Morphology and physical-chemical properties of celluloses obtained by different methods
NASA Astrophysics Data System (ADS)
Anpilova, A. Yu.; Mastalygina, E. E.; Mikhaylov, I. A.; Popov, A. A.; Kartasheva, Z. S.
2017-12-01
The morphology and structural characteristics of celluloses obtained by different methods were studied. The objects of the investigation are cellulose from pulp source, commercial celluloses produced by sodium and acid hydrolysis, laboratory produced cellulose from bleached birch kraft pulp, and cellulose obtained by thermooxidative catalytic treatment of maple leaves by peroxide. According to a complex analysis of cellulose characteristics, several types of celluloses were offered as modifying additives for polymers.
Gorshkova, Tatyana; Mokshina, Natalia; Chernova, Tatyana; Ibragimova, Nadezhda; Salnikov, Vadim; Mikshina, Polina; Tryfona, Theodora; Banasiak, Alicja; Immerzeel, Peter; Dupree, Paul; Mellerowicz, Ewa J.
2015-01-01
Contractile cell walls are found in various plant organs and tissues such as tendrils, contractile roots, and tension wood. The tension-generating mechanism is not known but is thought to involve special cell wall architecture. We previously postulated that tension could result from the entrapment of certain matrix polymers within cellulose microfibrils. As reported here, this hypothesis was corroborated by sequential extraction and analysis of cell wall polymers that are retained by cellulose microfibrils in tension wood and normal wood of hybrid aspen (Populus tremula × Populus tremuloides). β-(1→4)-Galactan and type II arabinogalactan were the main large matrix polymers retained by cellulose microfibrils that were specifically found in tension wood. Xyloglucan was detected mostly in oligomeric form in the alkali-labile fraction and was enriched in tension wood. β-(1→4)-Galactan and rhamnogalacturonan I backbone epitopes were localized in the gelatinous cell wall layer. Type II arabinogalactans retained by cellulose microfibrils had a higher content of (methyl)glucuronic acid and galactose in tension wood than in normal wood. Thus, β-(1→4)-galactan and a specialized form of type II arabinogalactan are trapped by cellulose microfibrils specifically in tension wood and, thus, are the main candidate polymers for the generation of tensional stresses by the entrapment mechanism. We also found high β-galactosidase activity accompanying tension wood differentiation and propose a testable hypothesis that such activity might regulate galactan entrapment and, thus, mechanical properties of cell walls in tension wood. PMID:26378099
Gorshkova, Tatyana; Mokshina, Natalia; Chernova, Tatyana; Ibragimova, Nadezhda; Salnikov, Vadim; Mikshina, Polina; Tryfona, Theodora; Banasiak, Alicja; Immerzeel, Peter; Dupree, Paul; Mellerowicz, Ewa J
2015-11-01
Contractile cell walls are found in various plant organs and tissues such as tendrils, contractile roots, and tension wood. The tension-generating mechanism is not known but is thought to involve special cell wall architecture. We previously postulated that tension could result from the entrapment of certain matrix polymers within cellulose microfibrils. As reported here, this hypothesis was corroborated by sequential extraction and analysis of cell wall polymers that are retained by cellulose microfibrils in tension wood and normal wood of hybrid aspen (Populus tremula × Populus tremuloides). β-(1→4)-Galactan and type II arabinogalactan were the main large matrix polymers retained by cellulose microfibrils that were specifically found in tension wood. Xyloglucan was detected mostly in oligomeric form in the alkali-labile fraction and was enriched in tension wood. β-(1→4)-Galactan and rhamnogalacturonan I backbone epitopes were localized in the gelatinous cell wall layer. Type II arabinogalactans retained by cellulose microfibrils had a higher content of (methyl)glucuronic acid and galactose in tension wood than in normal wood. Thus, β-(1→4)-galactan and a specialized form of type II arabinogalactan are trapped by cellulose microfibrils specifically in tension wood and, thus, are the main candidate polymers for the generation of tensional stresses by the entrapment mechanism. We also found high β-galactosidase activity accompanying tension wood differentiation and propose a testable hypothesis that such activity might regulate galactan entrapment and, thus, mechanical properties of cell walls in tension wood. © 2015 American Society of Plant Biologists. All Rights Reserved.
