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.

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.

Optimization of the Sustainable Production of Resistant Starch in Rice Bran and Evaluation of Its Physicochemical and Technological Properties.

In this study, the optimization of ultrasound (US) (850 kHz, 120 W) processing parameters (temperature, time, and power) for the enhanced production of resistant starch (RS) in rice bran (RB) matrixes was performed. The effect of US cavitation at different temperatures on the morphology, physicochemical properties, and mechanical performance of RS was evaluated. Ultrasonication at 40−70 °C temperatures affected the chemical structure, reduced the crystallinity of RS from 23.85% to between 18.37 and 4.43%, and increased the mechanical and thermal stability of RS pastes, indicating a higher tendency to retrograde. US treatment significantly (p < 0.05) improved the oil (OAC) and water (WAC) absorption capacities, swelling power (SP), solubility (WS), and reduced the least-gelation concentration (LGC). The mathematical evaluation of the data indicated a significant effect (p < 0.05) of the US parameters on the production of RS. The largest increment of RS (13.46 g/100 g dw) was achieved with US cavitation at 1.8 W/cm2 power, 40.2 °C temperature, and 18 min of processing time. The developed method and technology bring low-temperature US processing of rice milling waste to create a new sustainable food system based on modified rice bran biopolymers.

Integration of Ultrasound into the Development of Plant-Based Protein Hydrolysate and Its Bio-Stimulatory Effect for Growth of Wheat Grain Seedlings In Vivo.

This study was dedicated to increasing the efficiency of producing plant-based protein hydrolysate using traditional and non-traditional treatments. Low- and high frequency ultrasound (US) at different intensities were applied to corn steep liquor (CSL) at 50 °C for 30 min, and enzymatic hydrolysis was performed using industrially produced alkaline protease. The efficiency of US and enzymatic treatments was characterized by protein solubility (soluble protein (SP) content, hydrolyzed protein (HP) concentration, and free amino acid (FAA) profile) and kinetic parameters: Michaelis-Menten constant (KM) and apparent breakdown rate constant (kA). A significant effect of 37 kHz US pre-treatment for CSL enzymatic hydrolysis was found and resulted in the highest HP concentration (17.5 g/L) using the lowest enzyme concentration (2.1 g/L) and the shortest hydrolysis time (60 min). By using US pre-treatment, on average, a 2.2 times higher FAA content could be achieved compared to traditional hydrolysis. Additionally, results for the kinetic parameters kM and kA confirmed the potential of applying US treatment before hydrolysis. The effect of CSL protein hydrolysate on plant growth was tested in vivo on wheat grain seed germination and resulted in the significant increase in germination parameters compared to the control treatment. These findings indicate that by-products of starch industry could be a promising source for the production of low-cost sustainable biostimulants.

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%.

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.