Pub Date : 2023-11-10DOI: 10.3390/polysaccharides4040024
Petr Sitnikov, Philipp Legki, Mikhail Torlopov, Yulia Druz, Vasily Mikhaylov, Dmitriy Tarabukin, Irina Vaseneva, Maria Markarova, Nikita Ushakov, Elena Udoratina
This study has investigated the influence of cellulose nanocrystals (CNCs) with partially acetylated surfaces on the formation, stability, rheology and biodegradability of the Pickering emulsion in a crude oil/water (co/w) system. In all investigated systems, it was observed that the CNC concentrations of 7 mg/mL led to the emulsions showing stability over time. It was also noticed that the increase in concentration of background electrolyte (NaCl) leds to the droplets of emulsions becoming smaller. It was demonstrated that the rheology of the o/w emulsions of the oil products and crude oil stabilized by CNCs depends, to a large extent, on the colloid chemical properties of nanocellulose particles. Calculations and experimental methods were used to study the changes in the acid–base properties of CNCs on the surface of emulsion droplets, depending on a type of hydrophobic components (crude oil and liquid paraffin). The formation of Pickering emulsions leads to the oxidation of oil by Rhodococcus egvi in aerobic conditions becoming more effective, provided that the environment includes mineral salts of nitrogen, potassium and phosphorus. The results obtained present a scientific basis for the development of technologies for the disposal of oil spills on water surfaces.
{"title":"Efficient (Bio)emulsification/Degradation of Crude Oil Using Cellulose Nanocrystals","authors":"Petr Sitnikov, Philipp Legki, Mikhail Torlopov, Yulia Druz, Vasily Mikhaylov, Dmitriy Tarabukin, Irina Vaseneva, Maria Markarova, Nikita Ushakov, Elena Udoratina","doi":"10.3390/polysaccharides4040024","DOIUrl":"https://doi.org/10.3390/polysaccharides4040024","url":null,"abstract":"This study has investigated the influence of cellulose nanocrystals (CNCs) with partially acetylated surfaces on the formation, stability, rheology and biodegradability of the Pickering emulsion in a crude oil/water (co/w) system. In all investigated systems, it was observed that the CNC concentrations of 7 mg/mL led to the emulsions showing stability over time. It was also noticed that the increase in concentration of background electrolyte (NaCl) leds to the droplets of emulsions becoming smaller. It was demonstrated that the rheology of the o/w emulsions of the oil products and crude oil stabilized by CNCs depends, to a large extent, on the colloid chemical properties of nanocellulose particles. Calculations and experimental methods were used to study the changes in the acid–base properties of CNCs on the surface of emulsion droplets, depending on a type of hydrophobic components (crude oil and liquid paraffin). The formation of Pickering emulsions leads to the oxidation of oil by Rhodococcus egvi in aerobic conditions becoming more effective, provided that the environment includes mineral salts of nitrogen, potassium and phosphorus. The results obtained present a scientific basis for the development of technologies for the disposal of oil spills on water surfaces.","PeriodicalId":18775,"journal":{"name":"Natural Polysaccharides in Drug Delivery and Biomedical Applications","volume":"115 25","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135137647","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-11-02DOI: 10.3390/polysaccharides4040023
Ahmed Tara
Within the domain of starch modification, the study delved into cationization of wheat starch through a laboratory-scale twin-screw extruder, exploring various processing conditions. Cationic starch, a crucial component for enhancing paper attributes like dry strength and printability, took center stage. The focus shifted towards integration into papermaking, investigating the transformative potential of reactive extrusion. By contrasting it with conventional dry-process methodology, innovative strides were unveiled. The study extended to pilot-scale extrusion, bridging the gap between laboratory experimentation and potential industrial implementation. Infused with scientific rigor, the investigation navigated the benefits brought about by reactive extrusion. Empirical insights highlighted a significant reduction in the intrinsic viscosity of extruded starch, decreasing from 170 mL·g−1 (native starch) to 100 mL·g−1 at a specific mechanical energy (SME) input of 800 kWh·t−1, demonstrating remarkable stability despite increased mechanical treatment. Moreover, beyond the critical threshold of 220 kWh·t−1, retention efficiency reached a stable plateau at 78%. The study revealed that utilizing a larger extruder slightly improved the mechanical properties of the paper, emphasizing the advantage of scaling up the production process and the consistency of results across different extruder sizes.
