Gut microbiota fermentation of marine polysaccharides and its effects on intestinal ecology: An overview Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-19 Qingsen Shang, Hao Jiang, Chao Cai, Jiejie Hao, Guoyun Li, Guangli Yu
Rheological and morphological characterization of the culture broth during exopolysaccharide production by Enterobacter sp. Carbohydr. Polym. (IF 4.811) Pub Date : 2009-09-15 Vítor D. Alves, Filomena Freitas, Cristiana A.V. Torres, Madalena Cruz, Rodolfo Marques, Christian Grandfils, M.P. Gonçalves, Rui Oliveira, Maria A.M. Reis
Enterobacter sp. was grown on glycerol byproduct from the biodiesel industry for the production of a value-added exopolysaccharide (EPS). The culture broth was characterized in terms of its morphological and rheological properties throughout the cultivation run. Microscopic observations revealed the formation of cell aggregates surrounded by the EPS at the beginning of the cultivation run, while, at the end, aggregates were reduced and an EPS matrix with the cells embedded in it was observed. The apparent viscosity of the culture broth increased over time, which was attributed to the increase of the EPS concentration in the first period of the cultivation run. However, in the final stage, the creation of new polymer interactions within the complex culture broth was likely the reason for the viscosity increase observed, since there was not a significant variation of the EPS concentration, average molecular weight or chemical composition. The broth presented a Newtonian behavior at the beginning of the run, changing to pseudoplastic as the EPS concentration increased, and revealed to follow the Cox–Merz rule.
Fabrication of porous chitosan membranes composed of nanofibers by low temperature thermally induced phase separation, and their adsorption behavior for Cu2+ Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-18 Wang Qin, Jixiang Li, Jianbing Tu, Hongqin Yang, Qinhui Chen, Haiqing Liu
Structural and physicochemical changes in guar gum by alcohol–acid treatment Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-18 Dandan Li, Na Yang, Yao Zhang, Lunan Guo, Shangyuan Sang, Zhengyu Jin, Xueming Xu
The aim of this study was to evaluate the effects of alcohol-acid degradation on the structural and physicochemical characteristics of guar gum. Guar gum (50 wt.%) was treated with methanol, ethanol, 2-propanol, or 1-butanol containing 1 or 2 mL 36% hydrochloric acid at 75 °C for 30–240 min. The linear relationship between 1/Mw and time suggested that alcohol-acid degradation followed first-order kinetics with rate constants varying directly with the number of alcohol carbon atoms and acid concentration. Alcohol-acid treatment exerted no effect on the chemical and crystal structure of guar but significantly decreased shear viscosity, slightly increased solubility, mildly reduced thermostability, and dramatically darkened colour. This study extended the knowledge of the effect of alcohol on the acid hydrolysis of guar and will contribute to the development of a large-scale procedure for guar gum degradation.
Isolation, purification and structural characterization of a new water-soluble polysaccharide from Eremurus stenophyllus (boiss. & buhse) baker roots Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-18 Kambiz Jahanbin, Ali Abbasian, Maryam Ahang
A new water-soluble polysaccharide (ESPS-1), with the average molecular weight of 52.1 kDa and a specific optical rotation of +169.7° (c 1.0, H2O), was successfully isolated by warm-water extraction and then purified using DEAE-Cellulose and Sephadex G-100 columns from the roots of Eremurus stenophyllus. The results from chemical and instrumental tests including FT-IR, methylation and GC–MS analysis, periodate oxidation and smith degradation, partial acid hydrolysis, and NMR spectroscopy (1H, 13C, 1H-1H COSY, HMQC and HMBC) demonstrated that ESPS-1 was a 2-O-acetylgalactan, composed of galactose, arabinose and mannose in a molar ratio of about 10:3:1, respectively. It has a backbone of (1 → 6)-α-D-galactopyranosyl residues, with branches at O-3 consisting of α-D-Manp-(1 → 3)-α-L-Araf-(1 → 3)-α-L-Araf-(1 → 3)-α-L-Araf-(1→. The acetyl groups are substituted at O-2 of (1 → 6)-linked Galp and the degree of acetylation was about 14%.
Preparation of cationized starch from food industry waste biomass and its utilization in sulfate removal from aqueous solution Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-18 Katja Lappalainen, Johanna Kärkkäinen, Matti Niemelä, Harri Vartiainen, Olli Rissanen, Hanne Korva
In this work, untreated starch-rich potato peel waste was used as a starting material in preparation of cationized starch (CS)1 in water solution with 2-chloro-3-hydroxypropyltrimethylammonium chloride (CHPTAC) as the cationization reagent. The impact of various factors (activation time, temperature, reaction time, the amount of CHPTAC and NaOH) on the degree of substitution (DS) of CS was studied by using experimental design. The DS values were determined by 1H NMR. The highest DS (0.40) was obtained when the reaction time was 8 h, temperature 30 °C, the molar ratio of CHPTAC and NaOH to AGU 3 and 3.75, respectively. The prepared CS was successfully used to remove sulfate ions from an aqueous solution with ultrafiltration technique. Sulfate is a major pollutant of water bodies so development of efficient techniques for its removal is detrimental. The removal of sulfate in study was 74% at best.
A dextran with unique rheological properties produced by the dextransucrase from Oenococcus kitaharae DSM 17330 Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-18 Marlène Vuillemin, Florent Grimaud, Marion Claverie, Agnès Rolland-Sabaté, Catherine Garnier, Patrick Lucas, Pierre Monsan, Marguerite Dols-Lafargue, Magali Remaud-Siméon, Claire Moulis
A gene encoding a novel dextransucrase was identified in the genome of Oenococcus kitaharae DSM 17330 and cloned into E. coli. With a kcat of 691 s−1 and a half-life time of 111 h at 30 °C, the resulting recombinant enzyme −named DSR-OK- stands as one of the most efficient and stable dextransucrase characterized to date. From sucrose, this enzyme catalyzes the synthesis of a quasi linear dextran with a molar mass higher than 1 × 109 g/mol that presents uncommon rheological propertiessuch as a higher viscosity than that of the most industrially used dextran from L. mesenteroides NRRL-B-512F, a yield stress that was never described before for any type of dextran, as well as a gel-like structure. All these properties open the way to a vast array of new applications in health, food/feed, bulk or fine chemicals fields.
Structure and in vitro anticancer activity of sulfated O-polysaccharide from marine bacterium Poseidonocella pacifica KMM 9010T Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-17 Maxim S. Kokoulin, Alexandra S. Kuzmich, Anatoly I. Kalinovsky, Eugene S. Rubtsov, Lyudmila A. Romanenko, Valery V. Mikhailov, Nadezhda A. Komandrova
We presented the structure of the sulfated polysaccharide moiety and anticancer activity in vitro of the О-deacylated lipopolysaccharide (DPS) isolated from the marine bacterium Poseidonocella pacifica KMM 9010T. The structure of O-polysaccharide was investigated by chemical methods along with 1H and 13C NMR spectroscopy. The O-polysaccharide was built up of sulfated disaccharide repeating units consisted of D-rhamnose (D-Rhaр) and 3-deoxy-D-manno-oct-2-ulosonic acid (Kdop): →7)-β-Kdoр4Ac5S-(2→3)-β-D-Rhaр2S-(1→. We demonstrated that the DPS from P. pacifica KMM 9010T non-toxic for normal mouse epidermal cells (JB6 Cl41 cell line) and inhibited a colony formation of human colorectal carcinoma HT-29, breast adenocarcinoma MCF-7 and melanoma SK-MEL-5 cells in a dose-dependent manner.
