Synthesis and Characterization of Thermoresponsive Chitosan-graft-poly(N-isopropylacrylamide) Copolymers.

Thermoresponsive chitosan-graft-poly(N-isopropylacrylamide) (CS-g-PNIPAAm) copolymers of different composition were synthesized by free-radical polymerization of chitosan (CS) and N-isopropylacrylamide (NIPAAm) in aqueous solution using potassium persulfate (PPS) as an initiator. By changing the molar ratio of CS:NIPAAm from 1:0.25 to 1:10 graft copolymers with a CS backbone and different amounts of PNIPAM side chains were prepared. The chemical structure of the obtained CS-g-PNIPAAm copolymers was confirmed by FTIR and 1H NMR spectroscopy. 1H NMR spectra were also used to calculate the content of attached PNIPAAm side chains. Moreover, the lower critical solution temperature (LCST) behavior of synthesized copolymers was assessed by cloud point, differential scanning calorimetry and particle size measurements. The aqueous solutions of copolymers containing ≥12 molar percent of PNIPAAm side chains demonstrated LCST behavior with the phase separation at around 29.0-32.7 °C. The intensity of thermoresponsiveness depended on the composition of copolymers and increased with increasing content of poly(N-isopropylacrylamide) moieties. The synthesized thermoresponsive chitosan-graft-poly(N-isopropylacrylamide) copolymers could be potentially applied in drug delivery systems or tissue engineering.

Investigation of Bioactive Complexes of Chitosan and Green Coffee Bean or Artichoke Extracts.

The formation of water-insoluble complexes between chitosan (ChS) and caffeoylquinic acid (CQ) derivatives present in artichoke (AE) and green coffee bean (GCBE) extracts was investigated by the equilibrium adsorption method. The UPLC/HPLC analysis revealed that the phenolic compounds accounted for 8.1% and 74.6% of AE and GCBE respectively, and CQ derivatives were the predominant compounds. According to the applied Langmuir adsorption model, anionic compounds present in natural extracts were adsorbed onto the active centers of ChS, i.e., primary amino groups. The driving forces of adsorption were electrostatic interactions between cationic groups of ChS and anionic compounds of natural extracts. Chromatographic analysis revealed that not only CQ derivatives, but also other phenolic compounds of natural extracts were attached to ChS. The release of adsorbed compounds into different media as well as the bioactive properties of complexes were also studied. With the immobilization of bioactives onto ChS, increased and prolonged ABTS•+ radical scavenging activity and decreased antifungal activity against Fusarium graminearum and Botrytis cinerea were observed compared to those of ChS. The findings of the current study highlight that the adsorption approach could be used to successfully prepare water-insoluble complexes of ChS and components of natural extracts with prolonged antioxidant activity.

Production of Cationic Starch-Based Flocculants and Their Application in Thickening and Dewatering of the Municipal Sewage Sludge.

Polymer flocculants are used to promote solid-liquid separation processes in wastewater treatment technologies, and bio-based flocculants possess many advantages over conventional synthetic polymers. Potato starch microgranules were chemically modified and mechanically sheared to produce modified starch flocculants. The effectiveness of produced cationic starch (CS) and cross-linked cationic starch (CCS) flocculants in the thickening and dewatering of surplus activated sewage sludge was evaluated and compared with that of synthetic cationic flocculants (SCFs) The flocculation efficiency of SCF, CS, and CCS in sludge thickening was determined by measuring the filtration rate of treated surplus activated sludge. Comparing the optimal dose of SCFs and CCS flocculants needed for thickening, the CCS dose was more than 10 times higher, but a wide flocculation window was determined. The impact of used flocculants on the dewatering performance of surplus activated sludge at optimal dose conditions was investigated by measuring capillary suction time. The filtration efficiencies (dewaterability) of surplus activated sludge using SCF, CS, and CCS were 69, 67, and 72%, respectively. The study results imply that mechanically processed cross-linked cationic starch has a great potential to be used as an alternative green flocculant in surplus activated sludge thickening and dewatering operations in municipal sewage sludge treatment processes.