{"title":"Advancing Paper Industry Applications with Extruded Cationic Wheat Starch as an Environmentally Friendly Biopolymer","authors":"Ahmed Tara","doi":"10.3390/polysaccharides4040023","DOIUrl":"https://doi.org/10.3390/polysaccharides4040023","url":null,"abstract":"Within the domain of starch modification, the study delved into cationization of wheat starch through a laboratory-scale twin-screw extruder, exploring various processing conditions. Cationic starch, a crucial component for enhancing paper attributes like dry strength and printability, took center stage. The focus shifted towards integration into papermaking, investigating the transformative potential of reactive extrusion. By contrasting it with conventional dry-process methodology, innovative strides were unveiled. The study extended to pilot-scale extrusion, bridging the gap between laboratory experimentation and potential industrial implementation. Infused with scientific rigor, the investigation navigated the benefits brought about by reactive extrusion. Empirical insights highlighted a significant reduction in the intrinsic viscosity of extruded starch, decreasing from 170 mL·g−1 (native starch) to 100 mL·g−1 at a specific mechanical energy (SME) input of 800 kWh·t−1, demonstrating remarkable stability despite increased mechanical treatment. Moreover, beyond the critical threshold of 220 kWh·t−1, retention efficiency reached a stable plateau at 78%. The study revealed that utilizing a larger extruder slightly improved the mechanical properties of the paper, emphasizing the advantage of scaling up the production process and the consistency of results across different extruder sizes.","PeriodicalId":18775,"journal":{"name":"Natural Polysaccharides in Drug Delivery and Biomedical Applications","volume":"20 21","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135972862","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-10-04DOI: 10.3390/polysaccharides4040022
Juliana Botelho Moreira, Thaisa Duarte Santos, Camila Gonzales Cruz, Jéssica Teixeira da Silveira, Lisiane Fernandes de Carvalho, Michele Greque de Morais, Jorge Alberto Vieira Costa
The use of natural polymers has increased due to concern about environmental pollution caused by plastics and emerging pollutants from fossil fuels. In this context, polysaccharides from macroalgae and microalgae arise as natural and abundant resources for various biological, biomedical, and food applications. Different nanomaterials are produced from these polysaccharides to act as effective carriers in the food and pharmaceutical industry: drug and nutrient carriers, active compound encapsulation, and delivery of therapeutic agents to tumor tissues. Polysaccharides-based nanomaterials applied as functional ingredients incorporated into foods can improve texture properties and decrease the caloric density of food products. These nanostructures also present the potential for developing food packaging with antioxidant and antimicrobial properties. In addition, polysaccharides-based nanomaterials are biocompatible, biodegradable, and safe for medical practices to prevent and manage various chronic diseases, such as diabetes, obesity, and cardiovascular disease. In this sense, this review article addresses the use of algal polysaccharides for manufacturing nanomaterials and their potential applications in food and biomedical areas. In addition, the paper discusses the general aspects of algae as a source of polysaccharides, the nanomaterials produced from these polymers, as well as recent studies and the potential use of algal polysaccharides for industries.
{"title":"Algal Polysaccharides-Based Nanomaterials: General Aspects and Potential Applications in Food and Biomedical Fields","authors":"Juliana Botelho Moreira, Thaisa Duarte Santos, Camila Gonzales Cruz, Jéssica Teixeira da Silveira, Lisiane Fernandes de Carvalho, Michele Greque de Morais, Jorge Alberto Vieira Costa","doi":"10.3390/polysaccharides4040022","DOIUrl":"https://doi.org/10.3390/polysaccharides4040022","url":null,"abstract":"The use of natural polymers has increased due to concern about environmental pollution caused by plastics and emerging pollutants from fossil fuels. In this context, polysaccharides from macroalgae and microalgae arise as natural and abundant resources for various biological, biomedical, and food applications. Different nanomaterials are produced from these polysaccharides to act as effective carriers in the food and pharmaceutical industry: drug and nutrient carriers, active compound encapsulation, and delivery of therapeutic agents to tumor tissues. Polysaccharides-based nanomaterials applied as functional ingredients incorporated into foods can improve texture properties and decrease the caloric density of food products. These nanostructures also present the potential for developing food packaging with antioxidant and antimicrobial properties. In addition, polysaccharides-based nanomaterials are biocompatible, biodegradable, and safe for medical practices to prevent and manage various chronic diseases, such as diabetes, obesity, and cardiovascular disease. In this sense, this review article addresses the use of algal polysaccharides for manufacturing nanomaterials and their potential applications in food and biomedical areas. In addition, the paper discusses the general aspects of algae as a source of polysaccharides, the nanomaterials produced from these polymers, as well as recent studies and the potential use of algal polysaccharides for industries.","PeriodicalId":18775,"journal":{"name":"Natural Polysaccharides in Drug Delivery and Biomedical Applications","volume":"99 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135591385","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-10-02DOI: 10.3390/polysaccharides4040021
