Starch/Alkane Diol Materials: Unexpected Ultraporous Surfaces, Near-Isoporous Cores, and Films Moving on Water.
ABSTRACT: The aim of this study was to find alternative starch plasticizers to glycerol that yielded a less tacky material in high-moisture conditions without leading to starch crystallization. A range of glycerol films containing different potential plasticizers (linear alkane diols) were therefore produced, and it was shown that 1,3-propanediol, in combination with glycerol, was a possible solution to the problem. Several additional interesting features of the starch films were however also revealed. The larger diols, instead of showing plasticizing features, yielded a variety of unexpected structures and film properties. Films with 1,6-hexanediol and 1,7-heptanediol showed an ultraporous film surface and near-isoporous core. The most striking feature was that starch films with these two diols moved/rotated over the surface when placed on water, with no other stimulus than the interaction with water. Films with 1,8-octanediol and 1,10-decanediol did not show these features, but there was clear evidence of a structure with phase-separated crystallized diol in a starch matrix, as observed in high-resolution scanning electron microscopy (SEM) images.
Project description:Despite the need for sophisticated instrumentation, breath figure assembly (BFA) methods are restricted to produce macroporous films on a tiny scale so far. The current study narrates the fabrication of macroporous films in hollow fiber geometry which extends to adopt the method for continuous production of isoporous surfaces from commercially available low-priced polymer materials. The fabrication of the films in the hollow fiber geometry is carried out by a co-centric quadruple orifice spinneret through which four different liquids are co-extruded simultaneously: bore fluid (to fill the lumen of the fiber), support layer solution, glycerol, and an isoporous film forming solution through the outer most orifice. The extruded entities plunge into a coagulation bath after passing a definite air gap. The implementation of the concept of diffuse-in, droplet formation, and then condense-out behavior of glycerol in a co-extrusion method of hollow fiber spinning makes macroporous film formation possible in an interminable way sidestepping the use of breath figure assembly method. Moreover, the continuous film formation by the proposed mechanism is also authenticated in flat sheet geometry by employing two casting blades in a casting machine. The structure of the films is analyzed by scanning electron microscopy (SEM).
Project description:Whey protein isolate (WPI)-based cast films are very brittle, due to several chain interactions caused by a large amount of different functional groups. In order to overcome film brittleness, plasticizers, like glycerol, are commonly used. As a result of adding plasticizers, the free volume between the polymer chains increases, leading to higher permeability values. The objective of this study was to investigate the effect of partially substituting glycerol by hydrolysed whey protein isolate (h-WPI) in WPI-based cast films on their mechanical, optical and barrier properties. As recently published by the author, it is proven that increasing the h-WPI content in WPI-based films at constant glycerol concentrations significantly increases film flexibility, while maintaining the barrier properties. The present study considered these facts in order to increase the barrier performance, while maintaining film flexibility. Therefore glycerol was partially replaced by h-WPI in WPI-based cast films. The results clearly indicate that partially replacing glycerol by h-WPI reduces the oxygen permeability and the water vapor transmission rate, while the mechanical properties did not change significantly. Thus, film flexibility was maintained, even though the plasticizer concentration was decreased.
Project description:The aim of this work was to prepare sugar alcohol-based deep eutectic solvents (DES) and test them as starch plasticizers. Thermoplastic starch (TPS) films were obtained via a simple and convenient thermocompression method. Influence of starch/DES premixtures conditioning (preheating, storage time) on TPS properties was investigated. TPS/sorbitol (S)-based DES exhibited similar tensile strength (TS) (8.6 MPa) but twice higher elongation at the break (ε) (33%) when compared with TPS plasticized only with S. Extra treatment, i.e., heating or prolonged storage time, facilitated starch/DES plasticizing. Starch with selected DES was also extruded and the influence of preconditioning and extrusion rotational speed were subsequently studied on thermocompressed films. Extrusion at 100 rpm led to films with TS up to ca. 10 MPa and ε up to 52%. Some differences in film samples morphology obtained via two processing methods were observed. X-ray diffractograms revealed that extruded samples exhibited a V-type peak at 18.2°, with intensity depending on plasticizer total molecular size. Applied techniques (mechanical tests, XRD, Dynamic Mechanical Analysis (DMA), FTIR-Attenuated Total Reflection (ATR), and moisture sorption) indicated that S-based DES forms stronger interactions with starch than glycerol (G) only used as conventional plasticizer, thus leading to better mechanical properties and inhibited tendency to starch recrystallization (studied up to one year).