Bioplastics for Food Packaging: Environmental Impact, Trends and Regulatory Aspects.

The demand to develop and produce eco-friendly alternatives for food packaging is increasing. The huge negative impact that the disposal of so-called "single-use plastics" has on the environment is propelling the market to search for new solutions, and requires initiatives to drive faster responses from the scientific community, the industry, and governmental bodies for the adoption and implementation of new materials. Bioplastics are an alternative group of materials that are partly or entirely produced from renewable sources. Some bioplastics are biodegradable or even compostable under the right conditions. This review presents the different properties of these materials, mechanisms of biodegradation, and their environmental impact, but also presents a holistic overview of the most important bioplastics available in the market and their potential application for food packaging, consumer perception of the bioplastics, regulatory aspects, and future challenges.

Polysaccharide Matrices for the Encapsulation of Tetrahydrocurcumin-Potential Application as Biopesticide against Fusarium graminearum.

Cereals are subject to contamination by pathogenic fungi, which damage grains and threaten public health with their mycotoxins. Fusarium graminearum and its mycotoxins, trichothecenes B (TCTBs), are especially targeted in this study. Recently, the increased public and political awareness concerning environmental issues tends to limit the use of traditional fungicides against these pathogens in favor of eco-friendlier alternatives. This study focuses on the development of biofungicides based on the encapsulation of a curcumin derivative, tetrahydrocurcumin (THC), in polysaccharide matrices. Starch octenylsuccinate (OSA-starch) and chitosan have been chosen since they are generally recognized as safe. THC has been successfully trapped into particles obtained through a spray-drying or freeze-drying processes. The particles present different properties, as revealed by visual observations and scanning electron microscopy. They are also different in terms of the amount and the release of encapsulated THC. Although freeze-dried OSA-starch has better trapped THC, it seems less able to protect the phenolic compound than spray-dried particles. Chitosan particles, both spray-dried and lyophilized, have shown promising antifungal properties. The IC50 of THC-loaded spray-dried chitosan particles is as low as 0.6 ± 0.3 g/L. These particles have also significantly decreased the accumulation of TCTBs by 39%.

Interaction between cross-linked cationic starch microgranules and chlorogenic acid isomers in artichoke and green coffee bean aqueous extracts.

In the present study, the adsorption of phenolic compounds, first of all, chlorogenic acid isomers (chlorogenic, neo-chlorogenic and crypto-chlorogenic acids) predominant in the artichoke (AE) or green coffee bean (GCBE) extracts on cross-linked cationic starch having quaternary ammonium groups (CCS) has been investigated. The equilibrium adsorption studies showed that adsorption closely followed the Langmuir adsorption model, i.e. anionic substances of the extracts were interacting with quaternary ammonium groups of CCS. The UPLC-UV-MS/MS analysis showed that 8% and 17% of chlorogenic acid isomers of the total amount of adsorbed phenolics form AE and GCBE, respectively, were immobilized on CCS. The desorption study of phenolics from AE/CCS and GCBE/CCS complexes revealed that amount of desorbed AE or GCBE phenolics depended on the desorption medium. The antioxidant activity investigation showed that the immobilization of active components of extracts on CCS prevented the rapid loss of antioxidant activity. The results suppose that adsorption on modified starch technique can be successfully employed to remove important amounts of bioactive compounds from plant extracts by employing effective, sustainable and environmental friendly procedures.

Structure and properties of cationic starches synthesized by using 3-chloro-2-hydroxypropyltrimethylammonium chloride.