Yubia De Anda-Flores, Jaime Lizardi-Mendoza, Agustín Rascón-Chu, Judith Tanori-Cordova, Ana Luisa Martínez-López, Elizabeth Carvajal-Millan
Arabinoxylans (AXs) extracted from distillers dried grains with solubles (DDGSs) were treated with amylase, amyloglucosidase, and protease, to evaluate their effect on the polysaccharide capability to form covalent electro-sprayed nanoparticles. Enzymatically treated arabinoxylans (AXPPs) presented a significant decrease in protein content and molecular weight (31 and 37%, respectively), while the ferulic acid content and the arabinose-to-xylose ratio (A/X) were not statistically modified. The Fourier transform infrared spectra of the AXPPs showed a diminution in the intensity of amide I and amide II bands concerning AXs. The AXPP gels (1% w/v) induced via laccase registered a slight increase in the dimers of ferulic acid cross-linking content (9%) and the G’ value (27%) about the AX gels. The electro-sprayed nanoparticles of AXs and AXPPs (NAXs and NAXPPs, respectively) revealed a spherical and regular morphology via transmission electron microscopy. The nanoparticle diameter was not different for the NAXs and NAXPPs, while the NAXPPs show a significant reduction in Z potential value compared to NAXs. Confocal laser microscopy observations were conducted, to analyze the protein content in the AX network, and a decrease in illuminated areas was observed in the AXPP gels and the NAXPPs. These results indicate that the enzymatical treatment of an AX improves the polysaccharide gelling capability, but does not influence the fabrication of electro-sprayed covalent nanoparticles. NAXs and NAXPPs could be attractive biomaterials for diverse pharmaceutical and biomedical applications.
{"title":"Enzymatic Treatment of Ferulated Arabinoxylans from Distillers Dried Grains with Solubles: Influence on the Fabrication of Covalent Electro-Sprayed Nanoparticles","authors":"Yubia De Anda-Flores, Jaime Lizardi-Mendoza, Agustín Rascón-Chu, Judith Tanori-Cordova, Ana Luisa Martínez-López, Elizabeth Carvajal-Millan","doi":"10.3390/polysaccharides4040021","DOIUrl":"https://doi.org/10.3390/polysaccharides4040021","url":null,"abstract":"Arabinoxylans (AXs) extracted from distillers dried grains with solubles (DDGSs) were treated with amylase, amyloglucosidase, and protease, to evaluate their effect on the polysaccharide capability to form covalent electro-sprayed nanoparticles. Enzymatically treated arabinoxylans (AXPPs) presented a significant decrease in protein content and molecular weight (31 and 37%, respectively), while the ferulic acid content and the arabinose-to-xylose ratio (A/X) were not statistically modified. The Fourier transform infrared spectra of the AXPPs showed a diminution in the intensity of amide I and amide II bands concerning AXs. The AXPP gels (1% w/v) induced via laccase registered a slight increase in the dimers of ferulic acid cross-linking content (9%) and the G’ value (27%) about the AX gels. The electro-sprayed nanoparticles of AXs and AXPPs (NAXs and NAXPPs, respectively) revealed a spherical and regular morphology via transmission electron microscopy. The nanoparticle diameter was not different for the NAXs and NAXPPs, while the NAXPPs show a significant reduction in Z potential value compared to NAXs. Confocal laser microscopy observations were conducted, to analyze the protein content in the AX network, and a decrease in illuminated areas was observed in the AXPP gels and the NAXPPs. These results indicate that the enzymatical treatment of an AX improves the polysaccharide gelling capability, but does not influence the fabrication of electro-sprayed covalent nanoparticles. NAXs and NAXPPs could be attractive biomaterials for diverse pharmaceutical and biomedical applications.","PeriodicalId":18775,"journal":{"name":"Natural Polysaccharides in Drug Delivery and Biomedical Applications","volume":"26 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135829381","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-09-28DOI: 10.3390/polysaccharides4040020
Linara R. Yakupova, Anna A. Skuredina, Tatina Yu. Kopnova, Elena V. Kudryashova
