Methods for Assessment of Biodegradability of Plastic Films in Soil

Traditional and novel techniques were tested and compared for their usefulness in evaluating biodegrad-ability claims made for newly formulated “degradable” plastic film products. Photosensitized polyethylene (PE), starch-PE, extensively plasticized polyvinyl chloride (PVC), and polypropylene (PP) films were incorporated into aerobic soil. Biodegradation was measured for 3 months under generally favorable conditions. Carbon dioxide evolution, residual weight recovery, and loss of tensile strength measurements were supplemented, for some films, by gas chromatographic measurements of plasticizer loss and gel permeation chromatographic (GPC) measurement of polymer molecular size distribution. Six- and 12-week sunlight exposures of photosensitized PE films resulted in extensive photochemical damage that failed to promote subsequent mineralization in soil. An 8% starch-PE film and the plasticized PVC film evolved significant amounts of CO₂ in biodegradation tests and lost residual weight and tensile strength, but GPC measurements demonstrated that all these changes were confined to the additives and the PE and PVC polymers were not degraded. Carbon dioxide evolution was found to be a useful screening tool for plastic film biodegradation, but for films with additives, polymer biodegradation needs to be confirmed by GPC. Photochemical cross-linking of polymer strands reduces solubility and may interfere with GPC measurements of polymer degradation.     

The fate of ‘biodegradable’ plastics in municipal leaf compost

Summary Blends of starch with polypropylene, starch with polyethylene, polycaprolactone with polyethylene, and a copolymer of -hydroxybutyrate and -hydroxyvalerate (PHB/V) were exposed to degrading leaves in a municipal leaf composting operation. Every month for 6 months, duplicate samples were analyzed for changes in weight and tensile properties, and many of these samples were further analyzed for changes in molecular weight and surface morphology. All results were compared to controls which were incubated for 6 months in moist, sterile leaves at a leaf compost temperature. Very little change was noted for any of the polyolefin blends over the 6-month period. In contrast, PHB/V samples showed massive deterioration with substantial weight loss. Although there was a decrease in molecular weight and a loss of tensile properties in leaf-exposed PHB/V films, the sterile control films also showed similar changes, but without weight loss. Of the microbial isolates from film surfaces, only fungi possessed PHB/V depolymerase activity.     

Suitability of E-tongue Sensors to Assess Taste-Masking of Pediatric Liquids by Different Beverages Considering Their Physico-chemical Properties

Manipulation of liquid oral drugs by mixing them into foodstuff is a common procedure for taste-masking of OTC pharmaceuticals when administered to children. However, the taste-masking capability of such application media is not systematically evaluated, and recommendations for suitable media are hardly published. In this study, a sensor array of commercially available and self-developed electronic tongue sensors was employed to assess the taste-masking efficiency of eight different beverages (tap water, apple juice, carrot juice, fennel tea, fruit tea, milk, cocoa, and Alete meal to drink) on the OTC pharmaceuticals Ambroxol-ratiopharm®, Cetirizin AL, and Laxoberal® by multivariate data analysis. The Euclidean distances between each pure application medium and its corresponding drug mixture were used as an indicator for the taste-masking efficiency and correlated to the physico-chemical properties of the beverages. Thus, the pH value, the viscosity, as well as the fat and sugar content of the beverages were included, whereas only the viscosity appeared to be insignificant in all cases. The sugar content as well as the fat content and pH value emerged to be a significant variable in taste-masking efficiency for some of the tested drug products. It was shown that the applied electronic tongue sensors were capable to demonstrate the impact of the physico-chemical properties of the application media on their taste-masking capacity regardless of their non-selectivity towards these characteristics.     