Cationic starches (CS) with preserved microgranular structure were prepared from potato starch, with 3-chloro-2-hydroxypropyltrimethyl ammonium chloride as cationic reagent. CS with degree of substitution (DS) and reaction efficiency (RE) ranging from 0.05 to 0.84 and from 47.1% to 99.6%, respectively, were obtained by semidry cationization. The influence of the composition of reaction mixture on RE was investigated. CS with highest DS of 0.84 were obtained by using CaO additive. Meanwhile, without addition of CaO cationic starches with maximum DS of 0.28 were synthesized. Modified starches were characterized by means of Fourier transform infrared and X-ray powder diffraction spectroscopy, scanning electron microscopy, histological examination, Brabender viscoamilography, and solubility studies. It was confirmed that by addition of CaO into reaction mixture, the cationization proceeded in the deeper layers of the granules and attached cationic groups were more evenly distributed in the granule volume. Consequently, CS with high DS and cold water solubility were obtained.

Formation and characteristics of alginate and anthocyanin complexes.

Sodium alginates with different mannuronate to guluronate units ratio ALG1 and ALG2 were employed in the formation of insoluble complexes with anthocyanins (ATC) extracted from Vaccinium myrtilus by exploiting the electrostatic interaction between carboxylate groups of sodium alginate (ALG) and flavylium cations of ATC. Monomer composition of ALG1 and ALG2 was determined from the 13C CP-MAS NMR spectra. The amount of ATC incorporated into the complex depended on the type of ALG used, the ALG to ATC weight ratio and the total concentration of the components in the solution. ALG1 having higher amount of G-blocks was favourable in the complex formation with ATC. At ALG to ATC weight ratio being 0.4 to 1 and total concentration of 0.66 g/L, about 1.54 g of ATC per gram of ALG1 and about 1.24 g of ATC per gram of ALG2 was incorporated into the complex. Thermogravimetric analysis showed that the rate of ALG and ATC complex decomposition also depended on the type of ALG used and was 2.5 times higher for ALG2 and ATC complex compared to ALG1 and ATC complex. Furthermore, ALG/ATC complexes showed prolonged antioxidant activity when compared to ATC.

Thermogravimetric analysis of caffeic and rosmarinic acid containing chitosan complexes.

Thermal behaviour and stability of chitosan (CH) and phenolic acids complexes could be of high importance in regard both the practical applications and understanding the complex formation. Thermal degradation of insoluble complexes of CH and caffeic (CACH) or rosmarinic acid (RACH) was investigated in air and nitrogen atmosphere. Thermal decomposition of CACH proceeded in two stages, first of which was attributed to decarboxylation of adsorbed CA in the temperature interval from 150 °C to 200 °C, and second one was related to decomposition of CH backbone at temperatures higher than 200 °C. Thermal degradation of RACH proceeded in one stage at temperatures higher than 200 °C, in the broad temperature range and was related to decomposition of formed complex. Values of apparent activation energy (Ea) related to the second stage of thermal decomposition of CACH and decomposition of RACH at conversion values (α) from 0.1 to 0.8 were determined by using Flynn-Wall-Ozawa method. For CACH the dependence between Ea and α was very similar to that of CH and showed that products of CA thermal degradation formed in the first stage didn't influence the thermal degradation of CACH in the second stage. Meanwhile, for RACH, initially, values of Ea increased with an increase of conversion degree, at certain value of α reached the maximum which depended on the RA to CH molar ratio, and then decreased.

Adsorption of rosmarinic acid from aqueous solution on chitosan powder.

In present study the adsorption of rosmarinic acid (RA) on chitosan (CH) powder from aqueous solution have been investigated in order to obtain insoluble RA-CH complexes with high amount of RA. The pseudo-second kinetic model and the Langmuir adsorption model described the kinetic and equilibrium adsorption of RA on CH with high correlation coefficients. With the increase of adsorption temperature the rate of adsorption decreased but amount of adsorbed RA increased. It was established that adsorption of RA on CH occurred in two steps, and relevant adsorption mechanism was proposed. The formation of RA-CH with the molar ratio of RA to CH equal to 0.11, 0.22. 0.39, 0.6 and 0.8 was investigated by FT-IR and steady-state fluorescence spectroscopic techniques. By the increase of RA amount in RA-CH complexes the character of both FT-IR and fluorescence spectra changed. The antioxidant activity of RA-CH was investigated by ABTS method and showed that RA-CH having higher amount of adsorbed RA has prolonged antioxidant activity.