Cellulose nanomaterials as green nanoreinforcements for polymer nanocomposites
NASA Astrophysics Data System (ADS)
Dufresne, Alain
2017-12-01
Unexpected and attractive properties can be observed when decreasing the size of a material down to the nanoscale. Cellulose is no exception to the rule. In addition, the highly reactive surface of cellulose resulting from the high density of hydroxyl groups is exacerbated at this scale. Different forms of cellulose nanomaterials, resulting from a top-down deconstruction strategy (cellulose nanocrystals, cellulose nanofibrils) or bottom-up strategy (bacterial cellulose), are potentially useful for a large number of industrial applications. These include the paper and cardboard industry, use as reinforcing filler in polymer nanocomposites, the basis for low-density foams, additives in adhesives and paints, as well as a wide variety of filtration, electronic, food, hygiene, cosmetic and medical products. This paper focuses on the use of cellulose nanomaterials as a filler for the preparation of polymer nanocomposites. Impressive mechanical properties can be obtained for these materials. They obviously depend on the type of nanomaterial used, but the crucial point is the processing technique. The emphasis is on the melt processing of such nanocomposite materials, which has not yet been properly resolved and remains a challenge. This article is part of a discussion meeting issue `New horizons for cellulose nanotechnology'.
Resistant-hemicelluloses toward successive chemical treatment during cellulose fibre extraction
NASA Astrophysics Data System (ADS)
Naqiya, F. M. Z.; Ahmad, I.; Airianah, O. B.
2018-04-01
Lignocellulosic materials have high demand bio-polymers industries as it is rich in cellulose but other residues that still remain in the extracted cellulose might influence the ability of cellulose-rich material to interact with other polymers. In this study, cellulose fibre was extracted from oil palm frond (OPF) using alkali and bleaching treatment. The morphological changes of each sample after every treatment was observed using Scanning Electron Microscope (SEM) and was further chemically extracted and quantitatively evaluated via spectrophotometric method. The non-cellulosic component was found predominantly contained hemicelluloses and these remaining hemicelluloses were hydrolysed and the monosaccharides of hemicelluloses were visualised by Thin Layer Chromatography (TLC). Xylose, arabinose, mannose and glucose were detected and therefore, it is suggested that the plausible type of resistant-hemicelluloses in OPF extracted fibre are arabinoxylan, glucomannan and/or glucan.
Surface modification of cellulose using silane coupling agent.
Thakur, Manju Kumari; Gupta, Raju Kumar; Thakur, Vijay Kumar
2014-10-13
Recently there has been a growing interest in substituting traditional synthetic polymers with natural polymers for different applications. However, natural polymers such as cellulose suffer from few drawbacks. To become viable potential alternatives of synthetic polymers, cellulosic polymers must have comparable physico-chemical properties to that of synthetic polymers. So in the present work, cellulose polymer has been modified by a series of mercerization and silane functionalization to optimize the reaction conditions. Structural, thermal and morphological characterization of the cellulose has been done using FTIR, TGA and SEM, techniques. Surface modified cellulose polymers were further subjected to evaluation of their properties like swelling and chemical resistance behavior. Published by Elsevier Ltd.
Processing and characterization of natural cellulose fibers/thermoset polymer composites.
Thakur, Vijay Kumar; Thakur, Manju Kumari
2014-08-30
Recently natural cellulose fibers from different biorenewable resources have attracted the considerable attraction of research community all around the globe owing to their unique intrinsic properties such as biodegradability, easy availability, environmental friendliness, flexibility, easy processing and impressive physico-mechanical properties. Natural cellulose fibers based materials are finding their applications in a number of fields ranging from automotive to biomedical. Natural cellulose fibers have been frequently used as the reinforcement component in polymers to add the specific properties in the final product. A variety of cellulose fibers based polymer composite materials have been developed using various synthetic strategies. Seeing the immense advantages of cellulose fibers, in this article we discuss the processing of biorenewable natural cellulose fibers; chemical functionalization of cellulose fibers; synthesis of polymer resins; different strategies to prepare cellulose based green polymer composites, and diverse applications of natural cellulose fibers/polymer composite materials. The article provides an in depth analysis and comprehensive knowledge to the beginners in the field of natural cellulose fibers/polymer composites. The prime aim of this review article is to demonstrate the recent development and emerging applications of natural cellulose fibers and their polymer materials. Copyright © 2014 Elsevier Ltd. All rights reserved.
