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.     

Polyvinyl Alcohol (PVA)/Starch Bioactive Packaging Film Enriched with Antioxidants from Spent Coffee Ground and Citric Acid

The bioactive packaging polyvinyl alcohol (PVA)/starch films were prepared by incorporating combined antioxidant agents i.e. extracted spent coffee ground (ex-SCG) and citric acid. Effect of citric acid content on chemical compatibility, releasing of antioxidant, antibacterial activities, and physical and mechanical properties of PVA/starch incorporated ex-SCG (PSt-E) films was studied. The results of ATR-FTIR spectra showed that antioxidant agents of ex-SCG can penetrate into the film and the ester bond of blended films by citric acid was also observed. The presence of ex-SCG increased efficiency of antioxidant release and antimicrobial activity. The PSt-E film incorporated 30 wt% citric acid showed minimum inhibitory concentration against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). The incorporation of ex-SCG and citric acid into film showed a synergistic effect on antibacterial activity. The water resistance and kinetic moisture sorption improved with incorporation of citric acid. The tensile strength and biodegradability of samples were in range of 5.63–7.44 MPa and 65.28–86.64%, respectively. Based on this study, PSt-E film incorporated 30 wt% citric acid can be applied as novel food packaging materials.     

Ggum-poly(Itaconic Acid) Based Superabsorbents Via Two-Step Free-Radical Aqueous Polymerization for Environmental and Antibacterial Applications

Ggum-based conducting hydrogels possessing dye removal and antibacterial property were developed by two-step free-radical aqueous polymerization method. Conductivity was introduced with polyaniline (PANI) chains incorporated within the crosslinked network of Ggum-poly(itaconic acid) superabsorbent. The material properties of the synthesized samples were characterized using FTIR spectroscopy, thermal analysis and scanning electron microscopy techniques. Results showed that synthesized samples exhibited the best antibacterial activity against Gram-positive bacteria. Synthesized samples were found to be effective in removal of toxic methylene blue (MB) dye from the waste water. The adsorption kinetics of superabsorbents has been described by using pseudo first and pseudo second order kinetics models. Furthermore, application of hydrogels to improve the water retention properties of different soils was also studied for agricultural purpose.     

Effect of Gamma Radiation on the Properties of Crosslinked Chitosan Nano-composite Film

Chitosan nano-composite film crosslinked by citric acid and with glycerol as plasticizer and MgO as antibacterial agent was prepared by casting method. MgO nanoparticles were synthesized via calcination method in furnace at 500 °C for 4 h and characterized by X-ray diffraction and transmission electron microscope. The chitosan nano-composite film with composition chitosan/citric/glycerol/magnesium oxide (1 wt%:1 wt%:75 vol%:10 wt%) has high mechanical properties than other films. The effects of different irradiation doses on the mechanical, thermal and antibacterial activity were investigated. The tensile strength enhanced by increasing irradiation dose up to 10 kGy and the elongation negligible changed as irradiation dose increased. The thermal stability slightly increased up to dose 2.5 kGy then decreased with dose increment. The antimicrobial activity film was studied against white mulberry-borne bacterial pathogens either Gram positive or Gram negative bacteria and has positive impact of gamma irradiation on the antimicrobial activity. The use of the selected chitosan nano-composite film which irradiated by dose of 2.5 kGy and has magnesium oxide of average particle size 54.3 nm as new packaging materials found to improve storage quality and shelf-life of mulberry fruit.     