Eco-friendly films prepared from plantain flour/PCL blends under reactive extrusion conditions using zirconium octanoate as a catalyst Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-17 Tomy J. Gutiérrez, Vera A. Alvarez
Plantain flour (Musa ssp., group AAB, sub-group clone Harton)/poly(ε-caprolactone) (PCL) blends, containing glycerol as a plasticizer, were prepared by reactive extrusion (REx) in a twin-screw extruder using zirconium octanoate (Zr(Oct)4) as a catalyst, followed by thermo-compression molding for film development. The films were then characterized in terms of their: infrared (FTIR) spectra, water solubility, thermogravimetric (TGA) curves, differential scanning calorimetry (DSC) thermograms, and X-ray diffraction (XDR) diffractograms, as well as their microstructural, mechanical and antimicrobial properties in order to 1) compare the effects of PCLs with two different molecular weights (Mw) on the characteristics of the plantain flour/PCL blends, and 2) determine whether using Zr(Oct)4 in the production of active composite polymer materials improves their properties. The plantain flour/PCL blends were all developed successfully. The higher Mw PCL gave more hydrophobic and thermally stable films with improved mechanical properties. The addition of the Zr(Oct)4 catalyst to the plantain flour/PCL blends also resulted in films with similar characteristics to those described above, due to the cross-linking of the polymers. In addition, the films containing the catalyst showed antimicrobial activity against Escherichia coli O157:H7 and Staphylococcus aureus indicating a dual effect of Zr(Oct)4, and making it an attractive alternative for the development of active films.
Development of chitosan-sodium phytate nanoparticles as a potent antibacterial agent Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-17 Jie Yang, Hao Lu, Man Li, Jing Liu, Shuangling Zhang, Liu Xiong, Qingjie Sun
Chitosan nanoparticles have attracted considerable attention as a potential carrier for food and pharmaceutical applications. Herein, using natural sodium phytate as a gelation agent, we developed a new type of green and biocompatible chitosan nanoparticles. We discovered that the chitosan-sodium phytate nanoparticles exhibited potent antibacterial activities. The chitosan-sodium phytate nanoparticles prepared from low molecular weight (LMW, 140 ± 7 kDa) and medium molecular weight (MMW, 454 ± 21 kDa) chitosan were spherical. Under optimum conditions—with a ratio of LMW chitosan to sodium phytate of 24:1 and MMW chitosan to sodium phytate of 21:1—the sizes of the LMW and MMW chitosan nanoparticles were 20–80 and 80–100 nm, respectively, as observed by transmission electron microscopy. The formation mechanism of chitosan nanoparticles occurred through both electrostatic interactions and hydrogen bonds. No cytotoxicity for normal liver cells was found in chitosan-sodium phytate nanoparticles measured by methyl thiazolyl tetrazolium assay. Furthermore, the antimicrobial assays indicated that the antimicrobial activity of the LMW chitosan nanoparticles was greater than that of MMW chitosan nanoparticles. The minimum inhibition concentration values and half inhibiting concentration of LMW chitosan-sodium phytate nanoparticles for Escherichia coli were 1.5 and 0.8 mg/mL, respectively. In addition, the antimicrobial activity of chitosan nanoparticles against Gram-negative bacteria was better than that against Gram-positive bacteria. The newly developed chitosan-sodium phytate nanoparticles could be used as a potential antibacterial agent.
Chitosan as an effective inhibitor of multidrug resistant Acinetobacter baumannii Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-15 E.M. Costa, S. Silva, S. Vicente, M. Veiga, F. Tavaria, M.M. Pintado
Over the last two decades worldwide levels of antibiotic resistance have risen leading to the appearance of multidrug resistant microorganisms. Acinetobacter baumannii is a known skin pathogen which has emerged as a major cause of nosocomial outbreaks due to its capacity to colonize indwelling medical devices and natural antibiotic resistance. With chitosan being an effective antimicrobial agent against antibiotic resistant microorganisms, the aim of this work was to access its potential as an alternative to traditional antimicrobials in the management of A. baumannii growth. What the results showed was that both chitosan MW’s tested were active upon A. baumannii’s planktonic and sessile growth. For planktonic growth MICs and MBCs were obtained at relatively low concentrations (0.5–2 mg/mL) while for sessile growth chitosan proved to be a effective inhibitor of A. baumannii’s adhesion and biofilm formation. Considering these results chitosan shows a high potential for control of A. baumannii infections.
Hypoglycemic effect and mechanism of a pectic polysaccharide with hexenuronic acid from the fruits of Ficus pumila L. in C57BL/KsJ db/db mice Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-14 Jianjun Wu, Miaomiao Chen, Songshan Shi, Huijun Wang, Ning Li, Juan Su, Ruimin Liu, Zhenlin Huang, Hong Jin, Xueqing Ji, Shunchun Wang
In this study, a particular pectic polysaccharide (FPLP) was extracted and purified from the fruits of Ficus pumila Linn. through boiling water extraction, alcohol precipitation, diethylaminoethyl-Sepharose Fast Flow chromatography and Superdex™ G-75 gel filtration chromatography. Analysis of high-performance gel permeation chromatography, FTIR, GC–MS, methylation and 1D/2D NMR spectroscopy revealed that FPLP (Mw: 34.69 kDa) is a linear (1,4)-α-d-galacturonic acid binding 1.30% branched chain hexenuronic acid with 23.34% methyl esterification. Treatment with FPLP ameliorated hyperglycaemia in association with an improvement in hepatic glycogen metabolism in C57BL/KsJ db/db mice. The activation of IRS-1/PI3K/Akt/GSK3β/GS insulin signalling pathway and AMPK/GSK3β/GS signalling pathway and the regulation of glucokinase, phosphoenolpyruvate carboxykinase and glucose-6-phosphatase expressions involved in hepatic glycogenesis and glycogenolysis were considered the therapeutic mechanisms of FPLP. These results provide a new insight for investigating the effects of pectic polysaccharides on blood glucose control and suggest that FPLP is a promising nutraceutical for treatment of T2DM.
The effect of hydration on the material and mechanical properties of cellulose nanocrystal-alginate composites Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-14 Megan Smyth, Marie-Stella M’Bengue, Maxime Terrien, Catherine Picart, Julien Bras, E. Johan Foster
Alginate is commonly used in the form of hydrogels in biomedical applications. It is known to be highly sensitive to liquid exposure and can degrade or solubilize easily. This study attempts to improve the mechanical and material properties in various humidity conditions and in liquid immersion of thin alginate films with the addition of unmodified and oxidized cellulose nanocrystals (CNCs, CNC-Ts). CNCs and CNC-Ts were added to alginate composites in varying amounts, and the material and mechanical properties were measured in dry, humid, and liquid conditions. It was shown that the properties can be enhanced with the addition of nanocellulose as tested by liquid uptake, and mechanical testing. These results suggest that the addition of TEMPO-oxidized nanocellulose crystals improves the performance and longevity of alginate when exposed to phosphate buffer solution (PBS) compared to deionized water. This improved performance was shown to have a limited effect on the adhesion of mesenchymal stem cells (MSCs) to the surface of the nanocomposites.
Evaluation of disulfide bond-conjugated LMWSC-g-bPEI as non-viral vector for low cytotoxicity and efficient gene delivery Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-14 Gyeong-Won Jeong, Jae-Woon Nah
For efficient gene delivery, non-viral vectors should have high cellular uptake, excellent endosomal escape, and the ability to rapidly release the gene into the cytoplasm. Here, we developed a disulfide bond-conjugated bioreducible LMWSC-g-bPEI (LCP) composed of low molecular-weight water soluble chitosan (LMWSC), bPEI, and cystamine (Cys). The developed LCP had advantages such as low toxicity, great endosomal escape, and rapid release of pDNA into the cytoplasm. The polyplexes with LCP showed higher uptake into the nucleus and greater transfection efficiency than that without disulfide bond. Moreover, LCP polymer and polyplexes with LCP indicated lower cytotoxicity than bPEI 25 kDa. In addition, a gel retardation assay and particle size were analyzed to demonstrate the reduction-sensitive gene delivery system. Besides, intracellular uptake pathway of polyplexes was investigated by various endocytosis inhibitor and confirmed to internalization into cell via macropinocytosis. These results suggest that bioreducible LCP is a superb non-viral vector for efficient gene delivery.