Evaluation of thermal gelation behavior of different cellulose ether polymers by rheology
NASA Astrophysics Data System (ADS)
Balaghi, S.; Edelby, Y.; Senge, B.
2014-05-01
Hydroxypropylmethylcellulose (HPMC) and Methylcellulose (MC) are cellulose ethers which can be dispersed in water and used as thickeners, emulsifiers, binders, film formers, and water-retention agents due to their hydrophilic and hydrophobic characteristics. In this study, various types of HPMCs, in comparison with two types of MCs were examined. The formed gels of the different cellulose ethers showed specific and various structural formation and network properties. The degree of methylation (Meth.) and hydroxypropylation (HyPr.) affected drastically the heat-induced gelation of the examined cellulose ethers.
Gift, Alan D; Hettenbaugh, Jacob A; Quandahl, Rachel A; Mapes, Madison
2017-11-06
The effects of polymers on the anhydrate-to-hydrate transformation of carbamazepine (CBZ) was investigated. The three types of polymers studied were polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and substituted celluloses which included hydroxypropyl methylcellulose (HPMC) and methylcellulose (MC). Anhydrous CBZ was added to dilute aqueous polymer solutions and Raman spectroscopy measurements were collected to monitor the kinetics of the solution-mediated transformation to CBZ dihydrate. Polymers exhibiting the greatest inhibition were able to reduce the growth phase of the solution-mediated transformation and change the habit of the hydrate crystal indicating polymer adsorption to the hydrate crystal surface as the mechanism of inhibition. The results of the various polymers showed that short chain substituted celluloses (HPMC and MC) inhibited the CBZ transformation to a much greater extent than longer chains. The same trend was observed for PVP and PVA, but to a lesser extent. These chain length effects were attributed to changes in polymer confirmation when adsorbed on the crystal surface. Additionally, decreasing the percentage of hydroxyl groups on the PVA polymer backbone reduced the ability of the polymer to inhibit the transformation and changing the degree of substitutions of methyl and hydroxypropyl groups on the cellulosic polymer backbone had no effect on the transformation.
Salmonella promotes virulence by repressing cellulose production
Pontes, Mauricio H.; Lee, Eun-Jin; Choi, Jeongjoon; Groisman, Eduardo A.
2015-01-01
Cellulose is the most abundant organic polymer on Earth. In bacteria, cellulose confers protection against environmental insults and is a constituent of biofilms typically formed on abiotic surfaces. We report that, surprisingly, Salmonella enterica serovar Typhimurium makes cellulose when inside macrophages. We determine that preventing cellulose synthesis increases virulence, whereas stimulation of cellulose synthesis inside macrophages decreases virulence. An attenuated mutant lacking the mgtC gene exhibited increased cellulose levels due to increased expression of the cellulose synthase gene bcsA and of cyclic diguanylate, the allosteric activator of the BcsA protein. Inactivation of bcsA restored wild-type virulence to the Salmonella mgtC mutant, but not to other attenuated mutants displaying a wild-type phenotype regarding cellulose. Our findings indicate that a virulence determinant can promote pathogenicity by repressing a pathogen's antivirulence trait. Moreover, they suggest that controlling antivirulence traits increases long-term pathogen fitness by mediating a trade-off between acute virulence and transmission. PMID:25848006
