Asier M. Salaberria

Processing of α-chitin nanofibers by dynamic high pressure homogenization: characterization and antifungal activity against A. niger.

Chitin nano-objects become more interesting and attractive material than native chitin because of their usable form, low density, high surface area and promising mechanical properties. This work suggests a straightforward and environmentally friendly method for processing chitin nanofibers using dynamic high pressure homogenization. This technique proved to be a remarkably simple way to get α-chitin into α-chitin nanofibers from yellow lobster wastes with a uniform width (bellow 100 nm) and high aspect ratio; and may contributes to a major breakthrough in chitin applications. Moreover, the resulting α-chitin nanofibers were characterized and compared with native α-chitin in terms of chemical and crystal structure, thermal degradation and antifungal activity. The biological assays highlighted that the nano nature of chitin nanofibers plays an important role in the antifungal activity against Aspergillus niger.

Self-bonded composite films based on cellulose nanofibers and chitin nanocrystals as antifungal materials.

Cellulose nanofibers and chitin nanocrystals, two main components of agricultural and aquacultural by-products, were obtained from blue agave and yellow squat lobster industrial residues. Cellulose nanofibers were obtained using high pressure homogenization, while chitin nanocrystals were obtained by hydrolysis in acid medium. Cellulose nanofibers and chitin nanocrystals were characterized by X-ray diffraction, Atomic Force Microscopy and Infrared spectroscopy. Self-bonded composite films with different composition were fabricated by hot pressing and their properties were evaluated. Antifungal activity of chitin nanocrystals was studied using a Cellometer(®) cell count device, mechanical properties at tension were measured with a universal testing machine, water vapor permeability was evaluated with a thermohygrometer and surface tension with sessile drop contact angle method. The addition of chitin nanocrystals reduced slightly the mechanical properties of the composite. Presence of chitin nanocrystals influenced the growth of Aspergillus sp fungus in the surface of the composites as expected.

On chemistry of γ-chitin

The biological material, chitin, is present in nature in three allomorphic forms: α, β and γ. Whereas most studies have dealt with α- and β-chitin, only few investigations have focused on γ-chitin, whose structural and physicochemical properties have not been well delineated. In this study, chitin obtained for the first time from the cocoon of the moth (Orgyia dubia) was subjected to extensive physicochemical analyses and examined, in parallel, with α-chitin from exoskeleton of a freshwater crab and β-chitin from cuttlebone of the common cuttlefish. Our results, which are supported by13C CP-MAS NMR, XRD, FT-IR, Raman spectroscopy, TGA, DSC, SEM, AFM, chitinase digestive test and elemental analysis, verify the authenticity of γ-chitin. Further, quantum chemical calculations were conducted on all three allomorphic forms, and, together with our physicochemical analyses, demonstrate that γ-chitin is distinct, yet closer in structure to α-chitin than β-chitin.

Utilization of flax (Linum usitatissimum) cellulose nanocrystals as reinforcing material for chitosan films

Use of plastic based packaging tools is causing both health and economic problems. To overcome this situation, researchers are focusing on the use of different biomaterials such as chitosan and cellulose. The current study was conducted to check the effect of flax (Linum usitatissimum) cellulose nanocrystals (CNC) on mechanical and barrier properties of chitosan-based films. CNC was incorporated in different concentrations (5, 10, 20 and 30%). CNC was isolated from flax fiber using acid hydrolysis method. Tensile strength (TS) and young modulus (YM) values increased with the increase of CNC concentration. Chitosan film with 20% CNC revealed the highest YM value as 52.35MPa. No significant improvement was recorded in water vapor permeability due to overall lower film crystallinity. All the films were observed to be transparent up to an acceptable level. SEM and AFM analysis confirmed the homogeneity of films. A gradual enhancement was recorded in the antimicrobial activity of chitosan/CNC composite films. No significant improvement revealed in the thermal stability of composites.

Diatomite as a novel composite ingredient for chitosan film with enhanced physicochemical properties

Practical applications of biopolymers in different industries are gaining considerable increase day by day. But still, these biopolymers lack important properties in order to meet the industrial demands. In the same regard, in the current study, chitosan composite films are produced by incorporating diatomite soil at two different concentrations. In order to obtain a homogeneous film, glutaraldehyde was supplemented to chitosan solution as a cross-linker. Compositing diatomaceous earth to chitosan film resulted in improvement of various important physicochemical properties compared to control such as; enhanced film wettability, increase elongation at break and improved thermal stability (264-277°C). The microstructure of the film was observed to haveconsisted of homogeneously distributed blister-shaped structures arised due to the incorporation of diatomite. The incorporation of diatomite did not influence the overall antioxidant activity of the composite films, which can be ascribe to the difficulty radicals formation. Chitosan film incorporated with increasing fraction of diatomite revealed a notable enhancement in the antimicrobial activity. Additionally with the present study, for the first time possible interactions between chitosan/diatomite were determined via quantum chemical calculations. Current study will be helpful in giving a new biotechnological perspective to diatom in terms of its successful application in hydrophobic composite film production.