Sugar-cane bagasse derived cellulose enhances performance of polylactide and polydioxanone electrospun scaffold for tissue engineering Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-14 Honita Ramphul, Archana Bhaw-Luximon, Dhanjay Jhurry
Bagasse is a waste product of sugar extraction from sugar-cane with approximately 30% cellulose content. Cellulose was successfully extracted from sugar-cane bagasse using a modified mercerization-bleaching approach with a 40% yield. Extracted cellulose was converted to cellulose acetate for enhanced electrospinnability and blended with poly-l-Lactide or polydioxanone before solution electrospinning. Physico-chemical evaluation of the electrospun mats showed variable miscibility of blends. In vitro cell studies with L929 mouse fibroblast cells was quite conclusive as regards the biocompatibility of the blended mats with proliferative behavior of cells, extracellular matrix deposition and characteristic features of healthy cellular response. MTT assay indicated that the cellulose blended mats induced higher cell densities than the controls. Cellulose content influenced parameters such as fiber diameter, porosity and cell-matrix interaction of mats impacting on cell growth and behavior. Preliminary assessment of biomineralization potential of the mats by SEM showed nano-hydroxyapatite deposits on the electrospun fibers.
Sodium alginate: A promising biopolymer for corrosion protection of API X60 high strength carbon steel in saline medium Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-14 I.B. Obota, Ikenna B. Onyeachu, A.Madhan Kumar
Sodium alginate (SA), a polysaccharide biopolymer, has been studied as an effective inhibitor against the corrosion of API X60 steel in neutral 3.5% NaCl using gravimetric and electrochemical techniques (OCP, EIS and EFM). The inhibition efficiency of the SA increased with concentration but was lower at higher temperature (70 °C). Electrochemical measurements showed that the SA shifted the steel corrosion potential to more positive value and reduced the kinetics of corrosion by forming an adsorbed layer which mitigated the steel surface wetting, based on contact angle measurement. SEM-EDAX was used to confirm the inhibition of SA on API X60 steel surfaces. The SA adsorbs on the steel surface through a physisorption mechanism using its carboxylate oxygen according to UV–vis and ATR–IR measurements, respectively. This phenomena result in decreased localized pitting corrosion of the API X60 steel in 3.5% NaCl solution. Theoretical results using quantum chemical calculations and Monte Carlo simulations provide further atomic level insights into the interaction of SA with steel surface.
Antibacterial poly(ethylene oxide) electrospun nanofibers containing cinnamon essential oil/beta-cyclodextrin proteoliposomes Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-14 Lin Lin, Yajie Dai, Haiying Cui
A novel antibacterial packaging material was engineered by incorporating cinnamon essential oil/β-cyclodextrin (CEO/β-CD) proteoliposomes into poly(ethylene oxide) (PEO) nanofibers by electrospinning technique. Herein, PEO was a stabilizing polymer and used as electrospinning polymeric matrix for the fabrication of CEO/β-CD proteoliposomes nanofibers. The nanoliposomes were inlaid with protein are defined as proteoliposomes. Taking advantage of bacterial protease secreted from Bacillus cereus (B. cereus), the controlled release of CEO from proteoliposomes was achieved via proteolysis of protein in proteoliposomes. The CEO/β-CD inclusion complex was prepared by the aqueous solution method and characterized by Raman and FTIR spectroscopy. After the treatment of CEO/β-CD proteoliposomes nanofibers packaging, the satisfactory antibacterial efficiency against B. cereus on beef was realized without any impact on sensory quality of beef. This study demonstrated that the CEO/β-CD proteoliposomes nanofibers can significantly extend the shelf life of beef and have potential application in active food packaging.
Physical and functional properties of pectin-fish gelatin films containing the olive phenols hydroxytyrosol and 3,4-dihydroxyphenylglycol Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-14 Alejandra Bermúdez-Oria, Guillermo Rodríguez-Gutiérrez, Blanca Vioque, Fátima Rubio-Senent, Juan Fernández-Bolaños
This study describes the development of a composite edible film based on pectin and fish skin protein capable of protecting food from microbial attack and oxidative degradation. The film was prepared with glycerol as plasticizer and the antioxidant and antimicrobial phenolic compounds hydroxytyrosol (HT) and 3,4-dihydroxyphenylglycol (DHPG), extracted from olive fruit, as active agents. The influence of the concentration of plasticizer and active HT/DHPG on the mechanical and functional properties of the films was investigated, with values of water vapor permeability (WVP) between 0.13–0.22 g mm/h m2 kPa and oxygen permeability (OP) between 9.91–40.76 cm3 μm/m2 d kPa. The release behavior in water at different pH values was also evaluated. The antimicrobial capacity of the novel food coating was tested on strawberries, a fruit with high perishability. The bioactive edible film containing HT/DHPG preserved the strawberries against mold during storage with a significant delay in visible decay.
Non-cytotoxic hybrid bioscaffolds of chitosan-silica: sol-gel synthesis, characterization and proposed application Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-14 Athit Pipattanawarothai, Chomchai Suksai, Klaokwan Srisook, Thanida Trakulsujaritchok
Biohybrid chitosan-silica scaffolds were synthesized through the sol-gel and the freeze drying processes. Hydrolysis and condensation of chitosan with tetraethylorthosilicate (TEOS) in the presence of 3-isocyanatopropyl triethoxysilane (ICPTES) were successfully carried out. Results obtained from FTIR, swelling test and pyrolysis confirmed that the hybrid scaffolds containing covalent coupling between the organic and inorganic networks were formed with high crosslink density of Si-O-Si bridging and could be classified as the class II material. The hybridization also resulted in improvements on mechanical strength and stability comparing to the pure chitosan. In vitro investigations on the guided bone regeneration and the cytotoxicity were also performed. SEM-EDS was used to examine the proliferation of calcium phosphate mineral at the scaffold surface after an immersion in simulated body fluid. The results revealed that the hybrid scaffolds exhibited a rapid induction of calcium phosphate mineral without cytotoxicity effect, reflecting an excellent in vitro bone bioactivity which was superior to the pure chitosan scaffold.
Novel Bioactive Surface Functionalization of Bacterial Cellulose Membrane Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-14 Wei Shao, Jimin Wu, Hui Liu, Shan Ye, Lei Jiang, Xiufeng Liu
Quantification of 1,3-β-D-glucan from yeast added as a functional ingredient to bread Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-14 Anne Rieder, Simon Ballance, Ulrike Böcker, Svein Knutsen
Due to their immunomodulatory effect, 1,3-β-G from yeast are used as functional ingredients, but reliable methods for their detection in foods are lacking. We have adapted a method based on fluorescence detection with aniline blue to quantify the amount of five commercial yeast β-glucan preparations added to crisp or yeast-leavened bread. This assay detected yeast β-glucan preparations added to different breads with an average recovery of 90, 96, 99 and 105%, while one of the preparations was overestimated, with an average recovery of 157%. The presence of cereal 1,3-1,4-β-D-glucans did not interfere with assay performance. The addition of 1,3-β-G at 0.2 and 0.5 g/100 g is low compared to the recommended dose of 1,3-β-G per serving demonstrating assay sensitivity. However, more research is needed to fully understand 1,3-β-G conformation/structure on aniline blue interaction as well as the effect of baking on structure and dissolution properties of yeast β-glucans.
Sequential one-pot multienzyme synthesis of hyaluronan and its derivative Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-14 Shuang Li, Shuaishuai Wang, Xuan Fu, Xian-wei Liu, Peng George Wang, Junqiang Fang
Hyaluronan (HA) is a linear polysaccharide composed of repeating disaccharide units. It has been well documented to play an array of biological functions in cancer events. Here, we reported a sequential one-pot multienzyme (OPME) strategy for in vitro synthesis of HA and its derivatives. The strategy, which combined in situ sugar nucleotides generation with HA chain polymerization, could convert cheap monosaccharides into HA polymers without consuming exogenous sugar nucleotide donors. HA polymers (number-average molecular weight ranged from 1.5 × 104 to 5.5 × 105 Da) with over 70% yields were efficiently synthesized and purified from this one-pot system. More importantly, partial labeled HA derivative was further synthesized by metabolic incorporation of unnatural monosaccharide analogues into the sequential OPME system. Cross-linked HA hydrogel was achieved via copper (I)-catalyzed azide-alkyne cycloaddition and exhibited novel networks consisting of both inter- and intra-connected HA chains, which could facilitate the potential applications of this unique polysaccharide.
pH-sensitive carboxymethyl chitosan hydrogels via acid-labile ortho ester linkage for potential biomedical applications Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-14 Liefeng Hu, Panpan Zhang, Xin Wang, Xu Cheng, Jiejie Qin, Rupei Tang
Hydrogel systems with favorable biocompatibility and biodegradability are of much interest for application in biomaterials and tissue engineering. In this study, a new ortho ester-based acid-labile crosslink agent with dual-epoxy end groups was synthesized and crosslinked with carboxymethyl chitosan (CMCS) at different molar ratios to prepare a series of pH-sensitive hydrogels for drug delivering. Doxorubicin (DOX) was then readily loaded into the hydrogels and the in vitro release profiles indicated that the release rate increased rapidly while pH decreased from 7.4 to 5.0, which is consistent with the degradation rate of these hydrogels at corresponding pH conditions. In addition, results from MTT assay and flow cytometry demonstrated that these CMCS-based hydrogels and their degradation products have no cytotoxicity against SH-SY5Y and 293T cells. Therefore, the prepared acid-labile hydrogels could be applied in tumorous drug delivery systems and peritumoral implantation therapy by further optimization.