Observing cellulose biosynthesis and membrane translocation in crystallo
Morgan, Jacob L.W.; McNamara, Joshua T.; Fischer, Michael; Rich, Jamie; Chen, Hong-Ming; Withers, Stephen G.; Zimmer, Jochen
2016-01-01
Many biopolymers, including polysaccharides, must be translocated across at least one membrane to reach their site of biological function. Cellulose is a linear glucose polymer synthesized and secreted by a membrane-integrated cellulose synthase. In crystallo enzymology with the catalytically-active bacterial cellulose synthase BcsA-B complex reveals structural snapshots of a complete cellulose biosynthesis cycle, from substrate binding to polymer translocation. Substrate and product-bound structures of BcsA provide the basis for substrate recognition and demonstrate the stepwise elongation of cellulose. Furthermore, the structural snapshots show that BcsA translocates cellulose via a ratcheting mechanism involving a “finger helix” that contacts the polymer's terminal glucose. Cooperating with BcsA's gating loop, the finger helix moves ‘up’ and ‘down’ in response to substrate binding and polymer elongation, respectively, thereby pushing the elongated polymer into BcsA’s transmembrane channel. This mechanism is validated experimentally by tethering BcsA's finger helix, which inhibits polymer translocation but not elongation. PMID:26958837
Design and characterization of cellulose nanocrystal-enhanced epoxy hardeners
Shane X. Peng; Robert J. Moon; Jeffrey P. Youngblood
2014-01-01
Cellulose nanocrystals (CNCs) are renewable, sustainable, and abundant nanomaterial widely used as reinforcing fillers in the field of polymer nanocomposites. In this study, two-part epoxy systems with CNC-enhanced hardeners were fabricated. Three types of hardeners, Jeffamine D400 (JD400), diethylenetriamine (DETA), and (±)-trans-1,2- diaminocyclohexane (DACH), were...
Azzaoui, Khalil; Lamhamdi, Abdelatif; Mejdoubi, El Miloud; Berrabah, Mohammed; Hammouti, Belkheir; Elidrissi, Abderrahman; Fouda, Moustafa M G; Al-Deyab, Salem S
2014-10-13
The aim of this work is to develop composite materials with hydroxyapatite (HAp) mineral and organic matrix such as cellulosic polymers. We use cellulose acetate with different percentages, and then inorganic-organic films were fabricated by evaporation of solvent. The composite films were characterized using emission scanning electron microscopy (FEG-SEM), thermo-gravimetric analysis (TGA) and Fourier transform infra-red (FT-IR) spectra. Test results show that these films are uniform and have good ductility. A strong interaction existed between HAp and cellulosic polymers, and the method allows the production of very fine particles size of about 92 nm. We have developed a new chromatographic method for the quantification of bisphenol A (BPA) in samples of baby food. The result of this study demonstrates how to use this type of composite materials to remove pollutants. Copyright © 2014 Elsevier Ltd. All rights reserved.
Xuezhu Xu; Fei Liu; Long Jiang; J.Y. Zhu; Darrin Haagenson; Dennis P. Wiesenborn
2013-01-01
Both cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) are nanoscale cellulose fibers that have shown reinforcing effects in polymer nanocomposites. CNCs and CNFs are different in shape, size and composition. This study systematically compared their morphologies, crystalline structure, dispersion properties in polyethylene oxide (PEO) matrix, interactions...
