Biodegradable Chitosan-g-Poly(methacrylamide) Microspheres for Controlled Release of Hypertensive Drug

Chitosan-g-poly(methacrylamide) (CS-g-PMAAm) was synthesized by redox polymerization. The synthesized graft copolymers were used to prepare microspheres (MS) by water/oil (W/O) emulsion technique and cross-linked with glutaraldehyde (GA). Developed microspheres were encapsulated using enalapril maleate (ENAM) as a model drug (hypertension) and characterized by fourier transform infrared spectroscopy, differential scanning calorimetry and scanning electron microscopy. The physico-chemical properties of the microspheres were studied by calculating drug entrapment efficiency, and drug release kinetics. % of encapsulation efficiency (% EE) increased with increase in drug loading and methacrylamide (MAAm) content. The minimum % EE (65.2 ± 1.6) was observed in case of microsphere containing 40 % MAAm, 5 % ENAM and 10 mL glutaraldehyde. The release profiles indicate that formulation containing highest (10 mL) crosslinking agent microspheres has the slow release.     

Poly(Lactic Acid)-co-Aspartic Acid Copolymers: Possible Utilization in Drug Delivery Systems

The synthesis and characterization of poly(lactic acid)-co-aspartic acid copolymers (PLA-co-Asp) were presented. Subsequently, the synthesized PLA-co-Asp copolymers were tested as biodegradable carriers in drug delivery systems. PLA-co-Asp copolymers were synthesized by solution polycondensation procedure, using different molar ratios PLA/l-aspartic acid (2.33/1, 1/1, 1/2.33), manganese acetate and phosphoric acid as catalysts and N,N′-dimethyl formamide (DMF)/toluene as solvent mixture. The copolymers were characterized by FT-IR and ¹H-NMR spectroscopy, gel permeation chromatography (GPC), DSC and TG-DTG analyses. Diclofenac sodium, a non steroidal anti-inflammatory drug was subsequently loaded into PLA-co-Asp copolymers. The in vitro drug release experiments were done by dialysis of the copolymer/drug systems, in phosphate buffer solution (pH = 7.4, at 37 °C) and monitored by UV spectroscopy.     

Characterization of Atrazine-Loaded Biodegradable Poly(Hydroxybutyrate-Co-Hydroxyvalerate) Microspheres

Polyhydroxybutyrate-co-hydroxyvalerate microspheres (PHBV-MS) were prepared as a delivery system for the herbicide atrazine (ATZ). Characterization of the system included investigation of in vitro release properties and genotoxicity. ATZ − PHBV-MS particle diameters showed a size distribution range of 1–13 μm. Differential scanning calorimetry analyses indicated that ATZ was associated with the PHBV microparticles. The release profiles showed a different release behavior for the pure herbicide in solution, as compared with that containing ATZ-loaded PHBV-MS. Korsmeyer–Peppas model analyses showed that atrazine release from the microparticles occurred by a combination of diffusion through the matrix and partial diffusion through water-filled pores of the PHBV microparticles. A Lactuca sativa test result showed that the genotoxicity of ATZ-loaded PHBV-MP was decreased in relation to ATZ alone. The results demonstrate a viable biodegradable herbicide release system using atrazine for agrochemical purposes.     

A Novel Biodegradable Green Poly(l-Aspartic Acid-Citric Acid) Copolymer for Antimicrobial Applications

Poly (l-aspartic acid-citric acid) green copolymers were developed using thermal polymerization of aspartic acid (ASP) and citric acid (CA) followed by direct bulk melt condensation technique. Antibacterial properties of copolymer of aspartic acid based were investigated as a function of citric acid content. This study is focused on the microorganism inhibition performance of aspartic acid based copolymers. Results showed that inhibition properties increase with increasing citric acid content. Characterization of obtained copolymers was carried out with the help of infrared absorption spectra (FTIR), x-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermo gravimetric analysis (TGA). The antibacterial activity of copolymers against bacteria like E-coli, Bacillus and pseudomonas was investigated. The copolymers showed excellent antimicrobial activities against three types of microorganisms. Overall studies indicated that the above copolymers possess a broad wound dressing activity against above three types of bacteria and may be useful as antibacterial agents.     