Chemical modification of xanthan in the ordered and disordered states: an open route for tuning the physico-chemical properties Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-13 Céline Fantou, Audrey N. Roy, Emmanuelle Dé, Sébastien Comesse, Michel Grisel, Frédéric Renou
Preparation, characterization, and properties of fluorine-free superhydrophobic paper based on layer-by-layer assembly Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-13 Jin Yang, Hui Li, Tianqing Lan, Lincai Peng, Rongqi Cui, Hao Yang
A fluorine-free superhydrophobic paper was prepared by a facile method involving layer-by-layer deposition of cationic starch and sodium alginate together with subsequent modification of trichloromethylsilane has been reported in this article. The surface chemical compositions, potentials and surface morphologies of the modified papers were characterized, respectively. The wetting abilities and physical strength properties of the modified papers were investigated. After 4-time deposition of cationic starch/sodium alginate bilayer followed by trichloromethylsilane treatment, the water contact angle of modified paper reached up to 161.7°, and the tensile strength increased by 6.8% in comparison to that of pristine paper. This as-prepared superhydrophobic paper not only showed low bacterial adhesion property, self-cleaning behavior, water repellency, as well as high durability against deformation, chemical and time, but also kept a high strength property under high relative humidity condition, which might has a great application potential in the liquid paper packaging industry.
Two-step economical welan gum production by Sphingomonas sp. HT-1 from sugar industrial by-products Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-12 Xiaoliu Liu, Lijun Lin, Xiaoying Xu, Hao Zhang, Lingtian Wu, Ping Zhu, Sha Li, Hong Xu
A two-step fermentation strategy using glucose mother liquor (GML) for cell growth and xylose mother liquor (XML) for welan gum synthesis was used to alleviate uneconomic welan gum fermentation. This study revealed: (1) optimal initial GML concentration was 11.7 g/L (10 g/L sugars contained); (2) optimal XML feeding strategy was pseudo-exponential fed-batch and feeding time was 12th h to 54th h, amounting to 25.7 g/L XML (20 g/L sugars contained); and (3) in a 7.5-L bioreactor, welan gum concentration was 22.68 ± 0.50 g/L and its yield reached 0.756 g/g sugars with trace residual sugars. Compared with the cost of batch fermentation using glucose as sole carbon source, the final carbon source costs decreased by 61.40% and the welan gum yield increased by 50%. GML and XML can be used as inexpensive carbon sources for welan gum production with higher yield, giving them industrial application potential to produce value-added chemicals.
The performance of chitosan with bentonite microparticles as wet-end additive system for paper reinforcement Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-12 Mehdi Rahmaninia, Mostafa Rohi, Martin A. Hubbe, Seyed Majid Zabihzadeh, Omid Ramezani
In this research, the effect of bentonite micro-particles on the performance of chitosan as a new additive system for improving the dry strengths of acidic papermaking was studied. Chitosan, an abundant carbohydrate biopolymer, in 4 dosages (0, 0.75, 1.25 and 2% based on dry weight of pulp) was applied with bentonite in 4 dosages (0, 0.3, 0.6 and 0.9% based on oven-dry weight of pulp). Although the addition of chitosan up to 0.75% (without bentonite) improved tensile index and burst index, but the addition of more chitosan decreased all mechanical properties in comparison with the control sample. The application of bentonite in combination with chitosan had a significant impact on chitosan performance in mechanical properties. The best results were obtained with 0.3% bentonite consumption. Visual formation ranking had a proper correlation with this obtained results. The micro-kjeldahl indirectly confirmed chitosan retention in the treated paper with chitosan/bentonite.
From 2D to 3D: the morphology, proliferation and differentiation of MC3T3-E1 on silk fibroin/chitosan matrices Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-12 Da-Wei Li, Feng-Li He, Jin He, Xudong Deng, Ya-Li Liu, Yang-Yang Liu, Ya-Jing Ye, Da-Chuan Yin
It has been widely accepted that cell culture in two-dimensional (2D) conditions may not be able to represent growth in three-dimensional (3D) conditions. Systematic comparisons between 2D and 3D cell cultures are needed to appropriately use the existing 2D results. In this work, we conducted a comparative study between 2D and 3D cell cultures of MC3T3-E1 using the same type of material (a mixture of silk fibroin (SF) and chitosan (CS)). Our results showed 3D SF/CS scaffold exhibited different effects on cell culture compared with the 2D cases. 1) The cells grown in 3D scaffold showed multiple morphologies. 2) The proliferation of cells in 3D scaffold was long-term and sustainable. 3) Cell differentiation occurred throughout the entire 3D scaffold. The results showed that cell culture in 3D SF/CS scaffold exhibited different features than 2D cases and 3D SF/CS scaffold could be a promising material for 3D cell culture.
Molecular size is important for the safety and selective inhibition of intrinsic factor Xase for fucosylated chondroitin sulfate Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-12 Lufeng Yan, Junhui Li, Danli Wang, Ding Tian, Yaqin Hu, Xingqian Ye, Robert J. Linhardt, Shiguo Chen
Fucosylated chondroitin sulfate from sea cucumber Isostichopus badionotus (FCS-Ib) showed potent anticoagulant activities without selectivity. The present study focused on developing safe FCS-Ib oligomers showing selective inhibition of intrinsic factor Xase (anti-FXase) prepared through partial N-deacetylation–deaminative cleavage. The N-deacetylation degree was regulated by reaction time, controlling the resulting oligomer distribution. Structure analysis confirmed the selectivity of degradation, and 12 high purity fractions with trisaccharide-repeating units were separated. In vitro anticoagulant assays indicated a decrease in molecular weight (Mw) dramatically reduced activated partial thromboplastin time (APTT), thrombin time (TT), AT-dependent anti-FIIa and anti-FXa activities, while the oligomers retained potent anti-FXase activity until they fell below 3 kDa. Meanwhile, human FXII activation and platelet aggregation were markedly reduced with decreasing Mw and were moderate when under 12.0 kDa. Thus, fragments of 3–12.0 kDa should be safe and effective as selective inhibitors of intrinsic tenase complex for application as clinical anticoagulants.
Multivalent Cations-Triggered Rapid Shape Memory Sodium carboxymethyl cellulose/Polyacrylamide Hydrogels with Tunable Mechanical Strength Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-11 Nan Li, Guangxue Chen, Wei Chen, Jiahe Huang, Junfei Tian, Xiaofang Wan, Minghui He, Hongfang Zhang
A novel multivalent cations-triggered shape memory hydrogels were synthesized in a one-pot method, and interpenetrating double network was formed by chemically cross-linked polyacrylamide (PAM) network and physically cross-linked sodium carboxymethyl cellulose network. The temporary shape was fixed by complexation between a native biopolymer, sodium carboxymethyl cellulose (CMC), and transition metal ions, specifically Fe3+, Ag+, Al3+, Cu2+, Ni2+, and Mg2+. In particular, CMC-Fe3+ hydrogel exhibits excellent shape fixity ratio (95%). Therefore, we chose PAM/CMC1.0-Fe3+ hydrogel as the model material and further investigated its shape recovery process. It was found that a wide range of molecules and anions could be applied to break off the temporary cross-links between CMC and Fe3+. The PAM/CMC composite hydrogels also exhibited excellent tunable mechanical properties. The mechanical properties of the composite hydrogel can be adjusted by changing the cross-linking densities. The presented strategy could enrich the construction as well as application of biopolymers based shape memory hydrogels.