The aim of this work was to investigate the physico-chemical and biological properties of cyclodextrin-based polymers by the example of interaction with human serum albumin, erythrocytes, and bacteria to understand the prospects of their application as drug delivery systems. We synthesized polymers based on one of cyclodextrin derivatives with nonpolar (-CH3) or polar (-CH2CH(OH)CH3) substituents by crosslinking with 1,6-hexamethylene diisocyanate or succinic anhydride. The polymers form particles with an average size of ~200 nm in the aqueous solutions; their structures were confirmed by FTIR and 1H NMR. Cyclodextrin derivatives and their polymers did not affect the secondary structure content of human serum albumin, which might mean a mild effect on the structural and functional properties of the main blood plasma protein. Polymers extract drug molecules from albumin + drug complex by 8–10%, which was demonstrated using ibuprofen and bromophenol blue as model bioactive molecules for site I and site II in protein; thus, the nanoparticles might slightly change the drug’s pharmacokinetics. Using the hemolysis test, we found that polymers interact with red blood cells and can be assigned to non-hemolytic and slightly hemolytic groups as biocompatible materials, which are safe for in vivo use. The cyclodextrins and their polymers did not extract proteins from bacterial cell walls and did not demonstrate any antibacterial activity against Gram-positive and Gram-negative strains. Thus, the cyclodextrin-based polymers possess variable properties depending on the substituent in the monomer and linker type; demonstrated biocompatibility, biodegradability, and negligible toxicity that opens up prospects for their application in biomedicine and ecology.
{"title":"In Vitro Biological Properties of Cyclodextrin-Based Polymers: Interaction with Human Serum Albumin, Red Blood Cells and Bacteria","authors":"Linara R. Yakupova, Anna A. Skuredina, Tatina Yu. Kopnova, Elena V. Kudryashova","doi":"10.3390/polysaccharides4040020","DOIUrl":"https://doi.org/10.3390/polysaccharides4040020","url":null,"abstract":"The aim of this work was to investigate the physico-chemical and biological properties of cyclodextrin-based polymers by the example of interaction with human serum albumin, erythrocytes, and bacteria to understand the prospects of their application as drug delivery systems. We synthesized polymers based on one of cyclodextrin derivatives with nonpolar (-CH3) or polar (-CH2CH(OH)CH3) substituents by crosslinking with 1,6-hexamethylene diisocyanate or succinic anhydride. The polymers form particles with an average size of ~200 nm in the aqueous solutions; their structures were confirmed by FTIR and 1H NMR. Cyclodextrin derivatives and their polymers did not affect the secondary structure content of human serum albumin, which might mean a mild effect on the structural and functional properties of the main blood plasma protein. Polymers extract drug molecules from albumin + drug complex by 8–10%, which was demonstrated using ibuprofen and bromophenol blue as model bioactive molecules for site I and site II in protein; thus, the nanoparticles might slightly change the drug’s pharmacokinetics. Using the hemolysis test, we found that polymers interact with red blood cells and can be assigned to non-hemolytic and slightly hemolytic groups as biocompatible materials, which are safe for in vivo use. The cyclodextrins and their polymers did not extract proteins from bacterial cell walls and did not demonstrate any antibacterial activity against Gram-positive and Gram-negative strains. Thus, the cyclodextrin-based polymers possess variable properties depending on the substituent in the monomer and linker type; demonstrated biocompatibility, biodegradability, and negligible toxicity that opens up prospects for their application in biomedicine and ecology.","PeriodicalId":18775,"journal":{"name":"Natural Polysaccharides in Drug Delivery and Biomedical Applications","volume":"19 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135388417","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Providing safe drinking water free of heavy metal ions like iron and oxyanions like sulfate has become a worldwide issue. Starch, as one of the widely cheapest and available biomaterials, has demonstrated its capability to adsorb heavy metal ions from water in various scientific research, but in low adsorption rates. Therefore, this paper aims to prepare a biopolymer based on a starch–chitosan blend to raise the adsorption efficiency of starch. Two types of chitosan were used to modify potato starch (ps): low molecular chitosan (ch60) and high molecular chitosan (ch4000). Nano potato starch (n.ps) was prepared from potato starch and was also modified with both chitosans. The surface property, the morphology, the particle size, and the structure of the samples were analyzed. Moreover, the investigation of the samples by the zeta potential and charge density were evaluated to determine the charge of the adsorbents’ surface. Furthermore, the pseudo first order (PFO) and pseudo second order (PSO) were employed to examine the adsorption kinetic. The adsorption isotherms of Fe2+/3+ and SO42− were fitted employing Langmuir, Sips, and Dubinin-Radushkevich adsorption models. The maximum achieved sorption capacities from the FeSO4 solution for Fe2+/3+ were as follows: 115 mg/g for n.ps & ch4000, 90 mg/g for ps & ch4000, 80 mg/g for n.ps & ch60, and 61 mg/g for ps & ch60. Similarly, for SO42−, it was 192 mg/g for n.ps & ch4000, 155 mg/g for n.ps & ch60, 137 mg/g for ps & ch4000, and 97 mg/g for ps & ch60.