Application of Poly (Agar-Co-Glycerol-Co-Sweet Almond Oil) Based Organo-Hydrogels as a Drug Delivery Material

In this study, it was aimed to investigate the synthesis, characterization and drug release behaviors of organo-hydrogels containing pH-sensitive Agar (A), Glycerol (G), Sweet Almond oil (Wu et al. in J Mol Struct 882:107–115, 2008). Organo-hydrogels, which contained Agar, Glycerol and different amounts of Sweet Almond oil, were synthesized via the free-radical polymerization reaction with emulsion technique using glutaraldehyde or methylene bis acrylamide crosslinkers. Then, the degree of swelling, bond structures, blood compatibility and antioxidant properties of the synthesized organo-hydrogels were examined. In addition, Organo-hydrogels which loaded with Ceftriaxone and Oxaliplatin were synthesized with the same polymerization reaction and release kinetics were investigated. In vitro release studies were performed at media similar pH to gastric fluid (pH 2.0), skin surface (pH 5.5), blood fluid (pH 7.4) and intestinal fluid (pH 8.0), at 37 °C. The effects on release of crosslinker type and sweet almond oil amount were investigated. Kinetic parameters were determined using release results and these results were applied to zero and first-order equations and Korsmeyer-Peppas and Higuchi equations. Diffusion exponential was calculated for drug diffusion of organo-hydrogels and values consistent with release results were found.

     

Characterization and Release Kinetics of Allylthiosufinate and its Transforments from Poly(d,l-Lactide) Microspheres

In this work was described poly(d,l-lactide) microwave synthesis using tin(II) 2-ethylhexanoate initiated ring-opening polymerization. Polymerization was performed at 100 °C with monomer to initiator molar ratio ([M]/[I]) of 5,000 in 30 min. The achieved number average molar mass of obtained polymers (determined by gel permeation chromatography) was 102,320 g/mol, with the polydispersion index, Q, 2.80. Structural characterization was performed by FT-IR spectroscopy followed characteristic bands. For applicative purposes the obtained polymer was purified during the procedure of microsphere preparation. Biodegradable microspheres prepared from poly(d,l-lactide) have been widely studied in recent years and have become well established controlled drug delivery systems. In this work microspheres were loaded with allyl thiosulfinate (allicin) and its transforments products (ajoene and vinyldithiine), as pharmacological active substances. The morphology of the microspheres was analyzed using a scanning electron microscope. Allicin was synthesized by acid oxidation of allyl disufide and purification of obtained products by liquid–liquid extraction with diethyl ether. Obtained allicin, purity 73%, was transformed using microwave in acetone solution, at solvent boiling temperature, for 5 min. For the quality and quantity analysis of allicin and its transformation process was used LC/MS chromatography. (E)- and (Z)-ajoene were detected at retention time 3.1 and 3.3 min, respectively, whence 3-vynil-4H-1,2-dithiine and 2-vynil-4H-1,3-dithiine were detected at 4.3 and 4.8 min, respectively. Retention time of allicin was 2.93 min, according to liquid chromatography results. HPLC method was used for assessment of pharmaceutical substances (alicine and alicine transforments) releasing from microspheres at room temperature in solutions with different pH (pH = 3 and pH = 8) for 24 h.     

Miscibility Studies of Polysaccharide Xanthan Gum/PVP Blend

Miscibility characteristics of Xanthan gum and Poly (vinyl pyrrolidone) (PVP) in common solvent water were studied by viscometry, ultrasonic velocity and density techniques at 30 and 50 °C. Blend films of Xanthan gum/PVP were prepared by solution casting method and characterized by scanning electron microscopic (SEM) and differential scanning calorimeter (DSC) techniques. Using the viscosity data, interaction parameters of Chee’s (μ) and Sun’s (α) were computed to determine their miscibility. The values obtained revealed that blends were miscible when PVP content is up to 70% in blend at 30 °C. Xanthan gum/poly (vinyl pyrrolidone) blends showed miscibility in all composition at 50 °C. The results were then confirmed by ultrasonic velocity, density, and DSC techniques. Compatibility in the above compositions may be due to the formation of hydrogen bonding between the carbonyl group in PVP and hydroxyl group in Xanthan gum. Further, the results revealed that change in temperature had significant effect on the miscibility of Xanthan gum/Poly (vinyl pyrrolidone) blends.     