One pot synthesis of gold nanoparticles using chitosan with varying degree of deacetylation and molecular weight Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-11 Lijun Sun, Jin Li, Jun Cai, Lian Zhong, Guohui Ren, Qimin Ma
Gold nanoparticles (AuNPs) were synthesized in one-step by reducing gold salt using nontoxic and biodegradable chitosan as dual roles of reducing agent and stabilizer. The obtained AuNPs were characterized with UV–vis spectroscopy and transmission electron microscopy. The results indicated that control over the size and shape of AuNPs is achieved through the careful selection of experimental conditions, such as reaction temperature, reaction time, concentration of gold salt and chitosan, and chitosan molecular parameters, i.e., degree of deacetylation (DD) and molecular weight (MW). At low chitosan concentration (0.005% and 0.01% (w/v)), individual spherical AuNPs with average particle size around 10 nm were obtained regardless of chitosan DD and MW, while anisotropic AuNPs were obtained at concentration above 0.05% (w/v) for all investigated chitosan at the optimum condition (1 mL of 1 mmol/L HAuCl4 added to 3 mL of chitosan solution reacted for 120 min at 70 °C). The growth of larger polygonal AuNPs was promoted as the higher concentration and lower DD chitosan was used as reducing agent and stabilizer. Au nanoplate was synthesized by water-soluble chitosan (Mv 566 kDa, DD 53%) at concentration above 0.15% (w/v). Chitooligomers (Mv 2.4 kDa, DD 94%) showed the highest reduction ability for Au3+ and the synthesized AuNPs exhibited aggregation on morphology. It was considered that chitosan DD and concentration played a more important role than MW in the size and shape of AuNPs.
Novel starch based emulsion gels and emulsion microgel particles: Design, structure and rheology Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-11 Ophelie Torres, Nidia Mercado Tena, Brent Murray, Anwesha Sarkar
The chemical-free production of nanocelluloses from microcrystalline cellulose and their use as Pickering emulsion stabilizer Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-10 Jean Buffiere, Zoltán Balogh-Michels, Marc Borrega, Thomas Geiger, Tanja Zimmermann, Herbert Sixta
This paper takes a comparative approach in characterizing two types of nano-scale cellulosic particles obtained using chemical-free pathways, either by nearcritical water treatment or by high-shear homogenization from the same microcrystalline cellulose (MCC). The nearcritical water treatment efficiently depolymerized cellulose, producing a solid precipitated fraction of low-molecular-weight material containing cellulose II, while homogenization mechanically deconstructed MCC without altering its molecular structure. Both pathways yielded nanocellulose-like materials yet with different morphologies. The mechanically produced, rod-like particles were obtained with high yield. In contrast, the hydrothermal precipitate exhibited more hydrophobic ribbon-like particles that provided a greater level of particle-particle interaction. Both materials successfully acted as stabilizers for oil-in-water Pickering emulsions; however, the hydrothermally-produced material exhibited superior performance, with stable emulsions obtained upon addition of as low as 1.0 wt.% cellulose. These two pathways are highly relevant for altering the structure and properties of MCC and for formulating new, sustainably produced nanocellulose-based materials.
Investigation of Optimal Conditions for Production of Highly Crystalline Nanocellulose with Increased Yield via Novel Cr(III)-Catalyzed Hydrolysis: Response Surface Methodology Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-10 You Wei Chen, Hwei Voon Lee, Sharifah Bee Abd Hamid
For the first time, a highly efficient Cr(NO3)3 catalysis system was proposed for optimization the yield and crystallinity of nanocellulose end product. A five-level three-factor central composite design coupled with response surface methodology was employed to elucidate parameters interactions between three design factors, namely reaction temperature (x1), reaction time (x2) and concentration of Cr(NO3)3 (x3) over a broad range of process conditions and determine the effect on crystallinity index and product yield. The developed models predicted the maximum nanocellulose yield of 87% at optimum process conditions of 70.6 °C, 1.48 h, and 0.48 M Cr(NO3)3. At these conditions, the obtained nanocellulose presented high crystallinity index (75.3%), spider-web-like interconnected network morphology with the average width of 31.2 ± 14.3 nm. In addition, the yielded nanocellulose rendered a higher thermal stability than that of original cellulosic source and expected to be widely used as reinforcement agent in bio-nanocomposites materials.
Improving molar mass analysis of cellulose samples with limited solubility Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-10 Stephan Silbermann, Christian Weilach, Gerhard Kliba, Karin Fackler, Antje Potthast
Fully dissolved cellulose samples are a requirement for reliable size exclusion chromatography (SEC). Although most of the standard dissolving pulps can be completely dissolved in the N,N-dimethylacetamide/lithium chloride (DMAc/LiCl) solvent system, some cellulose samples (e.g., regenerated cellulose fibers) have poor solubility and therefore have a limited access to molar mass measurements. For improving the latter, different activation steps have been developed.In order to obtain complete solutions for subsequent SEC analysis, the scope of this study was to further improve established methods by elucidating the major influential factors of sample preparation. In addition, the degree of stretching in artificial fibers was examined for viscose fibers. Therefore, activation steps in DMAc or dimethyl sulfoxide (DMSO) and subsequent dissolution in DMAc/LiCl were analyzed with swelling and dissolution kinetics. The time needed for maximum swelling was found to be the optimum activation time for the application of light microscopy. Turbidity measurement was introduced to observe dissolution kinetics as an indicator of dissolution quality. Thus, the duration, as well as the number of steps toward dissolution, was optimized to enhance the throughput in the overall analysis of a large variety of hitherto poorly soluble cellulose samples. A comparison of the MMDs of completely soluble reference materials obtained with the intensified conventional method, and the developed method demonstrated that the latter has no adverse influence on the results.
Mixtures of ionic liquids as more efficient media for cellulose dissolution Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-09 Olga Stolarska, Anna Pawłowska-Zygarowicz, Ana Soto, Héctor Rodríguez, Marcin Smiglak
The ability to dissolve cellulose, by using mixtures of ionic liquids, has been studied and compared with results obtained for the corresponding single ionic liquids. The ionic liquid mixtures tested were a 3:7 mol/mol mixture of 1-ethyl-3-methylimidazolium chloride ([C2mim]Cl) and 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]), and the eutectic mixture (i.e., a 5.1:4.9 mol/mol ratio) of [C2mim]Cl and 1-butyl-3-methylimidazolium chloride (C4mim]Cl). The amount of dissolved cellulose was investigated at three different temperatures (323, 348, and 373 K) for each system. The greatest amount of dissolved cellulose was obtained for the [C2mim]Cl + [C2mim][OAc] mixture, at 373 K, and it was 40 g per 100 g of solvent. Moreover, attempts were made to lower the viscosity of the resulting systems and improve the dissolution capacity by addition of dimethylsulfoxide (DMSO) as co-solvent. Results showed that addition of DMSO at 50 mol% allows the dissolution of even greater amounts of cellulose (up to 43 g per 100 g of solvent). To the best of our knowledge, this is the largest ever reported amount of dissolved cellulose in ionic liquid media. Additionally, physical properties (density, surface tension, and viscosity) of the investigated ionic liquid mixtures were determined and compared with the values of the corresponding parent salts. The dissolved cellulose could be easily reconstituted from its solution in ionic liquid mixtures by addition of water. The regenerated cellulose was characterized by powder X-ray diffraction (pXRD), thermogravimetric analysis (TGA), and optical microscopy. The analyses confirmed the conversion of the crystal structure of cellulose from cellulose I to cellulose II during the dissolution and regeneration process.