Preparation and Characterization of Polyaniline and Ag/ Polyaniline Composite Nanoporous Particles and Their Antimicrobial Activities

Polyaniline (PANI) and Ag/PANI nanoporous composite were prepared by an oxidative polymerization method. The oxidation process of PANI nanoparticles was occurred using (NH₄)₂S₂O₈ while the oxidation process of Ag/PANI nanoporous composite was occurred using AgNO₃ under the effect of artificial radiation. The structural, morphological, and optical properties of the PANI and Ag/PANI nanoporous structures were studied using different characterization tools. The results confirm the formation of polycrystalline nanoporous PANI and spherical nanoporous composite of Ag/PANI particles. Antibacterial activity tests against gram-positive bacteria, Bacillus subtilis and Staphylococcus aureus, and gram-negative bacteria, Escherichia coli, and Salmonella species were carried out using different concentrations of PANI nanoparticles and Ag/PANI nanoporous composites. PANI has not antibacterial effect against all studied pathogens. In contrast, Ag/PANI nanoporous composites possessed antibacterial activity that is identified by the zone of inhibition. The inhibition zones of bacteria are in order; Salmonella species?>?S. aureus?>?B. subtilis?>?E. coli. The inhibition zones of all bacteria increased with increasing concentrations of Ag/PANI nanoporous composites from 200 to 400 ppm then decreased with further increasing of the dose concentrations to 600 ppm. Finally, a simplified mechanism based on the electrostatic attraction is presented to describe the antimicrobial activity of Ag/PANI nanoporous composite.     

Preparation of Water-Insoluble Antibacterial Materials with Surface-Grafted Material PSt/SiO<Subscript>2</Subscript> and Their Antibacterial Activity

Styrene (St) was graft-polymerized onto the surfaces of micro-sized silica gel particles, and the surface-grafted composite particles PSt/SiO₂ were obtained. With the surface-grafted composite particles PSt/SiO₂ as a starting material, water-insoluble antibacterial materials with quaternary ‘onium’ salt-type were synthesized via two polymer reaction steps. The grafted polystyrene was first chloromethylated, resulting in grafted particles CMPS/SiO₂, and then quaterisation (QN) and quaternary phosphonium reaction (QP) were conducted with triethylamine, tri-n-butylamine and triphenyl phosphine as reagents, respectively. Two kinds of water-insoluble antibacterial materials, QN-PSt/SiO₂ and QP-PSt/SiO₂ were prepared. Their antibacterial property was mainly investigated by using Escherichia coli (E. coli) as a model bacterium and by adopting colony count method. The relationship between the chemical structure of the antibacterial group and antimicrobial activity for the water-insoluble antibacterial materials was studied in detail, and their antibacterial mechanism was investigated by TTC-dehydrogenase activity determination and extracellular DNA and RNA measurement methods. The experimental results show that QN-PSt/SiO₂ and QP-PSt/SiO₂ possess strong antibacterial activity. The main factors affecting the antibacterial ability of the water-insoluble materials are the chemical structure of the antibacterial groups, the bound density of the antibacterial groups on the surface of the water-insoluble antibacterial materials as well as the pH value of the medium. QP-PSt/SiO₂ has stronger antibacterial activity than QN-PSt/SiO₂; the QN-PSt/SiO₂ prepared with tri-n-butylamine has stronger antibacterial activity than that prepared with triethylamine; the water-insoluble material with higher bound density of the antibacterial groups has stronger antibacterial ability; as the pH value of the medium is over the isoelectric point of E. coli, the antibacterial ability is strengthened with the increase of pH value.     

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.     

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.     

Effects of Inorganic Antiseptic on the Properties of Zein-Based Active Films

Zein, one of corn processing byproducts, has excellent film-forming ability. However, zein does not have intrinsic antibacterial or antioxidant activity which limits its direct applicability as active food packaging material. In the present study, the rod-shaped micro-sized ZnO crystals were incorporated into zein films to construct zein-based active films as active packaging material with antibacterial property. The morphologies, structural analysis and sizes of ZnO crystals were analyzed by field emission scanning electron microscope and X-ray diffraction. Prepared zein films were evaluated for ZnO loading and distribution. Furthermore, antibacterial activities on Gram-negative bacteria and Gram-positive bacteria were tested by using the disc diffusion method. Lastly, the stability of zein-based active films under the different storage temperature and humidity was investigated. The results showed that zein based-active films had well mechanical properties, stability and antibacterial activities, which were related to the sizes of ZnO crystals in films.     