{"title":"Ecological Sorption of Iron and Sulfate Ions onto Starch and Chitosan Biopolymer Blend","authors":"Rahma Boughanmi, Christine Steinbach, Niklas Gerlach, Marina Oelmann, Christoph Beutner, Simona Schwarz","doi":"10.3390/polysaccharides4030019","DOIUrl":"https://doi.org/10.3390/polysaccharides4030019","url":null,"abstract":"Providing safe drinking water free of heavy metal ions like iron and oxyanions like sulfate has become a worldwide issue. Starch, as one of the widely cheapest and available biomaterials, has demonstrated its capability to adsorb heavy metal ions from water in various scientific research, but in low adsorption rates. Therefore, this paper aims to prepare a biopolymer based on a starch–chitosan blend to raise the adsorption efficiency of starch. Two types of chitosan were used to modify potato starch (ps): low molecular chitosan (ch60) and high molecular chitosan (ch4000). Nano potato starch (n.ps) was prepared from potato starch and was also modified with both chitosans. The surface property, the morphology, the particle size, and the structure of the samples were analyzed. Moreover, the investigation of the samples by the zeta potential and charge density were evaluated to determine the charge of the adsorbents’ surface. Furthermore, the pseudo first order (PFO) and pseudo second order (PSO) were employed to examine the adsorption kinetic. The adsorption isotherms of Fe2+/3+ and SO42− were fitted employing Langmuir, Sips, and Dubinin-Radushkevich adsorption models. The maximum achieved sorption capacities from the FeSO4 solution for Fe2+/3+ were as follows: 115 mg/g for n.ps & ch4000, 90 mg/g for ps & ch4000, 80 mg/g for n.ps & ch60, and 61 mg/g for ps & ch60. Similarly, for SO42−, it was 192 mg/g for n.ps & ch4000, 155 mg/g for n.ps & ch60, 137 mg/g for ps & ch4000, and 97 mg/g for ps & ch60.","PeriodicalId":18775,"journal":{"name":"Natural Polysaccharides in Drug Delivery and Biomedical Applications","volume":"59 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135885313","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-09-08DOI: 10.3390/polysaccharides4030018
Sergio Paoletti, Ivan Donati
Calorimetric (from both isothermal micro-calorimetry and DSC), chiro-optical, viscometric and rheological data on aqueous solutions of pectic acid and low-methoxyl pectin (LMP), published over decades from different laboratories, have been comparatively revisited. The aim was to arrive at a consistent and detailed description of the behavior of galacturonan as a function of pH, i.e., of the degree of charging (as degree of dissociation, α) of the polyanion. The previously hypothesized pH-induced transition from a 31 to a 21 helix was definitely confirmed, but it has been shown, for the first time, that the transition is always coupled with loosening/tightening effects brought about by an increase in charge. The latter property has a twofold effect: the former effect is a purely physical one (polyelectrolytic), which is always a loosening one. However, in the very low range of pH and before the beginning of the transition, an increase in charge tightens the 31 helix by strengthening an intramolecular—but inter-residue—hydrogen bond. The value of the enthalpy change of 31 → 21 transition—+0.59 kcal·mol−1—is bracketed by those provided by theoretical modeling, namely +0.3 and +0.8 kcal·mol−1; the corresponding entropy value is also positive: +1.84 cal·mole r.u.−1·K−1. The enthalpic and the entropic changes in chain loosening amount only to about 23% of the corresponding 31 → 21 changes, respectively. Much like poly(galacturonic acid), the 31 conformation of LMP also stiffens on passing from pH = 2.5 to 3.0, to then start loosening and transforming into the 21 one on passing to pH = 4.0. Lowering the pH of a salt-free aqueous solution of LMP down to 1.6 brings about a substantial chain–chain association, which is at the root of the interchain junctions stabilizing the acid pH gels, in full agreement with the rheological results. A comparison of the enthalpic data reveals that, at 85 °C, LMP in acidic pH conditions has lost its initial order by about 2.3 times more than pectic acid brought from low charging to full neutralization (at α = 1.0) at 25 °C. A proper combination of experiments (enthalpic measurements) and theory (counterion condensation polyelectrolyte theory) succeeded in demonstrating, for the first time ever, a lyotropic/Hofmeister effect of the anion perchlorate in stabilizing the more disordered form of the 21 helix of galacturonan. The viscometric results in water showed that the 31 helix is capable of forming longer rheologically cooperative units compared with the 21 helix. Extrapolation to infinite ionic strength confirmed that, once all electrostatic interactions are cancelled, the elongation of the two helical forms is practically the same. At the same time, however, they indicated that the flexibility of the two-fold helix is more than fifteen times larger than that of the three-fold one. The result is nicely corroborated by a critical revisiting of 23Na relaxation experiments.