Biodegradation of cross-linked and cationic starches.

The biodegradability and the influence of the degree of substitution of cationic groups or cross-linking level of starch were studied by using enzymatic hydrolysis and two aerobic degradation methods. Cationic starches with a degree of substitution varying from 0 to 0.54 were obtained by modifying native potato starch with 2,3-epoxypropyltrimethylammonium chloride, while cross-linked starches with a degree of cross-linking varying from 0 to 92.5% were obtained by reaction of native potato starch with epichlorohydrin. Enzymatic hydrolysis experiment was performed using α-amylase preparation, and aerobic degradation studies were carried out in liquid and solid media by using ISO 14855-2 and 14851 standards methods. The dextrose equivalent, molecular weight, viscosity and biodegradability parameters were used to assess biodegradation process. Biodegradability of modified starches decreased with increasing degree of modification. The addition of cationic groups to starch to the extent >0.1 mol/molAGU reduced the biodegradability of starch derivatives, and CS became non-biodegradable when DS ≥ 0.54. The cross-linking of starch by building the alkyl chain cross-links between the polysaccharide macromolecules reduced ultimate biodegradability of starch derivatives, when the degree of cross-linking was higher than 92.5%.

Development of antioxidant food packaging materials containing eugenol for extending display life of fresh beef.

In this study, clove essential oil (CL) or eugenol (EU) containing cellulose acetate (CA) or acrylic component/hydrophobically modified starch (AC/S) coatings on corona treated oriented polypropylene film (OPP) were designed and investigated for their possible applications as antioxidant packaging materials for fresh meat. The antioxidant properties of the coatings were investigated by Vapour Phase-DPPH (2,2-diphenyl-1-picrylhydrazyl) assay. The CA coatings containing CL or EU showed 43-92% and 43-94% inhibition against DPPH free radicals through the vapour phase, respectively, whereas AC/S/CL and AC/S/EU coatings resulted in DPPH inhibition of 21-65% and 25-84%, respectively. AC/S/EU and CA/EU coatings on OPP containing from 0.32 ±â€¯0.03 to 6.40 ±â€¯0.14 g/m2 of EU were used to prepare packaging for fresh beef (Longissimus thoracis). After 14 days, the lipid oxidation in beef steaks kept in control and antioxidant packages was 3.33 and 1.00-1.22 mg of malondialdehyde per kilogram of meat, respectively. Moreover, red colour of beef in antioxidant packages was retained.

Active Packaging Applications for Food.

The traditional role of food packaging is continuing to evolve in response to changing market needs. Current drivers such as consumer's demand for safer, "healthier," and higher-quality foods, ideally with a long shelf-life; the demand for convenient and transparent packaging, and the preference for more sustainable packaging materials, have led to the development of new packaging technologies, such as active packaging (AP). As defined in the European regulation (EC) No 450/2009, AP systems are designed to "deliberately incorporate components that would release or absorb substances into or from the packaged food or the environment surrounding the food." Active packaging materials are thereby "intended to extend the shelf-life or to maintain or improve the condition of packaged food." Although extensive research on AP technologies is being undertaken, many of these technologies have not yet been implemented successfully in commercial food packaging systems. Broad communication of their benefits in food product applications will facilitate the successful development and market introduction. In this review, an overview of AP technologies, such as antimicrobial, antioxidant or carbon dioxide-releasing systems, and systems absorbing oxygen, moisture or ethylene, is provided, and, in particular, scientific publications illustrating the benefits of such technologies for specific food products are reviewed. Furthermore, the challenges in applying such AP technologies to food systems and the anticipated direction of future developments are discussed. This review will provide food and packaging scientists with a thorough understanding of the benefits of AP technologies when applied to specific foods and hence can assist in accelerating commercial adoption.