Evaluation of Poly(ethylene-terephthalate) Products of Chemical Recycling by Differential Scanning Calorimetry

Poly (ethylene-terephthalate), (PET) bottles waste was chemically recycled by glycolysis and hydrolysis. The depolymerization processes were carried out in different time intervals from 5 to 360 min, in two different molar ratios of PET/EG, 1:5 and 1:18 and at different temperatures. The PET glycolysis leads to formation of bis(2-hydroxy-ethyl)terephthalate (BHET) monomer and PET oligomers with hydroxyl and carboxyl end groups while PET hydrolysis is followed by formation of monomers terephthalic acid (TPA) and ethylene glycol (EG). Fractions of monomers and oligomers were further characterized by FTIR spectroscopy and by differential scanning calorimetry (DSC). The results show that DSC is successful method to describe the different structures of oligomers formed during chemical recycling of PET.     

Novel Environmentally Friendly Copolymers Carboxymethyl Starch Grafted Poly(Lactic Acid)

Modified natural polymers have been gaining increasing scientific interest for many years. In this study carboxymethyl starch (CMS) was grafted with L(+)-lactic acid (LA) in different molar ratios CMS/LA (1/36, 1/22 and 1/12), resulting carboxymethyl starch-g-poly(lactic acid) (CMS-g-PLA) copolymers. The grafting reaction was carried out by solution polycondensation procedure in toluene and stannous 2-ethyl hexanoate Sn(Oct)₂ as catalyst was utilized. Poly(lactic acid) (PLA) was synthesized in the same conditions with the copolymers for comparative analyses of the physico-chemical and thermal properties. The copolymers and PLA were structurally and morphologically characterized by FT-IR, ¹H-NMR spectroscopy, WAXD and SEM analyses, taking CMS as reference. The molecular weight of the copolymers, CMS and PLA were determined, using a dynamic light scattering technique. The thermal behavior of the products was studied by DSC and TG-DTG analyses. The CMS-g-PLA graft copolymers exhibited lower Tg and thermal stability than pure CMS.     

Formulation and Characterization of Sodium Alginate g-Hydroxy Ethylacrylate Bio-Degradable Polymeric Beads: In Vitro Release Studies

Novel type of highly swollen beads were prepared by grafting 2-hydroxyethylacrylate onto biodegradable Sodium alginate (SA) via free-radical polymerization using potassium persulphate as an initiator and Triprolidine hydrochloride as a model drug. Evidence of grafting was obtained by fourier transform infrared spectroscopic technique. Morphological properties of the beads were studied by SEM analysis. Thermal properties and crystallinity of the beads were characterized using differential scanning calorimetry and thermogravimetric analysis and X-ray diffraction techniques, respectively. Dissolution experiments were performed to study the release profiles at 37?°C in phosphate buffer solution (pH-7.4). Effect of monomer content, crosslinking agent and drug/polymer ratio on swelling properties and release profiles were also comparatively studied. A dissolution result concludes that drug release decreases with increasing crosslinker content. The highest release (96%) was obtained for the beads prepared with 0.5?mL crosslinking agent. Equilibrium swelling degree also supports the drug release profiles confirming SA-g-HEA beads showed better release profiles compare to plain SA beads.     

Biodegradable Chitosan Hydrogels for In Vitro Drug Release Studies of 5-Flurouracil an Anticancer Drug

Novel semi-interpenetrating network (semi-IPN) hydrogels based on biodegradable chitosan and poly(N-isopropylacrylamide-co-2-acrylamido-2-methyl-1-propanesulfonic acid) were prepared by free radical addition polymerization. Fourier transform infrared spectra and scanning electron microscopy were used to characterize the semi-IPN hydrogels and the results showed that chitosan and poly(N-isopropylacrylamide-co-2-acrylamide-2-methyl-1-propanesulfonic acid) semi-IPN hydrogels were coupled by the interaction of the functional groups present in NIPAAm, CS and AMPS units. The PNIPAAm and P(NIPAAm-AMPS)/CS hydrogels have lower critical solution temperature and the same was confirmed with the help of differential scanning calorimetry as well as with the temperature dependent swelling curves. The model anti cancer drug, 5-fluorouracil (5-FU) was loaded into the semi-IPN hydrogels, at ambient temperature. The 5-FU loading capacity and release behaviour were investigated with these hydrogels acting as carriers for controlled release. The released 5-FU concentration was calculated with the help of UV spectrophotometer at 266.5?nm.     

An Investigation into the Influence of C. moschata Leaves Extract on Physicochemical and Biological Properties of Biodegradable PCL/PLA Blend Film

Journal of Polymers and the Environment - Poly ε-caprolactone (PCL) synthesized by ring-opening polymerization method, and then it blended with polylactic acid (PLA). The blend was loaded with...     