Different effects of night versus day high temperature on rice quality and accumulation profiling of rice grain proteins during grain filling

High temperature has adverse effects on rice yield and quality. The different influences of night high temperature (NHT) and day high temperature (DHT) on rice quality and seed protein accumulation profiles during grain filling in indica rice ‘9311’ were studied in this research. The treatment temperatures of the control, NHT, and DHT were 28°C/20°C, 27°C/35°C, and 35°C/27°C, respectively, and all the treatments were maintained for 20 days. The result of rice quality analysis indicated that compared with DHT, NHT exerted less effect on head rice rate and chalkiness, whereas greater effect on grain weight. Moreover, the dynamic accumulation change profiles of 61 protein spots, differentially accumulated and successfully identified under NHT and DHT conditions, were performed by proteomic approach. The results also showed that the different suppressed extent of accumulation amount of cyPPDKB might result in different grain chalkiness between NHT and DHT. Most identified isoforms of proteins, such as PPDK and pullulanase, displayed different accumulation change patterns between NHT and DHT. In addition, compared with DHT, NHT resulted in the unique accumulation patterns of stress and defense proteins. Taken together, the mechanisms of seed protein accumulation profiles induced by NHT and DHT during grain filling should be different in rice, and the potential molecular basis is discussed in this study.     

Study of novel rosin-based biomaterials for pharmaceutical coating

The film forming and coating properties of Glycerol ester of maleic rosin (GMR) and Pentaerythritol ester of maleic rosin (PMR) were investigated. The 2 rosin-based biomaterials were initially characterized in terms of their physicochemical properties, molecular weight (Mw), and glass transition temperature (Tg). Films were produced by solvent evaporation technique on a mercury substrate. Dibutyl sebacate plasticized and nonplasticized films were characterized by mechanical (tensile zzzz strength, percentage elongation, and Young's modulus), water vapor transmission (WVT), and moisture absorption parameters. Plasticization was found to increase film elongation and decrease the Young's modulus, making the films more flexible and thereby reducing the brittleness. Poor rates of WVT and percentage moisture absorption were demonstrated by various film formulations. Diclofenac sodium-layered pellets coated with GMR and PMR film formulations showed sustained drug release for up to 10 hours. The release rate was influenced by the extent of plasticization and coating level. The results obtained in the study demonstrate the utility of novel rosin-based biomaterials for pharmaceutical coating and sustained-release drug delivery systems.     

A Tuneable Switch for Controlling Environmental Degradation of Bioplastics: Addition of Isothiazolinone to Polyhydroxyalkanoates

Controlling the environmental degradation of polyhydroxybutyrate (PHB) and polyhydroxyvalerate (P(HB-co-HV)) bioplastics would expand the range of their potential applications. Combining PHB and P(HB-co-HV) films with the anti-fouling agent 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOI, <10% w/w) restricted microbial colonisation in soil, but did not significantly affect melting temperature or the tensile strength of films. DCOI films showed reduced biofouling and postponed the onset of weight loss by up to 100 days, a 10-fold increase compared to unmodified films where the microbial coverage was significant. In addition, the rate of PHA-DCOI weight loss, post-onset, reduced by about 150%; in contrast a recorded weight loss of only 0.05% per day for P(HB-co-HV) with a 10% DCOI loading was observed. This is in stark contrast to the unmodified PHB film, where a recorded weight loss of only 0.75% per day was made. The ‘switch’ that initiates film weight loss, and its subsequent reduced rate, depended on the DCOI loading to control biofouling. The control of biofouling and environmental degradation for these DCOI modified bioplastics increases their potential use in biodegradable applications.     

Development of Orodispersible Films Containing Benzydamine Hydrochloride Using a Modified Solvent Casting Method

