasing Cu content, but the samples had slightly lower values than the corresponding polyethylene/Cu composites, probably because of the lower thermal conductivity of the wax. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Time–temperature–transformation cure diagrams of phenol–formaldehyde and lignin–phenol–formaldehyde novolac resins

In this study, the time–temperature– transformation (TTT) cure diagrams of the curing processes of several novolac resins were determined. Each diagram corresponded to a mixture of commercial phenol–formaldehyde novolac, lignin–phenol–formaldehyde novolac, and methylolated lignin–phenol–formaldehyde novolac resins with hexamethylenetetramine as a curing agent. Thermomechanical analysis and differential scanning calorimetry techniques were applied to study the resin gelation and the kinetics of the curing process to obtain the isoconversional curves. The temperature at which the material gelled and vitrified [the glass‐transition temperature at the gel point (_gelT_g)], the glass‐transition temperature of the uncured material (without crosslinking; T_g0), and the glass‐transition temperature with full crosslinking were also obtained. On the basis of the measured of conversion degree at gelation, the approximate glass‐transition temperature/conversion relationship, and the thermokinetic results of the curing process of the resins, TTT cure diagrams of the novolac samples were constructed. The TTT diagrams showed that the lignin–novolac and methylolated lignin–novolac resins presented lower T_g0 and _gelT_g values than the commercial resin. The TTT diagram is a suitable tool for understanding novolac resin behavior during the isothermal curing process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Studies on the critical phase‐transition behavior of cholesteric N‐phthaloyl chitosan/dimethyl sulfoxide solutions by five techniques

A selectively side‐modified chitosan derivative, N‐phthaloyl chitosan (PhthCs), was prepared. Five techniques, including circular dichroism (CD) spectropolarimetry, ultraviolet–visible (UV–vis) spectroscopy, small‐angle light scattering (SALS), polarized optical microscopy (POM), and differential scanning calorimetry (DSC), were simultaneously applied to investigate the order–disorder phase transition for the lyotropic PhthCs/dimethyl sulfoxide system. POM observations suggested that the critical concentration was 48 wt %, which agreed well with the DSC measurements. A four‐leaf SALS picture was recorded in biphasic solutions. The four‐leaf type became a circular symmetric scattering picture with a further increase in the concentration. A sharp peak at 330 nm was recorded in dilute isotropic solutions with CD measurements. The sharp peak turned into a broad tailed peak from 330 to 800 nm after the phase transition occurred. The sharp peak was induced by a chromophore (phthoyl group). The broad peak was attributed to the formation of short‐range‐ordered organization in the concentrated solutions. In UV–vis studies, when the system varied from isotropic to anisotropic, the absorption band turned into platform. These five techniques were proven to be feasible methods for measuring the phase transition of cholesteric liquid crystals. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 583–586, 2003     

Effect of poly(styrene‐co‐maleic anhydride) imidization on the miscibility and phase‐separation temperatures of poly(styrene‐co‐maleic anhydride)/poly(vinyl methyl ether) and poly(styrene‐co‐maleic anhydride)/ poly(methyl methacrylate) blends

The objective of this work was to study the miscibility and phase‐separation temperatures of poly(styrene‐co‐maleic anhydride) (SMA)/poly(vinyl methyl ether) (PVME) and SMA/poly(methyl methacrylate) (PMMA) blends with differential scanning calorimetry and small‐angle light scattering techniques. We focused on the effect of SMA partial imidization with aniline on the miscibility and phase‐separation temperatures of these blends. The SMA imidization reaction led to a partially imidized styrene N‐phenyl succinimide copolymer (SMI) with a degree of conversion of 49% and a decomposition temperature higher than that of SMA by about 20°C. We observed that both SMI/PVME and SMI/PMMA blends had lower critical solution temperature behavior. The imidization of SMA increased the phase‐separation temperature of the SMA/PVME blend and decreased that of the SMA/PMMA blend. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Novel amphiphilic polymer gel electrolytes based on (PEG‐b‐GMA)‐co‐MMA

Amphiphilic conetwork–structured copolymers containing different lengths of ethylene oxide (EO) chains as ionophilic units and methyl methacrylate (MMA) chains as ionophobic units were prepared by free radical copolymerization and characterized by FTIR and thermal analysis. Polymer gel electrolytes based on the copolymers complexed with liquid lithium electrolytes (dimethyl carbonate (DMC) : diethyl carbonate (DEC) : ethylene carbonate (EC) = 1 : 1 : 1 (W/W/W), LiPF₆ 1.0M) were characterized by differential scanning calorimetry and impedance spectroscopy. A maximum ion conductivity of 4.27 × 10^?4 S/cm at 25^oC was found for the polymer electrolyte based on (PEG2000‐b‐GMA)‐co‐MMA with long EO groups. Moreover, the effect of temperature on conductivity of the amphiphilic polymer electrolytes obeys the Arrhenius equation. The good room temperature conductivity of the polymer electrolytes is proposed to relate to the enhancement in the amorphous domain of the copolymers due to their amphiphilic conetwork structure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanical and barrier properties of edible starch–protein‐based films