Effect of different animal fat and plant oil additives on physicochemical, mechanical, antimicrobial and antioxidant properties of chitosan films

Practical application of chitosan-essential oil blend films is limited due to the uneconomical extraction procedure of essential oils from plants. This study aimed to produce chitosan films blended with low cost and commercially available oils and fats consumed in daily human diet (olive, corn and sunflower oils, butter and animal fats). The study also focused on how physicochemical, biological and mechanical properties of chitosan blend films were influenced by the incorporation of oils and fats with varying unsaturation degrees. Possible interactions of chitosan film matrix with incorporated oils or fats were investigated. Chitosan-olive oil film showed better surface morphology and higher thermal stability than the films with other unsaturated oils. Tensile strength, Youngs modulus and elongation at break were improved by 57.2%, 25.1% and 31.7% for chitosan-olive oil film, respectively. Chitosan-olive oil blend film had the highest antibacterial activity (almost equal to that of commercial antibiotic gentamicin). Edible films obtained from by incorporation of natural oils and fats into chitosan can help produce an environmentally friendly packaging material that is low cost and easily manufactured.

Triethyl Citrate (TEC) as a Dispersing Aid in Polylactic Acid/Chitin Nanocomposites Prepared via Liquid-Assisted Extrusion

The production of fully bio-based and biodegradable nanocomposites has gained attention during recent years due to environmental reasons; however, the production of these nanocomposites on the large-scale is challenging. Polylactic acid/chitin nanocrystal (PLA/ChNC) nanocomposites with triethyl citrate (TEC) at varied concentrations (2.5, 5.0, and 7.5 wt %) were prepared using liquid-assisted extrusion. The goal was to find the minimum amount of the TEC plasticizer needed to enhance the ChNC dispersion. The microscopy study showed that the dispersion and distribution of the ChNC into PLA improved with the increasing TEC content. Hence, the nanocomposite with the highest plasticizer content (7.5 wt %) showed the highest optical transparency and improved thermal and mechanical properties compared with its counterpart without the ChNC. Gel permeation chromatography confirmed that the water and ethanol used during the extrusion did not degrade PLA. Further, Fourier transform infrared spectroscopy showed improved interaction between PLA and ChNC through hydrogen bonding when TEC was added. All results confirmed that the plasticizer plays an important role as a dispersing aid in the processing of PLA/ChNC nanocomposites.

The Antifungal Activity of Functionalized Chitin Nanocrystals in Poly (Lactid Acid) Films

As, in the market, poly (lactic acid) (PLA) is the most used polymer as an alternative to conventional plastics, and as functionalized chitin nanocrystals (CHNC) can provide structural and bioactive properties, their combination sounds promising in the preparation of functional nanocomposite films for sustainable packaging. Chitin nanocrystals were successfully modified via acylation using anhydride acetic and dodecanoyl chloride acid to improve their compatibility with the matrix, PLA. The nanocomposite films were prepared by extrusion/compression approach using different concentrations of both sets of functionalized CHNC. This investigation brings forward that both sets of modified CHNC act as functional agents, i.e., they slightly improved the hydrophobic character of the PLA nanocomposite films, and, very importantly, they also enhanced their antifungal activity. Nonetheless, the nanocomposite films prepared with the CHNC modified with dodecanoyl chloride acid presented the best properties.

An inclusive physicochemical comparison of natural and synthetic chitin films

Natural and synthetic chitin films, obtained from the same source were produced and their physicochemical properties were examined comparatively. Firstly, natural chitin film was obtained from elytra of an insect (Oryctes nasicornis L.) and purity of the obtained chitin film (degree of acetylation: 79±2%) was demonstrated by solid state 13C nuclear magnetic resonance (13C NMR). Then, the synthetic film was produced by dissolving of natural chitin film in LiCl-DMAc. The obtained natural and synthetic films were characterized by AFM, TGA, DSC, FTIR, mechanical properties, light transmission and contact angle. The analyses result demonstrated that natural chitin film lost very important properties such as high thermal stability, transparency, nanofibrous nature, tensile strength, Youngs modulus and hydrophobicity after transforming the synthetic film.

Biological, mechanical, optical and physicochemical properties of natural chitin films obtained from the dorsal pronotum and the wing of cockroach

In previous studies, chitin-based films were produced from chitin nanofibers in dust form and fully characterized. However, chitin films naturally present in many organisms have not been isolated and characterized. Herein, structurally intact chitin films were successfully extracted from the dorsal pronotum and the wing of cockroach. Despite using the same extraction procedure, important differences were observed. Especially, hydrophobicity, transparency, antifungal and antibacterial biofilm activities of wing chitin film were recorded notably higher than those of chitin film from the dorsal pronotum. However, better mechanical properties were observed for chitin film from the dorsal pronotum. Notably, among the tested bacteria, two common pathogens could not form biofilms on the surface of the films. This study clearly demonstrated natural chitin films obtained from an insect can provide a new perspective to chitin-based applications where chitin films with high thermal stability, transparency, resistance to bacterial biofilm formation and antifungal activity are needed.