Equilibrium adsorption of caffeic, chlorogenic and rosmarinic acids on cationic cross-linked starch with quaternary ammonium groups.

In the present study, the equilibrium adsorption of caffeic acid (CA) and its derivatives, namely, chlorogenic (CGA) and rosmarinic (RA) acids on cationic cross-linked starch (CCS) with degree of substitution of quaternary ammonium groups of 0.42 have been investigated in relation to the structure and acidity of phenolic acids. The Langmuir, Freundlich and Dubinin-Radushkevich adsorption models have been used to describe the equilibrium adsorption of CA, CGA and RA from their initial solutions and solutions having the equimolar amount of NaOH at different temperatures. In the case of adsorption from the initial solutions of acids the values of adsorption parameters were closely related to the dissociation constants of investigated acids. According to the increasing effectiveness of adsorption, phenolic acids could be arranged in the following order: CA

Preparation and characterization of single and dual propylene oxide and octenyl succinic anhydride modified starch carriers for the microencapsulation of essential oils.

Hydroxypropylation with propylene oxide followed by esterification with octenyl succinic anhydride (OSA) was used to produce modified potato starch derivatives suitable for the encapsulation of essential oils. Caraway essential oil (EO) was encapsulated by spray-drying into enzymatically hydrolyzed dual/single modified and native starches. The EO microencapsulation efficiency in different modified starches, the retention of volatile aroma compounds, the emulsion particle size and the microstructure of the spray-dried encapsulated powdered products, as well as the compositional aroma changes taking place during the processing and storage for up to 8 months have been estimated. The increase of OSA content from 0.97 to 2.52% in the P-native structure and from 0.91% to 2.66% in P-HP resulted in the significant increase in the encapsulating capacity, evaluated as a percentage of the total EO retained, from 61.6 to 88.0% and 73.8% to 84.0%, respectively. However, the compositional changes of the microencapsulated caraway EO constituents were not remarkable. Additionally, the effect of pure and encapsulated caraway EO products on the oxidative stability of commercial rapeseed oil and mayonnaise was evaluated using the instrumental Oxipres method and it was shown that they were more effective in emulsion type products by the up to 1.8-fold increase in the oxidative stability of mayonnaise.

Preparation and properties of propylene oxide and octenylsuccinic anhydride modified potato starches.

Starch was dually chemically modified for developing food-grade ingredients of lower digestibility and their properties were compared to those of single modified and native starches. Hydroxypropylation with propylene oxide (HP) followed by esterification with octenylsuccinic anhydride (OSA) of potato starch (P-native) produced derivatives with lower digestibility than esterification solely with OSA. The dextrose equivalent, maltose and glucose contents, which were used as the main indicators for in vitro digestion, were lower for modified starches. P-HP0.2-OSA0.0200 derivative was the least digestible; the glucose and maltose contents were lowered by 28.3 and 42.1% compared to P-native. The aggregation behavior of enzymatically hydrolyzed starch derivatives was studied in aqueous solution by employing the fluorescence probe and dynamic light scattering techniques. The critical aggregation concentration for OSA modified and dually modified starches varied from 1.2 to 3 g/L and from 0.125 to 0.48 g/L, respectively, depending on the degree of OSA substitution. The study showed that above a critical concentration the hydrolyzates of modified starches tend to form the aggregates with different properties depending both on the degree of OSA substitution and chemical structure.

Thermal degradation and stability of cationic starches and their complexes with iodine.

Thermal degradation processes of cationic starch (CS) and CS-iodine complex were investigated by thermogravimetry (TG) in air and under nitrogen atmosphere at 10 °C min(-1) heating rate and compared. Moreover, the thermal stability of CS with different degree of substitution (DS) and their complexes with iodine was studied by TG under nitrogen atmosphere at different heating rates. The average E(a) values for CS were found to be slightly lower as compared to native starch, suggesting lower thermal stability of modified starches due to cationisation. The main thermodegradation event of native starch-iodine and CS-iodine complexes can be separated in two steps: the release of iodine in the range of 137-196 °C, followed by the subsequent iodine induced thermochemical degradation of polysaccharide macromolecules, which appears at lower temperatures than in the absence of iodine. "Blue" inclusion complex showed higher thermal stability than ionic CS-iodine complex.