Biodegradation of Pro-oxidant Filled Polypropylene Films and Evaluation of the Ecotoxicological Impact

The biodegradability of calcium stearate (CaSt) and cobalt stearate (CoSt) filled polypropylene (PP) films were investigated in this work. The PP films were prepared using melt blending technique followed by hot press moulding. On the basis of their tensile properties, the optimum amount of pro-oxidants was taken as 0.2 phr. Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were used for the characterization of optimized films. Presence of pro-oxidant in the PP was confirmed by the FTIR studies. Addition of pro-oxidants in the films decreased the thermal stability as revealed by TGA analysis. Crystallinity of the pro-oxidant filled PP decreased with addition of pro-oxidants as showen by DSC. The maximum biodegradation of CaSt and CoSt containing PP films was showen 7.65 and 8.34%, respectively with 0.2 phr. Both the microbial test and plant growth test (on corn and tomato) indicated that biodegradation intermediates were non toxic.     

Preparation and Properties of Biodegradable Poly(lactic acid)/Poly(butylene adipate-co-terephthalate) Blend with Epoxy-Functional Styrene Acrylic Copolymer as Reactive Agent

Poly (lactic acid) (PLA) and poly (butylene adipate-co-terephthalate) (PBAT) are biodegradable polyesters and can be blended by twin-screw extrusion. Epoxy-functional styrene acrylic copolymer (ESA) was used as reactive agent for PLA/PBAT blends and the mechanical properties, phase morphology, thermal properties, melt properties, and melt rheological behaviors of the blends were investigated. During thermal extrusion, ESA was mainly a chain extender for the PLA matrix but had no evident reaction with PBAT. The great improvement in the toughness of PLA based blends was achieved by the addition of PBAT of no less than 15 wt% and that of ESA of no more than 0.5 wt%. Although SEM micrographs and the reduced deviation of the terminal slope of G′ and G″ indicated better compatibility and adhesion between the two phases, the blend with ESA was still a two-phase system as indicated in DSC curves. Rheological results reveal that the addition of ESA increased the storage modulus (G′), loss modulus (G″) and complex viscosity of the blend at nearly all frequencies. The melt strength and melt elasticity of the blend are improved by addition of ESA.     

Process,Characterization and Biodegradability of Aliphatic Aromatic Polyester/Sisal Fiber Composites

The biodegradability, morphology, and mechanical properties of composite materials made of Poly(butylene adipate-co-terephthalate) (PBAT) and sisal fiber (SF) were evaluated. Composites containing acrylic acid-grafted PBAT (PBAT-g-AA/SF) exhibited noticeably superior mechanical properties due to greater compatibility between the two components. The dispersion of SF in the PBAT-g-AA matrix was highly homogeneous as a result of ester formation between the carboxyl groups of PBAT-g-AA and hydroxyl groups in SF and the consequent creation of branched and cross-linked macromolecules. Each composite was subjected to biodegradation tests in Rhizopus oryzae compost. Morphological observations indicated severe disruption of film structure after 60 days of incubation, and both the PBAT and the PBAT-g-AA/SF composite films were eventually completely degraded. Water resistance of PBAT-g-AA/SF was higher than that of PBAT/SF, although weight loss of composites buried in Rhizopus oryzae compost indicated that both were biodegradable, even at high levels of SF substitution. The PBAT-g-AA/SF films were more biodegradable than those made of PBAT, implying a strong connection between these characteristics and biodegradability.     

Biomedical Textiles Through Multifunctioalization of Cotton Fabrics Using Innovative Methoxypolyethylene Glycol-N-Chitosan Graft Copolymer

Multifunctioalization of cotton fabrics was developed by a novel finishing formulation. The method is based on chitosan-N-polyethylene glycol graft copolymer along with citric acid and sodium hypophosphite (SHP) as catalysts. Treatment of the cotton fabric resulted in the chemical attachment of the copolymer to the cotton fabric via bridging-based esterification where the latter involves reaction of one molecule of the polycarboxylic acid (citric acid) with both the amino group of the copolymer and the hydroxyl groups of cotton. Inclusion of the copolymer in the crosslinked structure of cotton as well as by hydrogen bonding and van der Waals forces are additionally possible. Synthesis of the copolymer was raised out by the reaction of chitosan with methoxy polyethylene glycol (MPEG) aldehyde followed by the reduction with sodium borohydride. MPEG was prepared by oxidation of PEG with acetic anhydride in dimethyl sulphoxide at room temperature. Methoxypolyethylene glycol-N-chitosan graft copolymer (MPEG-N-CTS) structure was confirmed by IR, NMR, X-RD and TGA techniques. The copolymer is soluble in water. The pad dry-cure method was used for the cotton fabrics treatment with aqueous solution of prepared copolymer along with citric acid and SHP. The so treated fabrics were monitored for copolymer content (expressed as N%), crease recovery, tensile strength, elongation at break, air permeability, water permeability, roughness, bursting strength and antibacterial activity. Fabric performances based on the outputs of these measurements advocate these multifunctionalized fabrics for use as medical textile.     