The mechanism for cleavage of three typical glucosidic bonds induced by hydroxyl free radical Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-09 Yujie Dai, Chunfu Shao, Yingai Piao, Huiqian Hu, Kui Lu, Tongcun Zhang, Xiuli Zhang, Shiru Jia, Min Wang, Shuli Man
A novel mechanism for cleavage of three typical α(1 → 2), α(1 → 4) and β(1 → 4) glucosidic bonds induced by hydroxyl free radical was examined with DFT theory at B3LYP/6–31 + G(d,p) level using PCM water solvent model. It was found that the hydrogen abstraction from the C<img border="0" alt="single bond" src="http://cdn.els-cdn.com/sd/entities/sbnd" class="glyphImg">H bonds outside the saccharide rings could induce the hydrogen transfer from the hydroxyl at the radical carbon to the oxygen atom of saccharide ring with the mediation of water, which led to the opening of saccharide ring and the breakage of glucosidic bonds. Alternatively, the hydrogen in <img border="0" alt="radical dot" src="http://cdn.els-cdn.com/sd/entities/rad" class="glyphImg">C<img border="0" alt="single bond" src="http://cdn.els-cdn.com/sd/entities/sbnd" class="glyphImg">OH outside the saccharide ring of maltose and sucrose could also transfer to the adjacent glucosidic oxygen atom with a water molecule mediation to make glucosidic bond break directly. Based on this study, it can be well explained the experimental results that the oxidation of some oligosaccharides with hydroxyl free radicals can produce molecules of glucose, fructose and other monosaccharides.
Benign Development of Cotton with Antibacterial Activity and Metal Sorpability Through Introduction Amino Triazole Moieties and AgNPs in Cotton Structure Pre-treated with Periodate Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-09 Amina L. Mohamed, Ahmed G. Hassabo, S. Shaarawy, A. Hebeish
The research work presented herein was undertaken with a view to develop, characterize and highlight modified cotton fabrics that acquire durable antibacterial activity in concomitant with high metal sorption capacity. The development is based on reacting cotton cellulose previously oxidized by sodium periodate-with 4 amino-1,2,4 triazole in presence and absence of silver nano particles (AgNPs). The idea behind the periodate pretreatment is to convert (via oxidative cleavge) the 2,3-vicinal diol of the anhydroglucose units of cotton into aldehyde groups. The latter are easily reacting with the triazole groups in the modified cotton.On the other hand AgNPs were fabricated as per the reduction method using bio-material extracted from the root of licorice. By virtue of its reducing action, the bio-material converts Ag+ ions to Agoo atom which is also stabilized Ag the bio-material in the form of cluster which is the agregate of about 5 Agoo. The clusters are cropped with the stabilizer thus forming silver nanoparticles.Measurement of the particle size displays a value of 8.7 nm.Charactrisation of triazole treated cotton fabrics reveals the presence of the triazole moieties inside the structure of cotton. Furthermore,Fabrictreated with triazole in presence and absence of AgNPs exhibits a relatively high antibacterial activity against gram-negative tested bacteria (E. coli) as compared to that of gram-positive tested bacteria (S. aureus). The metal sorption of triazole treated cotton fabrics was higher than those of untreated or periodate pretreated fabric due to the increase in nitrogen centers created along the cellulose chains. Experimental data were accomplished through Langmuir, Freundlich and Temkin sorption isotherm models. It was shown that sorption follows Langmuir isotherm model and suggests that the innovative fabric in question can adsorb metal ions from polluted dye bath.
Preparation and characterization of amorphous granular potato starches (AGPS) and cross-linked amorphous granular potato starches (CLAGPS) Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-08 Hui-yun Kim, Seon-Min Oh, Ji-Eun Bae, Jin-Hwa Yeom, Byung-Yong Kim, Hyun-Seok Kim, Moo-Yeol Baik
Amorphous granular potato starch (AGPS) was prepared through heat treatment of native potato starch (NPS) at 94 °C with 53% EtOH, while cross-linked amorphous granular potato starch (CLAGPS) was prepared through cross-linking of NPS with sodium trimetaphosphate/sodium tripolyphosphate (STMP/STPP, 99:1) and heat treatment. Light and polarized microscopy showed that both AGPS and CLAGPS maintained their granule shapes but lost birefringence. DSC and XRD of both AGPS and CLAGPS also revealed complete gelatinization. On the other hand, CLAGPS exhibited no RVA pasting viscosity and AGPS had a higher final viscosity than NPS or CLAGPS. AGPS had a higher RS content than gelatinized potato starch, while that of CLAGPS did not increase, despite the cross-linking modification. Thus, AGPS and CLAGPS had distinct physicochemical properties from each other and from NPS, suggesting their potential applicability to the food, textile, and paper industries.
Complexes between methyltestosterone and β-cyclodextrin for application in aquaculture production Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-08 Lucas Bragança de Carvalho, Kepa Koldo Burusco, Carlos Jaime, Tiago Venâncio, Aline Ferreira Souza de Carvalho, Luis David Solis Murgas, Luciana de Matos Alves Pinto
The inclusion complexes between 17-α-methyltestosterone (MT) and β-cyclodextrin (bCD) were prepared and characterized in dissolution and solid phase. The complex promoted a sixfold increment in solubility of the hormone. It has a limited solubility and stoichiometry of 2:1 (bCD:MT) determined by DSC, NMR and solubility experiments, the association constant Ka = 2846 L mol−1 and complex fraction of 76% (assessed by DOSY-NMR, in (1:3) DMSO/D2O). The association constant obtained in water by the solubility isotherms is 7540 L mol−1. 2D-ROESY experiments indicate the intermolecular orientation (complete inclusion of the hormone in the cavity). Simulations by molecular dynamics agreed with the formation of the inclusion complex 2:1. Release tests showed the slower release for the complexes, with 50% for lyophilization and 56% for malaxation. These results clearly demonstrate the complexation of MT in bCD, which formulations are promising for further applications involving this steroid in aquaculture, both for sexual reversal and in technologies of hormone in water sequestration.
Sodium and acidic alginate foams with hierarchical porosity: preparation, characterization and efficiency as a dye adsorbent Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-08 Asja Pettignano, Nathalie Tanchoux, Thomas Cacciaguerra, Thierry Vincent, Luca Bernardi, Eric Guibal, Françoise Quignard
Improved thermal stability of cellulose nanofibrils using low-concentration alkaline pretreatment Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-07 Hansol Lee, Jaya Sundaram, Lu Zhu, Yiping Zhao, Sudhagar Mani
Conjugation of paclitaxel to C-6 hexanediamine-modified hyaluronic acid for targeted drug delivery to enhance antitumor efficacy Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-07 Yangjian Chen, Fujun Peng, Xiaoda Song, Jicheng Wu, Wenbin Yao, Xiangdong Gao
Polymer-based paclitaxel (PTX) conjugates have demonstrated application potentials to improve the water solubility and enhance the efficiency of drug delivery. In this study, a novel HA-based drug conjugate, HA-6-PTX, was designed and successfully synthesized by chemically grafting PTX to the C-6 position of N-acetyl-d-glucosamine (GlcNAc) of hyaluronic acid (HA) using hexanediamine as the linker. Leaving the carboxylate of HA chain unaffected, the conjugate with drug loading as high as 21.8% showed an excellent water solubility of 168 mg/mL and exhibited increased drug release in the presence of hyaluronidase. Compared to free PTX, HA-6-PTX demonstrated increased cytotoxicity and enhanced apoptosis-inducing effect against HepG2 and A549 cells due to the increased celluar uptake of drug via HA-receptor mediated endocytosis. It was concluded that the HA-6-PTX conjugate could be potentially utilized for further exploration as targeted drug delivery to enhance antitumor efficacy.
Chemical property and impacts of different polysaccharide fractions from Fructus Mori. on lipolysis with digestion model in vitro Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-07 Chun Chen, Qiang Huang, Li-Jun You, Xiong Fu
Three polysaccharides (MFP-1, MFP-2, and MFP-3) were fractioned from mulberry fruits with 30%, 60%, and 90% (v/v) ethanol, respectively. The MFP-1 had the largest molecular weight of 838 kDa, followed by MFP-2 from 49.5 to 163 kDa, and then MFP-3 from 1.41 to 15.30 kDa. The three polysaccharides were composed of arabinose, galactose, glucose, mannose, xylose, and galacturonic acid but with different molar ratio. They also exhibited different surface morphology and thermogravimetric properties. In addition, the impact of the three polysaccharides on the digestion of lipid in a simulated saliva and gastrointestinal tract was investigated. The results indicated MFP-2 had the strongest ability to reduce the rate and extent of lipid digestion. These results have important implications for understanding the influence of polysaccharides on lipid digestion. The effect on retarding lipid digestion within the gastrointestinal tract might be important for the development functional food rich in oil to promote health.