Preparation, stability and antimicrobial activity of cationic cross-linked starch-iodine complexes.

Cationic cross-linked starch (CCS)-iodine complexes containing different amounts of quaternary ammonium groups (different degrees of substitution (DS)) and iodine have been obtained by iodine adsorption on CCS from aqueous iodine potassium iodide solution. Equilibrium adsorption studies showed that with an increase of DS the amount of iodine adsorbed on CCS and the affinity of iodine to CCS increased linearly. The influences of the DS of CCS and the amount of adsorbed iodine on the stability of CCS-iodine complexes in a solution of 0.02M sodium acetate and reactivity toward l-tyrosine have been investigated. At the same DS, the stability of CCS-iodine complexes decreased with an increase of the amount of adsorbed iodine. With increasing the DS, the stability of CCS-iodine complexes increased. The iodine consumption in the reaction with l-tyrosine increased significantly with an increase of the amount of adsorbed iodine. The influence of DS on iodine consumption was lower and depended on the amount of adsorbed iodine. The antibacterial activity of CCS-iodine complexes against Bacillus cereus, Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli was determined by the broth-dilution and spread-plate methods. The obtained results have demonstrated that an appropriate selection of the CCS-iodine complex composition (the DS of CCS and the amount of adsorbed iodine) could ensure good antimicrobial properties by keeping a low concentration of free iodine in the system. The main advantage of using CCS-iodine complexes as antimicrobial agents is the biodegradability of the polymeric matrix.

Cationic starch nanoparticles based on polyelectrolyte complexes.

Cationic starch nanoparticles were obtained by aqueous polyelectrolyte complex formation between cationic quaternary ammonium substituted starches and anionic sodium tripolyphosphate. The formation of nanosized starch particles of spherical shape was verified by dynamic light scattering and scanning electron microscopy measurements. The cationic starch nanoparticles of different constitution and containing various contents of free quaternary ammonium groups were produced and their zeta potential was modulated between +4 mV and +34 mV by varying polycation/polyanion ratio. Furthermore, the polyelectrolyte complex formation was confirmed by differential scanning calorimetry and FTIR analyses. The thermal stability of cationic starch nanoparticles increased with the introduction of polysalt into polyelectrolyte complex. The solubilization capacity of nanoparticles was varying with the concentration and composition as revealed by fluorescence probe experiments. The capability to accommodate hydrophobic pyrene quest molecule was decreasing with the increasing number of cationic groups in cationic starches and little depended on polyanion/polycation ratio in starch nanoparticles.

Adsorption of hexavalent chromium on cationic cross-linked starches of different botanic origins.

The influence of origin of native starch used to obtain cationic cross-linked starch (CCS) on the adsorption of Cr(VI) onto CCS has been investigated. CCS granule size is influenced by the botanic source of native starch. The equilibrium adsorption of Cr(VI) onto CCS was described by the Langmuir, Freundlich, Dubinin-Radushkevich and Temkin models. The more equal the adsorption energy of the quaternary ammonium groups in CCS granule as indicated by low value of change of Temkin adsorption energy DeltaE(T) the greater amount of Cr(VI) was adsorbed onto CCS. The value of DeltaE(T) decreased and sorption capacity of CCS increased with the decrease of CCS granule size and with the increase of number of amorphous regions in CCS granules. The affinity of dichromate anions increases and adsorption proceeds more spontaneously when Cr(VI) is adsorbed onto more amorphous CCS. Adsorption process of Cr(VI) onto such CCS is more exothermic and order of system undergoes major changes during adsorption. After the adsorption on CCS Cr(VI) could be regenerated by incineration at temperature of 800 degrees C.