The aim of this study was to develop benzydamine hydrochloride-loaded orodispersible films using the modification of a solvent casting method. An innovative approach was developed when the drying process of a small-scale production was used based on a heated inert base for casting the film. During this process, two types of film-forming maltodextrins for rapid drug delivery were used. They were plasticized with two different polyols (xylitol and sorbitol). Superdisintegrant Kollidon® CL-F was tested as an excipient that can induce faster disintegration of the prepared films. The influence of the formulation parameters (dextrose equivalent of film-forming maltodextrins, a type of plasticizer, and the presence of superdisintegrant) on the disintegration time, mechanical properties, and moisture content of films was statistically evaluated using a multivariate data analysis. Orodispersible films containing maltodextrin with lower dextrose equivalent value showed better mechanical properties (tensile strength ranged from 886.6?±?30.2 to 1484.2?±?226.9 N cm^?2), lower moisture content (0.5?±?0.0 to 1.2?±?0.2%), and shorter disintegration time (17.6?±?2.9 to 27.8?±?2.8 s). Films plasticized with xylitol showed shorter disintegration time (17.6?±?2.9 to 29.2?±?3.8 s) than films containing sorbitol (23.8?±?2.9 to 31.7?±?3.9 s). With the addition of superdisintegrant Kollidon® CL-F, a significant influence on disintegration time was not observed. The modified solvent casting method shows great promise in a small-scale laboratory production of orodispersible films, e.g., in a pharmacy lab.     

Extraction, characterization and potential applications of cellulose in corn kernels and Distillers’ dried grains with solubles (DDGS)

Cellulose with properties suitable for films and absorbents has been extracted from corn kernels and DDGS. Although DDGS is an inexpensive and abundant co-product that contains valuable components, it is currently not being used for industrial applications. DDGS contains about 9–16% cellulose by weight but the properties of cellulose in DDGS or even in corn kernels such as degree of polymerization (DP), morphology and crystallinity of cellulose have not been studied. In this study, cellulose was extracted from corn kernels and DDGS using alkali and enzymes. A minimum crude cellulose yield of 1.7% and 7.2% with cellulose content of 72% and 81% was obtained from corn kernels and DDGS, respectively. The solids obtained after extraction with cellulose contents ranging from 35% to 81% were made into films with tensile strength and elongation up to 42.5 MPa and 3.3%, respectively, using water and without any additional chemicals. The cellulose obtained holds water up to 9 times its weight and could therefore be used as an absorbent. The cellulose could also be used as paper, composites, lubricant and nutritional supplement.     

Enhanced microbial safety of channel catfish (Ictalurus punctatus) fillet using recently invented medium molecular weight water-soluble chitosan coating

Chitosan with higher molecular weight exhibited higher antimicrobial efficacy against foodborne pathogens. However, the poor water solubility of higher or medium molecular weight chitosan limits its applications. To overcome the challenge, our research team searched for simple preparation procedure for fast-dissolving medium molecular weight chitosan in water. Throughout the process, we were able to obtain a higher concentration of medium molecular weight water-soluble (MMWWS) chitosan (400 kDa). The MMWWS chitosan showed physicochemical properties that are suitable for edible coating. Antibacterial activities of 400-kDa chitosan coating prepared in acetic acid (1% v/v) or aspartic acid (1% or 3% w/v) were examined. The surface of catfish cubes was inoculated with six foodborne pathogens and then coated with chitosan solutions. The survival of each pathogen was evaluated during shelf life storage. Compared with the control, 3% w/v chitosan coating in aspartic acid solution exhibited the most effective antibacterial activities among other coating treatments, completely inhibiting Vibrio parahaemolyticus on the surface of catfish. The study suggested that chitosan dissolved in aspartic acid has the potential for use as an alternative antimicrobial coating for catfish fillet.     

Physical, mechanical, and antibacterial properties of chitosan/PEO blend films

Films formed by blending of two polymers usually have modified physical and mechanical properties compared to films made of the individual components. Our preliminary studies indicated that incorporation of chitosan in polyethylene oxide (PEO) films may provide additional functionality to the PEO films and may decrease their tendency to spherulitic crystallization. The objective of this study was to determine the correlation between chitosan/PEO weight ratio and the physical, mechanical, and antibacterial properties of corresponding films. Films with chitosan/PEO weight ratios from 100/0 to 50/50 in 10% increments were characterized by measuring thickness, puncture strength (PS), tensile strength (TS), elongation at break (%E), water vapor permeability (WVP), and water solubility (WS). Additionally, the films were examined by polarized microscopy, wide-angle X-ray diffraction (WAXD), and Fourier transform infrared (FTIR) spectroscopy, and their antibacterial properties were tested against Escherichia coli. The chitosan fraction contributes to antimicrobial effect of the films, decreases tendency to spherulitic crystallization of PEO, and enhances puncture and tensile strength of the films, while addition of the PEO results in thinner films with lower water vapor permeability. Films with 90/10 blend ratio of chitosan/PEO showed the most satisfactory PS, TS, %E, and antibacterial properties of all tested ratios.     