Magnetic nanohydrogel obtained by miniemulsion polymerization of poly(acrylic acid) grafted onto derivatized dextran Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-07 Rodolfo Debone Piazza, Eloiza da Silva Nunes, Wesley Renato Viali, Sebastião William da Silva, Fermin Herrera Aragón, José Antônio Huamaní Coaquira, Paulo César de Morais, Rodrigo Fernando Costa Marques, Miguel Jafelicci Júnior
This study describes the synthesis of magnetic nanohydrogels by miniemulsion polymerization technique. Dextran was derivatized by the glycidyl methacrylate to anchor vinyl groups on polysaccharides backbone, allowing its use as a macromonomer for miniemulsion polymerization, as confirmed by proton nuclear magnetic resonance spectroscopy (13C NMR). Magnetite nanoparticles were synthesized by coprecipitation, followed by air oxidation to maghemite. The results of X-ray diffractometry (XRD), Raman and transmission electron microscopy (TEM) analysis showed that maghemite nanoparticles were obtained with a diameter of 5.27 nm. The entrapment of iron oxide nanoparticles in a dextran nanohydrogel matrix was confirmed by thermogravimetric analysis (TGA), scanning transmission electron microscopy (STEM) and Zeta potential data. The magnetic nanohydrogels presented superparamagnetic behavior and were colloidal stable in physiological during 30 days. Our findings suggest that the synthesized magnetic nanohydrogel are potential candidates for use in drug delivery systems due to its physicochemical and magnetic properties.
Chitosan hydrogels embedding hyper-crosslinked polymer particles as reusable broad-spectrum adsorbents for dye removal Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-06 Martina Salzano de Luna, Rachele Castaldo, Rosaria Altobelli, Lucia Gioiella, Giovanni Filippone, Gennaro Gentile, Veronica Ambrogi
Choline Chloride vs Choline Ionic liquids for starch thermoplasticization Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-06 Paul Decaen, Agnès Rolland-Sabaté, Sophie Guilois, Vanessa Jury, Nadine Allanic, Gaël Colomines, Denis Lourdin, Eric Leroy
Native starch containing 12% water was melt processed in presence of 23% of various plasticizers at 120 °C, either by simple compression molding or by extrusion using a laboratory scale microcompounder. Glycerol, a typical starch plasticizer, was used as a reference and compared to three choline salts: raw choline chloride (which is a solid in dry state with a melting point above 300 °C), and two ionic liquids synthesized from this precursor (choline acetate and choline lactate, liquids below 100 °C). These ionic plasticizers were shown to allow a more efficient melting of native starch in both processes. The investigation of macromolecular structure changes during processing shows that this efficiency can be ascribed to a starch chain scission mechanism, resulting in lower specific mechanical energy input need for starch thermoplasticization compared to glycerol plasticized starch. Compared to the synthesized ionic liquids, raw commercial choline chloride leads to a good compromise between limited chain scission, and final water uptake and thermomechanical properties.
Dilational rheology of oil/water interfaces covered by amphiphilic polysaccharides derived from dextran Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-06 Jacques Desbrières, Edeluc López-Gonzalez, Antonio Aguilera-miguel, Véronique Sadtler, Philippe Marchal, Christophe Castel, Lionel Choplin, Alain Durand
This work studied the adsorption at dodecane/water interface of amphiphilic polysaccharides derived from dextran (a nonionic bacterial polysaccharide) by random attachment of phenoxy groups along the chains (between 10 and 20 attached phenoxy groups per 100 glucose repeat units). The long-time kinetics of interfacial tension decrease was satisfactorily described assuming diffusion-limited adsorption of hydrophobic units (over 4 hours). Dilational rheology of dodecane/water interface was studied for the first time with that kind of amphiphilic polysaccharides and evidenced a significant elastic component. For all dextran derivatives, experimental results were conveniently described using Lucassen-van den Tempel model which assumed diffusion-limited of surface active species. The characteristic frequency increased with the number of attached phenoxy groups and its order of magnitude (10−3-10−2 rad.s−1) was consistent with estimations based on the previous model. Experimental results were compared to those obtained with commercial stabilizers like Pluronics (L64, P105, F68 and F127) and Tween 80.
Morphological, structural and functional properties of starch granules extracted from the tubers and seeds of Sphenostylis stenocarpa Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-06 Paul Malumba, Lynn Doran, Wilfried Zanmenou, Sylvanus Odjo, Joseph Katanga, Christophe Blecker, François Béra
Sphenostylis stenocarpa (Hochst. ex A. Rich.) Harms, is a legume widely recognized in Africa for its edible starchy tuber and seeds. In the present morphological, structural and functional properties of starch extracted from the tubers and seeds of a same accession of this plant were characterized and compared. With smaller and more angular granules, tuber starch displayed higher resistance toward amylolysis and gelatinization than seed starch. The amylolysis of seed starch resulted in fragmented granules with typical layered structures of growth rings. During their hydrothermal treatments, both tuber and seed starches showed condensed ghosts even at 95 °C. This high resistance toward hydrothermal degradation was considered as the basis of the typical pasting properties of these two materials. Both seed and tuber starch exhibited A-type crystalline pattern. Under non-oxidative combustion tuber starch presented a degradation peak at 310 °C while seed starch was degraded around 302 °C.
Production of pectin-whey protein nano-complexes as carriers of orange peel oil Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-06 Sanaz Ghasemi, Seid Mahdi Jafari, Elham Assadpour, Morteza Khomeiri
Orange peel oil is one of the most common flavorings used in the food industry which is volatile under environmental conditions. Encapsulation is the best way to protect it and control its release. One of the nanoencapsulation systems for food bioactive ingredients is complexation method, which entraps the core materials in a complex of two different biopolymers. In this study, orange peel oil was nanoencapsulated by pectin-whey protein nanocomplexes. After determining the optimum nanocomplex suspensions containing orange peel oil based on the stability, viscosity, and color, they were formulated in three different pH values (3, 6 and 9) and converted into powdered forms by freeze drying. The analysis of size and zeta potential of nanocomplexes revealed that the smallest particles formed in pH = 6. The encapsulation efficiency of the powders at pH = 3, 6 and 9 were 88, 84, and 70%, respectively and there was a reverse linear correlation between encapsulation efficiency and the color index (b*). The microstructure and the morphology of the nanocomplex powders was investigated by SEM and AFM and the results showed that more spherical particles are formed in pH = 3. FTIR analysis determined that there was a chemical reaction and bond formation between whey proteins and pectin as a sharp band was appeared in 991 cm−1.
Safe Therapeutics of Murine Melanoma Model Using A Novel Antineoplasic, The Partially Methylated Mannogalactan From Pleurotus eryngii Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-06 S.M.P. Biscaia, E.R. Carbonero, D.L. Bellan, B.S. Borges, C.R. Costa, G.R. Rossi, J.P. Gonçalves, C.M. Melo, F.A.R. Lívero, A.C. Ruthes, R. Zotz, E.V. Silva, C.C. Oliveira, A. Acco, H.B. Nader, R. Chammas, M. Iacomini, C.R.C. Franco, E.S. Trindade
A heteropolysaccharide was isolated by cold aqueous extraction from edible mushroom Pleurotus eryngii (“King Oyster”) basidiocarps and its biological properties were evaluated. Structural assignments were carried out using mono- and bidimensional NMR spectroscopy, monosaccharide composition, and methylation analyses. A mannogalactan having a main chain of (1 → 6)-linked α-d-galactopyranosyl and 3-O-methyl-α-d-galactopyranosyl residues, both partially substituted at OH-2 by β-d-Manp (MG-Pe) single-unit was found. Biological effects of mannogalactan from P. eryngii (MG-Pe) were tested against murine melanoma cells. MG-Pe was non-cytotoxic, but reduced in vitro melanoma cells invasion. Also, 50 mg/kg MG-Pe administration to melanoma-bearing C57BL/6 mice up to 10 days decreased in 60% the tumor volume compared to control. Additionally, no changes were observed when biochemical profile, complete blood cells count (CBC), organs, and body weight were analyzed. Mg-Pe was shown to be a promising anti-melanoma molecule capable of switching melanoma cells to a non-invasive phenotype with no toxicity to melanoma-bearing mice.