{"title":"pH Effects on the Conformations of Galacturonan in Solution: Conformational Transition and Loosening, Extension and Stiffness","authors":"Sergio Paoletti, Ivan Donati","doi":"10.3390/polysaccharides4030018","DOIUrl":"https://doi.org/10.3390/polysaccharides4030018","url":null,"abstract":"Calorimetric (from both isothermal micro-calorimetry and DSC), chiro-optical, viscometric and rheological data on aqueous solutions of pectic acid and low-methoxyl pectin (LMP), published over decades from different laboratories, have been comparatively revisited. The aim was to arrive at a consistent and detailed description of the behavior of galacturonan as a function of pH, i.e., of the degree of charging (as degree of dissociation, α) of the polyanion. The previously hypothesized pH-induced transition from a 31 to a 21 helix was definitely confirmed, but it has been shown, for the first time, that the transition is always coupled with loosening/tightening effects brought about by an increase in charge. The latter property has a twofold effect: the former effect is a purely physical one (polyelectrolytic), which is always a loosening one. However, in the very low range of pH and before the beginning of the transition, an increase in charge tightens the 31 helix by strengthening an intramolecular—but inter-residue—hydrogen bond. The value of the enthalpy change of 31 → 21 transition—+0.59 kcal·mol−1—is bracketed by those provided by theoretical modeling, namely +0.3 and +0.8 kcal·mol−1; the corresponding entropy value is also positive: +1.84 cal·mole r.u.−1·K−1. The enthalpic and the entropic changes in chain loosening amount only to about 23% of the corresponding 31 → 21 changes, respectively. Much like poly(galacturonic acid), the 31 conformation of LMP also stiffens on passing from pH = 2.5 to 3.0, to then start loosening and transforming into the 21 one on passing to pH = 4.0. Lowering the pH of a salt-free aqueous solution of LMP down to 1.6 brings about a substantial chain–chain association, which is at the root of the interchain junctions stabilizing the acid pH gels, in full agreement with the rheological results. A comparison of the enthalpic data reveals that, at 85 °C, LMP in acidic pH conditions has lost its initial order by about 2.3 times more than pectic acid brought from low charging to full neutralization (at α = 1.0) at 25 °C. A proper combination of experiments (enthalpic measurements) and theory (counterion condensation polyelectrolyte theory) succeeded in demonstrating, for the first time ever, a lyotropic/Hofmeister effect of the anion perchlorate in stabilizing the more disordered form of the 21 helix of galacturonan. The viscometric results in water showed that the 31 helix is capable of forming longer rheologically cooperative units compared with the 21 helix. Extrapolation to infinite ionic strength confirmed that, once all electrostatic interactions are cancelled, the elongation of the two helical forms is practically the same. At the same time, however, they indicated that the flexibility of the two-fold helix is more than fifteen times larger than that of the three-fold one. The result is nicely corroborated by a critical revisiting of 23Na relaxation experiments.","PeriodicalId":18775,"journal":{"name":"Natural Polysaccharides in Drug Delivery and Biomedical Applications","volume":"3 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136362679","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-08-30DOI: 10.3390/polysaccharides4030017
Adam Tabacof, V. Calado, N. Pereira
Lactic acid is a molecule used abundantly in the food, cosmetic, and pharmaceutical industries. It is also the building block for polylactic acid, a biodegradable polymer which has gained interest over the last decade. Seaweeds are fast growing, environmentally friendly, and economically beneficial. The Rhodophyta, Kappaphycus alvarezii, is a carrageenan-rich alga, which can be successfully fermented into lactic acid using lactic acid bacteria. Lactobacillus pentosus is a versatile and robust bacterium and an efficient producer of lactic acid from many different raw materials. Bioreactor strategies for lactic acid fermentation of K. alvarezii hydrolysate were tested in 2-L stirred-tank bioreactor fermentations, operating at 37 °C, pH 6, and 150 rpm. Productivity and yields were 1.37 g/(L.h) and 1.17 g/g for the pulse fed-batch, and 1.10 g/(L.h) and 1.04 g/g for extended fed-batch systems. A 3.57 g/(L.h) production rate and a 1.37 g/g yield for batch fermentation operating with an inoculum size of 0.6 g/L was recorded. When applying fed-batch strategies, fermentation products reached 91 g/L with pulse feed and 133 g/L with constant continuous feed. For control and comparison, a simple batch of synthetic galactose-rich Man-Sharpe-Rugosa (MRS) media was fermented at the same conditions. A short study of charcoal regenerability is shown. A scheme for a third-generation lactic acid biorefinery is proposed, envisioning a future sustainable large-scale production of this important organic acid.