The present investigation dealt with the mechanical properties, water‐vapor transmission behavior at different relative humidity conditions, and DSC thermograms of edible films formulated using various proteins (casein, gelatin, albumin) in combination with starch and nonthermal as well as intense thermal blending. Nonthermal blended film showed in the DSC thermogram a double T_g, indicating poor miscibility of the components and, hence, a poor film‐forming property. However, the DSC thermogram of all the films based on intense thermal blending showed a single T_g, indicating the complete molecular miscibility of the components. Casein‐based film showed a lower water‐vapor transmission rate, water gain at different relative humidity conditions, and higher tensile strength compared to its counterparts containing gelatin and albumin. Since the casein–starch blend gave better film properties, a blend of hydrophobic carnauba wax and casein was prepared to compare the properties of hydrophilic–hydrophilic and hydrophobic–hydrophilic blends. Both these blends compared well with respect to the water‐vapor transmission rate. Wax‐based film showed multiphased behavior in the DSC thermograms and the percent elongation was lower as compared to the casein–starch blend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 64–71, 2003     

Polyurethanes based on 2,2‐Dinitropropane‐1,3‐diol and 2,2‐bis(azidomethyl)propane‐1,3‐diol as potential energetic binders

On the base of 2,2‐bis(azidomethyl)propane‐1,3‐diol (BAMP) and 2,2‐dinitropropane‐1,3‐diol (DNPD) four different polyurethanes were synthesized in a polyaddition reaction using hexamethylene diisocyanate (HMDI) and diisocyanato ethane (DIE). The obtained prepolymers were mainly characterized using vibrational spectroscopy (IR) and elemental analysis. For determination of low and high temperature behavior, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used. Investigations concerning friction and impact sensitivities were carried out using a BAM drop hammer and friction tester. The energetic properties of the polymers were determined using bomb calorimetric measurements and calculated with the EXPLO5 V6.02 computer code. The obtained values were compared with the glycidyl azide polymer (GAP). The compounds turned out to be insensitive toward friction (>360 N) and less sensitive toward impact (40 J). The good physical stabilities, along with their sufficient thermal stability (170–210 °C) and moderate energetic properties renders these polymers into potential compounds for applications as binders in energetic formul;ations. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43991.     

Improvements in the thermal conductivity and mechanical properties of phase‐change microcapsules with oxygen‐plasma‐modified multiwalled carbon nanotubes

The thermal properties and mechanical properties are the key factors of phase‐change microcapsules (microPCMs) in energy‐storage applications. In this study, microPCMs based on an n‐octadecane (C18) core and a melamine–urea–formaldehyde (MUF) shell supplemented with O₂‐plasma‐modified multiwalled carbon nanotubes (CNTs) were synthesized through in situ polymerization. Meanwhile, two different addition methods, the addition of modified CNTs into the emulsion system or into the polymer system, were compared and examined. Scanning electron microscopy micrographs showed that the microPCMs were spherical and had a broadened size distribution. Fourier transform infrared testing demonstrated that the modified CNTs did not affect C18 coated by MUF resin. The results indicate that the thermal conductivity and mechanical properties of the microPCMs were remarkably improved by the addition of a moderate amount of modified CNTs, but the heat enthalpy and encapsulated efficiency decreased slightly. Moreover, the thermal conductivity and mechanical properties of microPCMs modified with CNTs directly added to the polymer system were superior to those with CNTs added to emulsion system. In particular, when 0.2 g of modified CNTs were added to the polymer system, the thermal conductivity of the microPCMs was improved by 225%, and the breakage rates of the microPCMs at 4000 rpm for 5, 10, and 20 min decreased by 74, 72, and 60%, respectively, compared with that of the microPCMs without modified CNTs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45269.     

Synthesis and characterization of polyethylene glycol acrylate crosslinking copolymer as solid–solid phase change materials

A kind of crosslinking copolymer as solid–solid phase change material (PCM) is synthesized by copolymerization. The scope of PCM applications is often severely limited by their heat stablility and phase transition state. The solid–solid phase change materials we obtained retain basic state during phase change transitions. The crosslinking polymer is heat stable under 300° and the latent heat of crystalline and latent heat of melting is on the average of 120 J/g and 140J/g, respectively. The property of thermal stability and heat storaged is related to crosslinking density of the gel. The property of thermal stability and high latent heat may expand the scope of PCMs applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39755.     