Isolation of Cellulose-II Nanospheres from Flax Stems and their Physical and Morphological Properties Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-06 Jérémy Astruc, Malladi Nagalakshmaiah, Gaétan Laroche, Michel Grandbois, Saïd Elkoun, Mathieu Robert
In this study, cellulose-II nanospheres (CNS) were extracted from flax fibers and analyzed to understand the crystalline, functional and morphological properties by means of X-ray Diffraction (X-RD), Fourier Transform Infrared (FT-IR) and Scanning Electron Microscopy (SEM). FT-IR and SEM results indicate the effective removal of extractives, lignin and hemicellulose. X-RD results clearly show the transformation from cellulose-I to cellulose-II during the mercerization process. Further, the resulting cellulose fibers were treated with sulfuric acid in order to obtain cellulose nanospheres (CNS). The morphology was measured by SEM, Transmission Electron Microscopy (TEM) and Atomic Force Microscopy (AFM). The size distribution and the surface charge of CNS were investigated by Small-Angle X-ray Scattering (SAXS) and Nanosizer. The results indicate a size distribution of CNS between 20 and 90 nm moderately dispersed. Finally, the transversal elastic modulus of CNS-II was determined by using AFM, and results reveal the range varying from 6 to 25 GPa.
In vitro fermentability of xylo-oligosaccharide and xylo-polysaccharide fractions with different molecular weights by human faecal bacteria Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-06 Ai Ling Ho, Ondrej Kosik, Alison Lovegrove, Dimitris Charalampopoulos, Robert A. Rastall
Xylo-oligosaccharides and xylo-polysaccharides (XOS, XPS) produced by autohydrolysis of the fibre from oil palm empty fruit bunches (OPEFB) were purified using gel filtration chromatography to separate the XOS and XPS from the crude autohydrolysis liquor. Six mixed fractions of refined XOS and XPS with average degree of polymerisation (avDP) of 4-64 were obtained. These were characterised in terms of their composition and size by HPLC, MALDI-ToF-MS (selected fractions) and carbohydrate gel electrophoresis (PACE). They were assessed in batch culture fermentations using faecal inocula to determine their ability to modulate the human faecal microbiota in vitro by measuring the bacterial growth, organic acid production and the XOS assimilation profile. The gut microbiota was able to utilise all the substrates and there was a link between the avDP with the fermentation properties. In general, XOS/XPS preparations of lower avDP promote better Bifidobacterium growth and organic acid production.
Novel apigenin-loaded sodium hyaluronate nano-assemblies for targeting tumor cells Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-06 Ting Zhao, Yue He, Huali Chen, Yan Bai, Wenjing Hu, Liangke Zhang
Synthesis, characterisation and physicochemical properties of hydrophobically modified inulin using long-chain fatty acyl chlorides Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-06 Lingyu Han, I. Ratcliffe, P.A. Williams
A series of inulin derivatives were synthesized in aqueous solution using acyl chlorides with varying alkyl chain length (C10-C16). They were characterised using a number of techniques including MALDI TOF-MS, 1H NMR and FTIR and their degree of substitution determined. The solution properties of the hydrophobically modified inulins were investigated using dye solubilisation and surface tension and it was confirmed that the molecules aggregated in solution above a critical concentration (critical aggregation concentration, CAC). The value of the CAC was found to be reasonably consistent between the different techniques and was shown to decrease with increasing hydrophobe chain length. It was found that the C10, C12 and C14 derivatives formed stable oil-in-water emulsions and the emulsion droplet size decreased with increasing alkyl chain length. The C16 derivative was not able to produce stable oil-in-water emulsions; however, it was able to form stable water-in-oil emulsions. The fact that the derivatives are able to form micellar-like aggregates and stabilise emulsions makes them suitable candidates for the encapsulation and delivery of active compounds with potential application in food, cosmetic, personal care and pharmaceutical formulations.
Fabrication and characterization of chitin nanofibers through esterification and ultrasound treatment Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-06 Qian Wang, Xiaoxia Yan, Yanjiao Chang, Lili Ren, Jiang Zhou
Chitin nanofibers were prepared from commercially available chitin powder via esterification modification and subsequent ultrasound treatment. The obtained chitin nanofibers were characterized using dynamic light scattering (DLS), scanning electron microscopy (SEM), Fourier transform infrared (FTIR), 13C CP-MAS (cross-polarization under magic-angle spinning) solid state nuclear magnetic resonance (NMR), elemental analysis, and X-ray diffraction (XRD). Results showed that the esterification of chitin with maleic anhydride significantly improved the ultrasound disintegration of chitin fibrils into nanofibers. With increasing power and time, the ultrasound treatment yielded smaller chitin nanofibers with narrower size distribution, and the diameter of the chitin nanofibers could reach ∼15 nm. The effect of the ultrasound treatment on degree of acetylation and degree of substitution of the chitin nanofibers was negligible. However, crystallinity of the chitin nanofibers increased with increase in power and time of the ultrasound treatment.
Characterization of crystalline linear (1 → 3)-α-d-glucan synthesized in vitro Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-05 Kayoko Kobayashi, Takuto Hasegawa, Ryosuke Kusumi, Satoshi Kimura, Makoto Yoshida, Junji Sugiyama, Masahisa Wada
We investigated the crystal structure and molecular arrangement of the linear (1 → 3)-α-d-glucan synthesized by glucosyltransferase GtfJ cloned from Streptococcus salivarius using sucrose as a substrate. The synthetic products had two morphologies: wavy fibril-like crystals as major and thin lamellae as minor products. Their structures were analyzed using electron microdiffraction, synchrotron X-ray powder diffraction, and solid-state 13C NMR spectroscopy. The fibrils and lamellae had the same allomorphic form but different molecular arrangements. The wet crystals were in a hydrated form, which converted into an anhydrous form with a significant decrease in crystallinity on drying. The hydrated and anhydrous forms had an extended-chain conformation with 2/1 helix, and the hydrated form was estimated to contain one water molecule per glucose residue. The long glucan chains were folded in the fibril crystals, while the short, extended chains were arranged perpendicular to the base plane of the lamellae.
The potential of brown-algae polysaccharides for the development of anticancer agents: An update on anticancer effects reported for fucoidan and laminaran Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-05 K.K. Asanka Sanjeewa, Jung Suck Lee, Won-Suck Kim, You-Jin Jeon
Linear polymers of β and γ cyclodextrins with a polyglutamic acid backbone as carriers for doxorubicin Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-04 Valentina Oliveri, Francesco Bellia, Maurizio Viale, Irena Maric, Graziella Vecchio
Synthesis of oxidized β-cyclodextrin with high aqueous solubility and broad-spectrum antimicrobial activity Carbohydr. Polym. (IF 4.811) Pub Date : 2017-09-01 Youxin Ye, He Ren, Shu Zhu, Huan Tan, Xinying Li, Defu Li, Changdao Mu
Oxidized β-cyclodextrins with different oxidation levels were prepared using hydrogen peroxide as the oxidant and copper sulfate as the catalyst. The physicochemical, antimicrobial and antifungal properties of oxidized β-cyclodextrin were systematically studied. The results showed that the oxidation level of oxidized β-cyclodextrin was successfully controlled by adjusting the dosage of hydrogen peroxide. The aqueous solubility of oxidized β-cyclodextrin was highly improved as expected. However, oxidation changed the morphology and partly reduced the crystallinity of oxidized β-cyclodextrin due to the introduced carbonyl and carboxyl groups. It is interesting that oxidized β-cyclodextrin presented a broad-spectrum antimicrobial activity, which was efficiently improved with the increasing oxidation level. Growth of A. niger spores was efficiently inhibited in the presence of oxidized β-cyclodextrin. Moreover, oxidized β-cyclodextrin could effectively extend the storage time of apple. In summary, oxidized β-cyclodextrin shows potential as antimicrobial and antifungal agents in food industry.
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