{"title":"Lactic Acid Fermentation of Carrageenan Hydrolysates from the Macroalga Kappaphycus alvarezii: Evaluating Different Bioreactor Operation Modes","authors":"Adam Tabacof, V. Calado, N. Pereira","doi":"10.3390/polysaccharides4030017","DOIUrl":"https://doi.org/10.3390/polysaccharides4030017","url":null,"abstract":"Lactic acid is a molecule used abundantly in the food, cosmetic, and pharmaceutical industries. It is also the building block for polylactic acid, a biodegradable polymer which has gained interest over the last decade. Seaweeds are fast growing, environmentally friendly, and economically beneficial. The Rhodophyta, Kappaphycus alvarezii, is a carrageenan-rich alga, which can be successfully fermented into lactic acid using lactic acid bacteria. Lactobacillus pentosus is a versatile and robust bacterium and an efficient producer of lactic acid from many different raw materials. Bioreactor strategies for lactic acid fermentation of K. alvarezii hydrolysate were tested in 2-L stirred-tank bioreactor fermentations, operating at 37 °C, pH 6, and 150 rpm. Productivity and yields were 1.37 g/(L.h) and 1.17 g/g for the pulse fed-batch, and 1.10 g/(L.h) and 1.04 g/g for extended fed-batch systems. A 3.57 g/(L.h) production rate and a 1.37 g/g yield for batch fermentation operating with an inoculum size of 0.6 g/L was recorded. When applying fed-batch strategies, fermentation products reached 91 g/L with pulse feed and 133 g/L with constant continuous feed. For control and comparison, a simple batch of synthetic galactose-rich Man-Sharpe-Rugosa (MRS) media was fermented at the same conditions. A short study of charcoal regenerability is shown. A scheme for a third-generation lactic acid biorefinery is proposed, envisioning a future sustainable large-scale production of this important organic acid.","PeriodicalId":18775,"journal":{"name":"Natural Polysaccharides in Drug Delivery and Biomedical Applications","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77230307","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-08-20DOI: 10.3390/polysaccharides4030016
G. D. Díaz Bukvic, E. Rossi, M. Errea
Adsorption processes, due to their technical simplicity and cost-effectiveness, have arisen as one of the most well-known, straightforward solutions to water pollution. In this context, polysaccharides, due to their abundance, biodegradability, and biocompatibility, are appealing raw materials for the design of adsorbents. Moreover, some of them, such as chitosan, can be obtained from organic waste products, and their use additionally contributes to solving another concerning problem: organic waste accumulation. Unfortunately, due to their low adsorption capacities and/or physicochemical properties, native polysaccharides are not suitable for this purpose. However, there are alternatives that can overcome these physical or chemical limitations, often taking advantage of the versatility of their polyhydroxylated structure. In this context, this review aims to present an overview of the advances from 2019 onwards in the design of new adsorbents for water treatment from cellulose, alginate, chitosan, and starch, addressing the two main strategies reported in the literature: the preparation of either polysaccharide-based composites or polysaccharide derivatives. It is important to point out that, herein, special emphasis is placed on the relationship between the chemical structure and the efficiency as adsorbents of the analyzed materials, in an attempt to contribute to the rational design of adsorbents obtained from polysaccharides.