Optimal designs for constant‐heating‐rate differential scanning calorimetry experiments for polymerization kinetics: nth‐order kinetics

Optimal designs have been constructed for differential scanning calorimetry (DSC) experiments conducted under constant‐heating‐rate conditions for materials that are a priori assumed to follow nth‐order kinetics. Two different operating scenarios are considered, including single‐scan and multiscan DSC experiments for eight different kinetic parameter combinations representing a range of typical polymeric curing reactions. The resulting designs are studied to determine which kinetic model parameters are influential in determining the optimal design. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of salts in the Hofmeister series and solvent isotopes on the gelation mechanisms for hydroxypropylmethylcellulose hydrogels

The effects of various inorganic salts and isotopic solvents on the thermal gelation behavior of hydroxypropylmethylcellulose (HPMC) in aqueous solutions were examined by micro-differential scanning calorimetry and rheological measurements. It was found that salting-out salts, such as NaCl, promoted the sol–gel transition of HPMC at a lower temperature. An analysis of solvent isotope effects on the changes in the temperature at maximum heat capacity (T_m) with salt concentration showed that interchain hydrogen bonding (hydrogen bonding between the hydroxyl groups of different HPMC chains) was involved in the sol–gel transition, and its strength depended on the temperature and salt concentration. It was demonstrated that the effectiveness of anionic species in changing the T_m of the HPMC solutions was in the sequence of the Hofmeister series. Anionic species play a role in reducing T_m by their influence on the structure of the water, which in turn affects interactions between hydroxyl groups and water molecules, interchain hydrogen bonding, and the strength of the water cages prohibiting hydrophobic association. Rheological and microcalorimetric results indicated that the change in the thermodynamics of gelation of the HPMC aqueous solution was determined by the salt types and concentration, and the effect of monovalent salts was found to be more cooperative than that of multivalent salts on the sol–gel transition. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Release of fluorescent markers from phase‐separated gelatin‐maltodextrin hydrogels

Genipin‐crosslinked gelatin‐maltodextrin phase‐separated hydrogels consisting of gelatin‐continuous or bicontinuous microstructures were developed to regulate swelling and release behavior of four fluorescent markers of varying molecular weights [(fluorescein (332 Da) and FITC‐dextrans (FD) (4000–250,000 Da)]. Bicontinuous hydrogels showed significantly greater swelling than gelatin‐continuous hydrogels under all conditions (at pH 1.5 and 7.4 and three genipin/gelatin crosslinking ratios) (P < 0.05). With both microstructures, fluorescein showed the largest release rate and total release followed by FD 4000 Da, FD 40,000 Da, and FD 250,000 Da (P < 0.05). Marker molecular weight, pH, and crosslink ratio all affected the rate and amount of release. The mode of transport for the solvent and all markers was Fickian or slightly anomalous, with diffusional exponent (n) values ranging from 0.35 to 0.64. These results demonstrated that with the proper combination of crosslink density, solvent pH, and microstructure, hydrogels with a specified swelling behavior may be developed. This, coupled with a marker of appropriate size, can lead to controllable levels and rates of release. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis,spectral, and thermal characterization of photosensitive poly(ether–ester)s containing α,β‐unsaturated ketone moieties in the main chain derived from 2,6‐bis[4‐(3‐hydroxypropyloxy)‐3‐methoxybenzylidene]cyclohexanone

A series of photosensitive poly(ether–ester)s containing α,β‐unsaturated ketone moieties in the main chain were synthesized from 2,6‐bis[4‐(3‐hydroxypropyloxy)‐3‐methoxybenzylidene]cyclohexanone (BHPMBCH) and aliphatic and aromatic diacid chlorides. The diol precursor, BHPMBCH, was synthesized from 2,6‐bis(4‐hydroxy‐3‐methoxybenzylidene)cyclohexanone and 3‐bromo‐1‐propanol. The solubility of the polymers was tested in various solvents. The intrinsic viscosity of the synthesized polymers, determined by an Oswald viscometer, was found to be 0.06–0.80 g/dL. The molecular structures of the monomer and polymers were confirmed by Fourier transform infrared, ultraviolet–visible, ¹H‐NMR, and ¹³C‐NMR spectral analyses. The thermal properties were studied with thermogravimetric analysis and differential scanning calorimetry. The thermogravimetric analysis data revealed that the polymers were stable up to 220°C and started degrading thereafter. The thermal stability initially increased with increasing spacer length and then decreased due to negative effects of the spacer. The self‐extinguishing properties of the synthesized polymers were studied by the determination of the limiting oxygen index values with Van Krevelen's equation. In addition, the photocrosslinking properties of the polymer chain were studied with UV spectroscopy, and we observed that the rate of photocrosslinking increased significantly with increasing methylene carbon chain length of the acid spacer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011