Reactive Blending of Biodegradable Polymers: PLA and Starch

Poly(lactic acid) (PLA) and starch are important biodegradable polymers. Mechanical properties of blends of PLA and starch using conventional processes were very poor because of incompatibility. In this study, PLA and starch were blended with a reactive agent during the extrusion process. The affects of the reactive blending were investigated and significant improvements were confirmed by measuring the tensile strength and elongation at break, IR spectra, and DSC.     

Investigation on the Influence of EVA Content on the Mechanical and Thermal Characteristics of Poly(lactic acid) Blends

Poly(lactic acid) (PLA) has gained considerable attention nowadays as a biocompatible polymer owing to its advantage of being prepared from renewable resources. PLA exhibits excellent tensile strength, fabricability, thermal plasticity and biocompatibility properties comparable to many petroleum based plastics. However, low heat distortion temperature, brittleness and slow crystallization rate limit the practical applications of PLA. In order to address these limitations, an attempt has been made in the current work to prepare binary blends of PLA with ethylene vinyl acetate (EVA) at different compositions via melt mixing technique. Systematic investigation on the mechanical properties, thermal degradation and crystallization behavior for PLA-EVA blends was carried out. The impact strength of binary blends of PLA–EVA was found to increase significantly by 176% for 15 wt% of EVA compared to virgin PLA. This is due to the strong interfacial adhesion among PLA and EVA resulting in brittle to ductile transition. Scanning electron microscopy analysis for impact fractured surfaces of binary blends of PLA implied the toughening effect of PLA by EVA. Thermogravimetry analysis results revealed that the activation energy of PLA–EVA blends decreased with increase in EVA content in the PLA matrix. While, differential scanning calorimetry results obtained for PLA–EVA blends revealed the improvement in crystallinity when compared with neat PLA. The effect of EVA on non-isothermal melt crystallization kinetics of PLA was also examined via DSC at various heating rates. Decreasing trend in the t_1/2 values indicated the faster rate of crystallization mechanism after addition of EVA in the PLA matrix.     

Action of soil microorganisms on PCL and PHBV blend and films

Poly(hydroxybutyrate-co-valerate) (PHBV) and poly(ε-caprolactone) (PCL) PCL/PHBV (4:1) blend films were prepared by melt-pressing. The biodegradation of the films in response to burial in soil for 30 days was investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG). The PHBV film was the most susceptible to microbial attack, since it was rapidly biodegraded via surface erosion in 15 days and completely degraded in 30 days. The PCL film also degraded but more slowly than PHBV. The degradation of the PCL/PHBV blend occurred in the PHBV phase, inducing changes in the PCL phases (interphase) and resulting in an increase of its crystalline fraction.     

Poly[(R)-3-hydroxy butyrate] Melt Processing: Strategy for Prevention of Degradation Reactions

Poly[(R)-3-hydroxy butyrate] (PHB) as well as all the components of the poly[(R)-3-hydroxy alkanoate]s (PHAs) family tend to degrade during processing at temperatures above their melting point via a hydrolytic mechanism induced by moisture attack and a concerted reaction mechanism induced by temperature. Therefore, the PHAs stabilization in the molten state is particularly important for production of biodegradable ecocompatible plastic items of commercial value. In order to refrain the indicated negative degradation effects, PHB was melt processed in a torque rheometer in the presence of a polymeric carbodiimide agent. Processed specimens were characterized by using FTIR, GPC, DSC, TGA and tensile properties. GPC analysis showed that the increase of the additive content in the formulation resulted in an increase of PHB molecular weight. However, decreasing in PHB thermal stability, glass transition temperature and mechanical properties, was observed with the increase of the additive amount. This behaviour most likely arises from the formation of new chemical structures promoted by the presence of the additive aimed at preventing the onset of hydrolitic processes.