{"title":"Polysaccharides as Economic and Sustainable Raw Materials for the Preparation of Adsorbents for Water Treatment","authors":"G. D. Díaz Bukvic, E. Rossi, M. Errea","doi":"10.3390/polysaccharides4030016","DOIUrl":"https://doi.org/10.3390/polysaccharides4030016","url":null,"abstract":"Adsorption processes, due to their technical simplicity and cost-effectiveness, have arisen as one of the most well-known, straightforward solutions to water pollution. In this context, polysaccharides, due to their abundance, biodegradability, and biocompatibility, are appealing raw materials for the design of adsorbents. Moreover, some of them, such as chitosan, can be obtained from organic waste products, and their use additionally contributes to solving another concerning problem: organic waste accumulation. Unfortunately, due to their low adsorption capacities and/or physicochemical properties, native polysaccharides are not suitable for this purpose. However, there are alternatives that can overcome these physical or chemical limitations, often taking advantage of the versatility of their polyhydroxylated structure. In this context, this review aims to present an overview of the advances from 2019 onwards in the design of new adsorbents for water treatment from cellulose, alginate, chitosan, and starch, addressing the two main strategies reported in the literature: the preparation of either polysaccharide-based composites or polysaccharide derivatives. It is important to point out that, herein, special emphasis is placed on the relationship between the chemical structure and the efficiency as adsorbents of the analyzed materials, in an attempt to contribute to the rational design of adsorbents obtained from polysaccharides.","PeriodicalId":18775,"journal":{"name":"Natural Polysaccharides in Drug Delivery and Biomedical Applications","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83497212","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-07-24DOI: 10.3390/polysaccharides4030015
M. Horn, V. Martins, A. Plepis
Mechanical, barrier, and thermal properties of films based on blends of corn starch and chitosan plasticized with ethylene glycol, glycerol, and sorbitol were investigated. Starch amylopectin variation was explored, and contents of 100% and 73% were employed to blend with chitosan and polyols. The findings showed that high amylopectin content has a significant effect (p < 0.05), resulting in films with lower tensile strength (TS) and reduced water vapor permeability (WVP). On the other hand, the incorporation of polyols showed a significantly high (p < 0.05) elongation at break (EB) for films plasticized with glycerol and sorbitol at high amylopectin content. For chitosan/73% amylopectin film, the addition of plasticizers exhibited no significant difference (p < 0.05) among the samples for TS and WVP results. The amylopectin content played no influence in the degradation stability of the films measured by thermogravimetry (TGA). However, amylopectin content influences the endothermic peak temperature observed by differential scanning calorimetry (DSC) analysis. A reduction of about 15 °C was noticed for the film prepared with high amylopectin content, a behavior correlated to its amorphous structure, capable of retaining more water than a crystalline region.
{"title":"Effect of Amylopectin Content on Mechanical, Barrier and Thermal Properties of Plasticized Starch/Chitosan Films","authors":"M. Horn, V. Martins, A. Plepis","doi":"10.3390/polysaccharides4030015","DOIUrl":"https://doi.org/10.3390/polysaccharides4030015","url":null,"abstract":"Mechanical, barrier, and thermal properties of films based on blends of corn starch and chitosan plasticized with ethylene glycol, glycerol, and sorbitol were investigated. Starch amylopectin variation was explored, and contents of 100% and 73% were employed to blend with chitosan and polyols. The findings showed that high amylopectin content has a significant effect (p < 0.05), resulting in films with lower tensile strength (TS) and reduced water vapor permeability (WVP). On the other hand, the incorporation of polyols showed a significantly high (p < 0.05) elongation at break (EB) for films plasticized with glycerol and sorbitol at high amylopectin content. For chitosan/73% amylopectin film, the addition of plasticizers exhibited no significant difference (p < 0.05) among the samples for TS and WVP results. The amylopectin content played no influence in the degradation stability of the films measured by thermogravimetry (TGA). However, amylopectin content influences the endothermic peak temperature observed by differential scanning calorimetry (DSC) analysis. A reduction of about 15 °C was noticed for the film prepared with high amylopectin content, a behavior correlated to its amorphous structure, capable of retaining more water than a crystalline region.","PeriodicalId":18775,"journal":{"name":"Natural Polysaccharides in Drug Delivery and Biomedical Applications","volume":"20 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90737052","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}