Project description:Starch-based films with phenolic extracts could replace the use of petroleum-based plastics. In this study, octenyl succinate starch (OSS) films with pecan nutshell extract (PSE) or hazelnut skin extract (HSE) were prepared. The water resistance, as well as the optical, physical, mechanical, and biodegradable properties of these films, were investigated. The PSE and HSE improved the water resistance (decreasing the solubility to 17% and increasing the contact angle to 96.80°) and UV-light barrier properties of the films. For PSE and HSE, as their concentrations increased, the film rigidity decreased since these extracts acted as plasticizers. Micrographs obtained by scanning electron microscopy (SEM) depicted a homogeneous surface as a result of extracts dispersion through the polymeric matrix and the interactions between the phenolic compounds (PC) of the extracts and the OSS. The phenolic extracts from nut by-products and octenyl succinic anhydride (OSA) starch could be used to develop films to replace the conventional plastics.
Project description:This study was conducted to improve the properties of thin films prepared from orange waste by the solution casting method. The main focus was the elimination of holes in the film structure by establishing better cohesion between the major cellulosic and pectin fractions. For this, a previously developed method was improved first by the addition of sugar to promote pectin gelling, then by the addition of maleic anhydride. Principally, maleic anhydride was introduced to the films to induce cross-linking within the film structure. The effects of concentrations of sugar and glycerol as plasticizers and maleic anhydride as a cross-linking agent on the film characteristics were studied. Maleic anhydride improved the structure, resulting in a uniform film, and morphology studies showed better adhesion between components. However, it did not act as a cross-linking agent, but rather as a compatibilizer. The middle level (0.78%) of maleic anhydride content resulted in the highest tensile strength (26.65 ± 3.20 MPa) at low (7%) glycerol and high (14%) sugar levels and the highest elongation (28.48% ± 4.34%) at high sugar and glycerol levels. To achieve a uniform film surface with no holes present, only the lowest (0.39%) level of maleic anhydride was necessary.
Project description:More and more attention has been paid to environmentally friendly bio-based renewable materials as the substitution of fossil-based materials, due to the increasing environmental concerns. In this study, regenerated cellulose films with enhanced mechanical property were prepared via incorporating different plasticizers using ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as the solvent. The characteristics of the cellulose films were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), thermal analysis (TG), X-ray diffraction (XRD), 13C Solid-state cross-polarization/magic angle spinning nuclear magnetic resonance (CP/MAS NMR) and tensile testing. The results showed that the cellulose films exhibited a homogeneous and smooth surface structure. It was noted that the thermal stability of the regenerated cellulose film plasticized with glycerol was increased compared with other regenerated cellulose films. Furthermore, the incorporation of plasticizers dramatically strengthened the tensile strength and improved the hydrophobicity of cellulose films, as compared to the control sample. Therefore, these notable results exhibited the potential utilization in producing environmentally friendly cellulose films with high performance properties.
Project description:Biodegradable packaging in food materials is a green technology based novel approach to replace the synthetic and conventional packaging systems. This study is aimed to formulate the biodegradable cassava starch based films incorporated with cinnamon essential oil and sodium bentonite clay nanoparticles. The films were characterized for their application as a packaging material for meatballs. The cassava starch films incorporated with sodium bentonite and cinnamon oil showed significant antibacterial potential against all test bacteria; Escherichia coli, Salmonella typhimurium and Staphylococcus aureus. Antibacterial effect of films increased significantly when the concentration of cinnamon oil was increased. The cassava starch film incorporated with 0.75% (w/w) sodium bentonite, 2% (w/w) glycerol and 2.5% (w/w) cinnamon oil was selected based on physical, mechanical and antibacterial potential to evaluate shelf life of meatballs. The meatballs stored at ambient temperature in cassava starch film incorporated with cinnamon oil and nanoclay, significantly inhibited the microbial growth till 96 h below the FDA limits (106 CFU/g) in foods compared to control films that exceeded above the limit within 48 h. Hence cassava starch based film incorporated with essential oils and clay nanoparticles can be an alternate approach as a packaging material for food industries to prolong the shelf life of products.