Biodegradability and mechanical properties of starch films from Andean crops

Different Andean crops were used to obtain starches not previously reported in literature as raw material for the production of biodegradable polymers. The twelve starches obtained were used to prepare biodegradable films by casting. Water and glycerol were used as plasticizers. The mechanical properties of the starch based films were assessed by means of tensile tests. Compost tests and FTIR tests were carried out to assess biodegradability of films. The results show that the mechanical properties (UTS, Young's modulus and elongation at break) of starch based films strongly depend on the starch source used for their production. We found that all the starch films prepared biodegrade following a three stage process and that the weight loss rate of all the starch based films tested was higher than the weight loss rate of the cellulose film used as control.     

Edible films made from natural resources; microcrystalline cellulose (MCC), methylcellulose (MC) and corn starch and polyols-Part 2

Aqueous blends of microcrystalline cellulose (MCC) or methyl cellulose (MC) and corn starch with or without polyols were extruded, hot pressed and studied, after their conditioning at different relative humidities, in terms of their thermal, mechanical and water and gas permeability properties. An increase in water or polyol content showed a considerable increase in percentage elongation but also a decrease in the tensile strength of films. The presence of high cellulose contents increased the tensile strength and decreased the water vapour transmission of films. The development of crystallinity with time resulted in a decrease of both gas and water permeability. Several semiempirical models for calculation of gas permeability and tensile strength and tensile and flexural moduli were applied. The obtained values were compared to those experimentally determined and with the ones reported in the literature. On several occasions, quite significant discrepancies were found which were attributed to differences in molecular weight, percentage crystallinity and polymorphism.     

The plasticizing mechanism and effect of calcium chloride on starch/poly(vinyl alcohol) films

Starch/poly(vinyl alcohol) (PVA) films were prepared with calcium chloride (CaCl(2)) as the plasticizer. The micro morphology of pure starch/PVA film and CaCl(2) plasticized starch/PVA film was observed by scanning electron microscope. The interaction between CaCl(2) and starch/PVA molecules was investigated by Fourier transform infrared spectroscopy. The influence of CaCl(2) on the crystalline, thermal and mechanical properties of starch/PVA films was studied by X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and tensile testing, respectively. The results indicated that CaCl(2) could interact with starch and PVA molecules and then effectively destroy the crystals of starch and PVA. Starch/PVA films plasticized with CaCl(2) became soft and ductile, with lower tensile strength and higher elongation at break compared with pure starch/PVA film. The water content of starch/PVA film would increase with the addition of CaCl(2). This is an important cause of the plasticization of CaCl(2) on starch/PVA film.     

Characterization of films made with chayote tuber and potato starches blending with cellulose nanoparticles

The aim of this study was to characterize chayotextle starch films reinforced with cellulose (C) and cellulose nanoparticle (CN) (at concentrations of 0.3%, 0.5%, 0.8% and 1.2%), using thermal, mechanical, physicochemical, permeability, and water solubility tests. C was acid-treated to obtain CN. The films were prepared by casting; potato starch and C were used as the control. The solubility of the starch films decreased with the addition of C and CN compared with its respective film without C and CN. No statistical difference (α = 0.05) was found in the films added with different concentrations of C and CN. In general, the mechanical properties were improved with the addition of C and CN, and higher values of tensile strength and elastic modulus were determined in the films reinforced with CN. The melting temperature and enthalpy increased with the addition of C and CN, and the values of both thermal parameters were higher in the films with CN than with C; the enthalpy value of the film decreased when the concentration of C or CN increased in the composite. Low concentration of C and CN is better distributed in the matrix film. The addition of C and CN in the starch films improved some mechanical, barrier, and functional properties.     