The basic properties of poly(lactic acid) produced by the direct condensation polymerization of lactic acid

Poly(lactic acids) with high molecular weights have been synthesized by direct condensation polymerization of lactic acid. These polymers have good mechanical properties and can be processed into products such as cups, film, and fiber, which can be used as compostable materials. This polymerization method can be applied to the synthesis of copolymers of lactic acid and other hydroxyacids. The properties of poly(lactic acid) and copolymers synthesized by the direct process are different from those of polymers obtained by the conventional lactide process.     

Environmentally-Friendly Synthesis of Ag Nanoparticles by Fusarium sporotrichioides for the Production of PVA/Bentonite/Ag Composite Nanofibers

Membranes and filters made of nanofibers can have many medicines and water treatment applications. The use of silver nanoparticles (AgNPs) with antibacterial activity in these structures improve their efficiency. However, due to the toxicity of the compounds used in the chemical synthesis of AgNPs, in this study, AgNPs were obtained through a biological process using Fusarium sporotrichioides. AgNPs preparation conditions were optimized, including F. sporotrichioides medium and AgNO₃ concentration. Next, a PVA nanofiber membrane with bentonite and AgNPs (Bio-AgNPs or Chem-AgNPs) was prepared using electrospinning. The optimal conditions for the production of Bio-AgNPs were the culture of F. sporotrichioides in the MGYP culture medium and 12 M of AgNO₃. The Bio-AgNPs particle size and zeta potential were 58 nm and ??16.8 mV, respectively, with antibacterial activity. The PVA/NB/AgNPs nanofibers operation conditions included 7.5% w/w PVA, 3% w/w bentonite, and AgNPs 5% w/w at a voltage of 11 kV, feed rate of 0.5 mL/h, and 15 cm distance between the needle and the collector. The average diameter of the PVA/NB/Bio-AgNPs nanofibers was 230 nm. Also, the presence of silver in the nanofibers was confirmed through EDX and XRD methods. The antibacterial assay of the nanofibers showed that the inhibition zone of PVA/NB/Bio-AgNPs against E. coli and S. aureus was 0.62 and 0.36 mm, which is better than PVA/NB/Chem-AgNPs and comparable with chloramphenicol. The produced membrane is suitable for water treatment, food packaging, and wound dressing because of its good thermal, mechanical, and antibacterial properties.

     

Large-scale experiments for microbiological evaluation of measures for safeguarding sulfidic mine waste

In the framework of a German-Romanian scientific cooperation, experiments were performed to evaluate feasible and cheap techniques for the safe storage of mine waste to prevent acid rock drainage (ARD). A large four-chamber percolator (4CP) was installed in a waste heap at Ilba Mine, Romania, to test the effect of biocides and alkaline layers on the bacteria causing acid rock drainage (ARD). The 4CP consisted of four chambers each containing 65 m3 of sulfidic waste material. The 4CP enabled the transfer of laboratory results to a technical scale. The detergent sodiumdodecylsulfate (SDS) was proved to be active against the leaching bacteria. Organotrophic micro-organisms were not effected by the SDS application. The alkaline layers caused an increase of pH, however, a decrease of cell numbers was measured only in adjacent ore layers, but not in the whole ore body. A rapid evaluation of the effects of these countermeasures on ARD formation became possible by microcalorimetric activity measurements for bioleaching.     