Project description:BACKGROUND:Diols are important monomers for the production of plastics and polyurethanes, which are widely used in our daily life. The medium-chain diols with one hydroxyl group at its subterminal end are able to confer more flexibility upon the synthesized materials. But unfortunately, this type of diols has not been synthesized so far. The strong need for advanced materials impelled us to develop a new strategy for the production of these novel diols. In this study, we use the remodeled P450BM3 for high-specificity production of 1,7-decanediol. RESULTS:The native P450BM3 was capable of converting medium-chain alcohols into corresponding α, ω1-, α, ω2- and α, ω3-diols, with each of them accounting for about one third of the total diols, but it exhibited a little or no activity on the short-chain alcohols. Greatly improved regiospecificity of alcohol hydroxylation was obtained by laboratory evolution of P450BM3. After substitution of 12 amino acid residues (J2-F87A), the ratio of 1,7-decanediol (ω-3 hydroxylation) to total decanediols increased to 86.8 % from 34.0 %. Structure modeling and site-directed mutagenesis demonstrated that the heme end residues such as Ala(78), Phe(87) and Arg(255) play a key role in controlling the regioselectivity of the alcohol hydroxylation, while the residues at the mouth of substrate binding site is not responsible for the regioselectivity. CONCLUSIONS:Herein we employ an engineered P450BM3 for the first time to enable the high-specificity biosynthesis of 1,7-decanediol, which is a promising monomer for the development of advanced materials. Several key amino acid residues that control the regioselectivity of alcohol hydroxylation were identified, providing some new insights into how to improve the regiospecificity of alcohol hydroxylation. This report not only provides a good strategy for the biosynthesis of 1,7-decanediol, but also gives a promising approach for the production of other useful diols.
Project description:Amphotericin B possesses high activity against Candida spp. with low risk of resistance. However, Amphotericin B's high molecular weight compared to other antifungal drugs, such as miconazole and clotrimazole, and poor water solubility hampers its efficacy at the physiological conditions of the oropharyngeal cavity (saliva pH, limited volume for dissolution) and thereby limits its clinical use in oropharyngeal candidiasis. We have prepared fast-dissolving orodispersible films with high loading (1% w/w) using solvent casting that enables amphotericin B to remain solubilised in saliva in equilibrium between the monomeric and dimeric states, and able to produce a local antifungal effect. Optimisation of the amphotericin B-loaded orodispersible films was achieved by quality by design studies combining dextran and/or maltodextrin as dextrose-derived-polymer film formers with cellulose-derived film formers (hydroxypropylmethyl/hydroxypropyl cellulose in a 1:4 weight ratio), sorbitol for taste masking, microcrystalline cellulose (Avicel 200) or microcrystalline cellulose-carboxymethylcellulose sodium (Avicel CL-611) for enhancing the mechanical strength of the film, and polyethylene glycol 400 and glycerol (1:1 w/w) as plasticizers. The optimised amphotericin B orodispersible films (containing 1% AmB, 25% dextran, 25% maltodextrin, 5% sorbitol, 10% Avicel 200, 10% polyethylene glycol 400, 10% glycerol, 3% hydroxypropylmethyl cellulose acetate succinate, 12% hydroxypropyl cellulose) possessed a fast disintegration time (60 ± 3 s), quick release in artificial saliva (>80% in 10 min), high burst strength (2190 mN mm) and high efficacy against several Candida spp. (C. albicans, C. parapsilosis and C. krusei) (>15 mm inhibition halo). Amphotericin B orodispersible films are stable for two weeks at room temperature (25 °C) and up to 1 year in the fridge. Although further toxicological and in vivo efficacy studies are required, this novel Amphotericin B orodispersible films is a promising, physicochemically stable formulation with potential wide application in clinical practice, especially for immunocompromised patients suffering from oropharyngeal candidiasis.
Project description:The vertical depth distributions of amine oxide surfactants, N,N-dimethyldodecyl amine N-oxide (DDAO) and N,N-dimethyltetradecyl amine N-oxide (DTAO), in poly(vinyl alcohol) (PVA) films were explored using neutron reflectometry (NR). In both binary and plasticized films, the two deuterated surfactants formed a single monolayer on the film surface with the remaining surfactant homogeneously distributed throughout the bulk of the film. Small-angle neutron scattering and mechanical testing revealed that these surfactants acted like plasticizers in the bulk, occupying the amorphous regions of PVA and reducing its glass-transition temperature. NR revealed little impact of plasticizer (glycerol) incorporation on the behavior of these surfactants in PVA. The surfactant molecular area in the segregated monolayer was smaller for DTAO than for DDAO, indicating that the larger molecule was more densely packed at the surface. Surface tension was used to assess the solution behavior of these surfactants and the effect of glycerol incorporation. Determination of molecular area of each surfactant on the solution surface revealed that the structures of the surface monolayers are remarkably consistent when water is placed by the solid PVA. Incorporation of glycerol caused a decrease of molecular area for DDAO and increase in molecular area for DTAO both in solution and in PVA. This suggests that the head group interactions, which normally limit the minimum area per adsorbed molecule, are modified by the length of the alkyl tail.