pH-Amplified multilayer films based on hyaluronan: influence of HA molecular weight and concentration on film growth and stability

In this study, we investigate the growth and internal properties of polyelectrolyte multilayer films made of poly(l-lysine) and hyaluronan (PLL/HA) under pH-amplified conditions, that is, by alternate deposition of PLL at high pH and HA at low pH. We focus especially on the influence of the molecular weight of HA in this process as well as on its concentration in solution. Film growth was followed by quartz crystal microbalance and by infrared spectroscopy to quantify the deposited mass and to characterize the internal properties of the films, including the presence of hydrogen bonds and the ionization degree of HA in the films. Film growth was significantly faster for HA of high molecular weight (1300 kDa) as compared with 400 and 200 kDa. PLL was found to exhibit a random structure once deposited in the films. Furthermore, we found that PLL-ending films are more stable when they are placed in PBS than their HA counterparts. This was explained on the basis of more cohesive interactions in the films for PLL-ending films. Finally, we quantified PLL(FITC) diffusion into the films and observed that PLL diffusion is enhanced when PLL is paired with the HA of high MW. All together, these results suggest that besides purely physicochemical parameters such as variation in pH, the molecular weight of HA, its concentration in solution, and the possibility to form intermolecular HA association play important roles in film growth, internal cohesion, and stability.     

Transglutaminase‐modified wool keratin film and its potential application in tissue engineering

Transglutaminase (TGase) catalyzes the cross‐linking of many proteins and has been widely used to improve the properties of certain protein‐based materials. Keratin is considered as a promising biomaterial candidate following traditional chemical modification. In this study, the effect of TGase on the properties of a wool keratin film was investigated. The TGase‐modified film was applied to drug release and cell proliferation. Treatment with TGase (30 U/g keratin) for 18 h at 40°C increased the tensile strength of the film from 5.18 ± 0.15 MPa to 6.22 ± 0.11 MPa and decreased the elongation at break from 83.47 ± 1.79% to 72.12 ± 3.02%. The stability of the film in PBS and in artificial gastric juice was also improved. A rougher surface and a more compact cross‐section were observed by scanning electron microscopy photographs of the TGase‐treated film. SDS‐PAGE analysis confirmed that higher molecular weight proteins were formed in the TGase‐modified keratin solution and film. The results of the drug release assay using diclofenac indicated that both films with and without TGase treatment led to a high initial release in PBS, which was more constant in artificial gastric juice. The enzyme treatment led to a lower drug release rate from the film. Cell culture experiments suggested that the TGase‐mediated cross‐linked keratin film shows a good biocompatibility and that it can be used for tissue engineering applications.     

Structural effects of terminal groups on nonenzymatic and enzymatic degradations of end-capped poly(L-lactide)

Poly(L-lactide) (PLLA) with various alkyl ester chain end groups were synthesized by ring-opening polymerization of L-lactide in the presence of zinc alkoxide as a catalyst. The structural effect of chain end groups on the rate of enzymatic and nonenzymatic degradations for amorphous films of PLLA were investigated at 37 degrees C in a Tris-HCl buffer solution (pH 8.6) with proteinase K and at 60 degrees C in a phosphate buffer solution (pH 7.4), respectively. The rate of enzymatic degradation for PLLA films was dependent on the carbon numbers of alkyl ester chain end groups, and the rates of PLLA samples with dodecyl (C12), tridecyl (C13), and tetracocyl (C14) ester end groups were much lower than those of the other samples. The surface morphologies of PLLA films after enzymatic degradation were characterized by scanning electron microscopy. After the enzymatic degradation, non-end-capped PLLA, PLLA with methyl (C1) and hexyl (C6) ester chain ends, were degraded homogeneously by proteinase K and the film surface was very smooth. In contrast, the PLLA with alkyl ester chain ends of carbon numbers over 12 were degraded heterogeneously by the enzyme, and the sponge-like network structure was formed on the film surface. These results indicated that the long alkyl ester groups at the chain ends of PLLA molecules aggregated in the amorphous films and the erosion rate was depressed due to the coverage of the aggregated terminal groups on the film surface. For the nonenzymatic degradation, the molecular weight of non-end-capped PLLA was remarkably decreased with progress of degradation. In contrast, the molecular weight of the end-capped PLLA gradually reduced at the initial stage of degradation and then the rate of degradation was accelerated. The decreases of molecular weight of PLLA by autocatalyzed degradation were retarded by the capping of carboxyl chain ends.     