Solvent-Free Polymerization of l-Aspartic Acid in the Presence of d-Sorbitol to Obtain Water Soluble or Network Copolymers

l-Aspartic acid was thermally polymerized in the presence of d-sorbitol with the goal of synthesizing new, higher molecular weight water soluble and absorbent copolymers. No reaction occurred when aspartic acid alone was heated at 170 or 200 °C. In contrast, heating sorbitol and aspartic acid neat or with ammonium hydroxide gave a mixture of water soluble and insoluble copolymers of polysuccinimide and sorbitol. In the presence of phosphoric acid, sorbitol aspartate ester copolymers having both water soluble and highly swollen gel components were formed. These results indicate that polysaccharides such as sorbitol can readily react to form copolymer ester/amides with aspartic acid and such copolymers may have utility as biodegradable water soluble and swellable polyampholytes.     

Microbial degradation of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) in compost

The microbial degradation of tensile test pieces made of poly(3-hydroxybutyrate) [P(3HB)] or copolymers with 10% [P(3HB-co-10%3HV)] and 20% [P(3HB-co-20%3HV)] 3-hydroxyvaleric acid was studied in small household compost heaps. Degradation was measured through loss of weight (surface erosion) and changes in molecular weight and mechanical strength. It was concluded, on the basis of weight loss and loss of mechanical properties, that P(3HB) and P(3HB-co-3HV) plastics were degraded in compost by the action of microorganisms. No decrease inM _w could be detected during the degradation process. The P(3HB-co-20%3HV) copolymer was degraded much faster than the homopolymer and P(3HB-co-10%3HV). One hundred nine microbial strains capable of degrading the polymersin vitro were isolated from the samples used in the biodegradation studies, as well as from two other composts, and identified. They consisted of 61 Gram-negative bacteria (e.g.,Acidovorax facilis), 10 Gram-positive bacteria (mainlyBacillus megaterium), 35Streptomyces strains, and 3 molds.     

Suspension Polymerization of Poly(l-lactide-co-p-dioxanone) in Supercritical Carbon Dioxide

Biodegradable copolymers of l-lactide(l-LA) and p-dioxanone(PDO) were synthesized in supercritical carbon dioxide (scCO₂) with stannous octoate as the ring-opening catalyst and a fluorocarbon polymer surfactant as an stabilizer. Fine powderous products were achieved when more than 90% (w/w) l-LA was fed. Scanning electron micrographic images and laser diffraction particle size analysis of the products showed the mean diameter of particles greatly increased as the content of PDO increased. The obtained polymers had the number-average molecular weights ranging from 15,000 to 26,000 g mol⁻¹ (polydispersity index ranging from 1.3 to 2.1) according to the gel permeation chromatography measurements. The polymer structure was characterized by NMR spectroscopy, indicating the formation of copolymers. Thermal properties of the obtained polymers investigated using differential scanning calorimetry showed that the morphology of products was directly relevant to the crystallinity of the copolymers. The polymerization of l-LA and PDO copolymers in scCO₂ is also proposed as a novel production technique for high-purity, biodegradable polymers.     

Synthesis of Polylactide-b-Poly (Dimethyl Siloxane) Block Copolymers and Their Blends with Pure Polylactide

The synthesis of polylactide (PLA)-b-poly (dimethyl siloxane) (PDMS) linear block copolymers and their use in blends with pure-PLA are described. PLA-b-PDMS linear block copolymers were obtained by the transesterification reaction in chloroform solution between poly(dimethyl siloxane) bis (2-aminopropyl ether) (molecular weight 2,000?Da) with PLA in the presence of stannous octoate. Molecular weights (Mw) of the block copolymers were varied from 53,800 to 63,600?Da while that of pristine PLA was 73,600?Da. The copolymers obtained were purified by fractional precipitation and then characterized by ¹H NMR, FTIR, GPC, viscometry and DSC techniques. Blends of pure PLA with PLA-b-PDMS block copolymers displayed improved elastic properties (elongation up to 140%) compared to pure PLA (elongation ~9%). Thermal, mechanical and morphological characterization of the blends were also conducted.     