Microstructural characterization of yam starch films

Yam starch films were produced by thermal gelatinization of starch suspensions using different starch and glycerol concentrations and were compared to control samples without glycerol. Films were characterized by polarized light microscopy, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermomechanical analysis (TMA), X-ray diffraction, water vapor permeability (WVP) and water sorption isotherms. The polarized light microscopy and DSC data showed that starch gelatinization for film formation was complete. Plasticized films have a homogeneous structure as observed by SEM. At water activities >0.43, glycerol increased the equilibrium moisture content of the films due to its hydrophilic character. X-ray pattern of the yam films could be assigned to a B-type starch; during storage this pattern remained almost the same, however a slight recrystallization process could be observed. Amylopectin retrogradation was not observed by DSC with storage time of the films. Glass transition temperatures of films with glycerol were lower than those of control films as measured by DSC and TMA. WVP of yam starch films increased with the presence of glycerol.     

Bionanocomposites based on pea starch and cellulose nanowhiskers hydrolyzed from pea hull fibre: Effect of hydrolysis time

By hydrolyzing pea hull fibres (PHF) for different times (t) with sulfuric acid, a series of pea hull fibre-derived nanowhisker (PHFNW-t) dispersions was prepared. The PHFNW-t dispersions were then blended with pea starch (PS) to fabricate bionanocomposite films (PS/PHFNW-t). The effect of t on the structure and properties of the PHFNW-t nanowhiskers and those of the corresponding PS/PHFNW-t nanocomposite films were investigated. The length (L), diameter (D) and L/D values of the PHFNW-t ranged from 240 to 400 nm, 7 to 12 nm, and 32.22 to 36.00, respectively. The PS/PHFNW-t nanocomposite films exhibited higher ultraviolet absorption, transparency, tensile strength, elongation at break, and water-resistance than both the neat PS film and the PS/PHF film (as a control with a t of 0 h). The PS/PHFNW-8 film showed the highest transparency, tensile strength, and elongation at break among the PS/PHFNW-t films, due to the high L/D of PHFNW-8. These results revealed that the length of hydrolysis time had a great effect on the structure (including L, D and L/D) of the PHFNW-t nanowhiskers, as well as on the structure and performance of the resulting PS/PHFNW-t films. For preparation of PHFNW-t nanowhiskers and corresponding PS/PHFNW-t films, the most suitable hydrolysis time, in this work, is 8 h.     

In vitro hydrolysis of blends from enantiomeric poly(lactide)s. 3. Homocrystallized and amorphous blend films

Homocrystallized and amorphous enantiomeric blend films were prepared from the melt of high molecular weight poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) (1:1) by crystallization and quenching, respectively. A phosphate-buffered solution was used to investigate effects of homocrystallinity via in vitro hydrolysis as well as crystallization process during the hydrolysis, which was performed for a period of 24 months at 37 degrees C and pH 7.4. Results derived from gravimetry, gel permeation chromatography, and tensile testing showed that hydrolyzability was higher for the homocrystallized film than for the amorphous film. Thus, probable mechanisms are proposed for the enhanced hydrolysis of the homocrystallized blend film compared with that of the amorphous blend film. The hydrolysis rate constant (k) values of the homocrystallized and amorphous films estimated from the changes in number-average molecular weight (M(n)) were 5.00 x 10(-3) and 3.32 x 10(-3) day(-1), respectively. Moreover, hydrolyzability of equimolar enantiomeric poly(lactic acid) blends can be altered in the k range of 0.73 x 10(-3) and 5.00 x 10(-3) day(-1) by varying their crystalline species, crystallinity, or molecular weights.