Isolation and Identification of Microorganisms Able to Grow on the Polyester Amide BAK 1095

The polyester amide BAK 1095 is fully degraded by microorganisms. Bacteria that can grow on this polymer were isolated from various environments, such as freshwater, saltwater, arable land, woodland and compost. The mechanism of polymer degradation was examined using selected isolates. It was discovered that the bacteria selectively cleave the polymer at its ester bonds, releasing low-molecular water-soluble oligoamides. These can then be metabolised by other microorganisms [1, 2, 3]. The isolates were also tested for their ability to break down other ester-containing polymers such as Degranil W 50, a linear polyester urethane urea. Eight of the 12 strains examined were also able to break down this polymer.The isolated microorganisms predominantly belong to the genus Bacillus. Mesophilic, halophilic and thermophilic species were isolated. The studies show that polyester amide-degrading bacteria occur in numerous ecosystems and provide data on the microbial breakdown of random copolymers. Information was also obtained on the mechanism involved in the microbial breakdown of polyester amides.     

Studies on the enzymatic and fungal degradation of cross-linked gelatin and its graft copolymers

Glutaraldehyde cross-linked gelatin was graft copolymerized with acrylic acid, acrylamide, vinyl acetate, methyl acrylate, and methyl methacrylate either individually or in combination. The enzymatic and fungal degradation of these graft copolymers with trypsin, pepsin, and mixed cultures ofAspergillus niger, Penicillium ochrochloron, Penicillium funiculosum, andTrichoderma viride was studied for short and extended periods. The weight loss suffered by the samples, the weight of biomass formed, the nitrogen content, and the pH of the culture medium were determined. With the help of these data, the extent of utilization of graft copolymers by fungi as a sole source of carbon was estimated. The samples with less than 100% grafting and with a ratio of polymethyl methacrylate content (L) to polyacrylic acid (H) content (L/H values) lower than 1.0 were readily and extensively degraded.IICT Communication No. 3375.     

Citric Acid and Vitamin C as Coupling Agents for the Surface Coating of ZrO<Subscript>2</Subscript> Nanoparticles and Their Behavior on the Optical,Mechanical, and Thermal Properties of Poly(vinyl alcohol) Nanocomposite Films

A series of bio-nanocomposites (BNC)s were fabricated through solution casting method. At first, the surfaces of ZrO₂ NPs were functionalized with citric acid and Vitamin C as green modifier agents. Then, PVA as polymer matrix was embedded with different contents (4, 8 and 12 wt%) of modified ZrO₂ (m-ZrO₂) NPs with the aim of ultrasonic irradiation process. The resulting BNCs were studied by various techniques. Thermal stability of obtained BNCs was enhanced after NPs’ addition to the PVA matrix. Optical activity of these new BNCs makes them potential candidate for UV shielding material. Lastly, the tensile strengths of the BNCs were increased in comparison to the pure PVA.     

Synthesis, Characterization, and Hydrolytic Degradation of Copolymers of 2-Methylene-1,3-dioxepane with Ethylene and with Styrene

2-Methylene-1,3-dioxepane (MDP) was copolymerized with ethylene (E) at a pressure of approximately 1000 psi and a temperature of approximately 70°C with AIBN as the free radical initiator. The copolymers obtained, poly(MDP-co-E), were characterized by elemental analysis, IR, ¹H-NMR and ¹³C-NMR spectroscopy, DSC, and GPC. The copolymers contained 2–15 mol% ester units. MDP was also copolymerized with styrene (S) at 120°C with di-t-butyl peroxide as the initiator to prepare the copolymer, poly(MDP-co-S). The number-average molecular weights of both types of copolymers were in the range of 6000 to 11,000, and the weight-average molecular weights were in the range of 9000 to 17,000. The melting temperatures of poly(MDP-co-E) decreased with increasing ester unit content in the copolymer. For the MDP-S copolymers, the glass transition temperatures decreased with increasing ester unit content. Both poly(MDP-co-E) and poly(MDP-co-S) were degraded by methanolysis, and their molecular weights decreased by the expected amounts based on the ester unit content.