Synthetic Polymers as Gasoline Thickening Agents
1944-10-02
Polyvinyl Ethers —---- 71 2. Vistanex and Synthetic Rubbers — 73 3. Ethyl Cellulose 7* a. Solubility Studies 75 b. Gel Preparation — 75 c...Surveillance Tests —- 77 d. Static Firing Tests 78 e. Ethyl Cellulose as a Methacrylate Extender 78 f. Modification of Ethyl Cellulose 78 4...Miscellaneous Polymers 79 5. Emulsions 81 6. Pactices 81 B. Preparation of Polymers not nov in Commercial Production— ---——--— 81 1. Cellulose Esters
Stability Enhancement of Polymeric Sensing Films Using Fillers
NASA Technical Reports Server (NTRS)
Lin, Brian; Shevade, Abhijit; Ryan, Margaret Amy; Kisor, Adam; Yen, Shiao-Pin; Manatt, Kenneth; Homer, Margie; Fleurial, Jean-Pierre
2006-01-01
Experiments have shown the stability enhancement of polymeric sensing films on mixing the polymer with colloidal filler particles (submicron-sized) of carbon black, silver, titanium dioxide, and fumed silicon dioxide. The polymer films are candidates for potential use as sensing media in micro/nano chemical sensor devices. The need for stability enhancement of polymer sensing films arises because such films have been found to exhibit unpredictable changes in sensing activity over time, which could result in a possible failure of the sensor device. The changes in the physical properties of a polymer sensing film caused by the sorption of a target molecule can be measured by any of several established transduction techniques: electrochemical, optical, calorimetric, or piezoelectric, for example. The transduction technique used in the current polymer stability experiments is based on piezoelectric principles using a quartz-crystal microbalance (QCM). The surface of the QCM is coated with the polymer, and the mass uptake by the polymer film causes a change in the oscillating frequency of the quartz crystal. The polymer used for the current study is ethyl cellulose. The polymer/ polymer composite solutions were prepared in 1,3 dioxolane solvent. The filler concentration was fixed at 10 weight percent for the composites. The polymer or polymer composite solutions were cast on the quartz crystal having a fundamental frequency of about 6 MHz. The coated crystal was subjected to a multistage drying process to remove all measurable traces of the solvent. In each experiment, the frequency of oscillation was measured while the QCM was exposed to clean, dry, flowing air for about 30 minutes, then to air containing a known concentration of isopropanol for about 30 minutes, then again to clean dry air for about 30 minutes, and so forth. This cycle of measurements for varying isopropanol concentrations was repeated at intervals for several months. The figure depicts some of the sensing film stability results for ethyl cellulose polymer, ethyl cellulose-carbon black, and ethyl cellulose-silicon dioxide composite systems. An ethyl cellulose film exhibited a marked decline in response in the first few months of study and settled to a steady average response after about four months. However, response varied widely around the average response for ethyl cellulose film. In contrast, ethyl cellulose- carbon black and ethyl cellulose-silicon dioxide composites also declined in the early months, but showed more repeatable sensing film activity after the initial decline. Similar trends were observed in experiments for ethyl cellulose-titanium dioxide and ethyl cellulose-silver composites.
Yottha Srithep; Ronald Sabo; Craig Clemons; Lih-Sheng Turng; Srikanth Pilla; Jun Peng
2012-01-01
Using natural cellulosic fibers as fillers for biodegradable polymers can result in fully biodegradable composites. Biodegradable composites were prepared using nanofibrillated cellulose (NFC) as the reinforcement and poly (3-hydroxybutyrate-co-3-hydroxyvalerate, PHBV) as the polymer matrix. The objective of this study was to determine how various additives (i.e.,...
Paper Actuators Made with Cellulose and Hybrid Materials
Kim, Jaehwan; Yun, Sungryul; Mahadeva, Suresha K.; Yun, Kiju; Yang, Sang Yeol; Maniruzzaman, Mohammad
2010-01-01
Recently, cellulose has been re-discovered as a smart material that can be used as sensor and actuator materials, which is termed electro-active paper (EAPap). This paper reports recent advances in paper actuators made with cellulose and hybrid materials such as multi-walled carbon nanotubes, conducting polymers and ionic liquids. Two distinct actuator principles in EAPap actuators are demonstrated: piezoelectric effect and ion migration effect in cellulose. Piezoelectricity of cellulose EAPap is quite comparable with other piezoelectric polymers. But, it is biodegradable, biocompatible, mechanically strong and thermally stable. To enhance ion migration effect in the cellulose, polypyrrole conducting polymer and ionic liquids were nanocoated on the cellulose film. This hybrid cellulose EAPap nanocomposite exhibits durable bending actuation in an ambient humidity and temperature condition. Fabrication, characteristics and performance of the cellulose EAPap and its hybrid EAPap materials are illustrated. Also, its possibility for remotely microwave-driven paper actuator is demonstrated. PMID:22294882
Paper actuators made with cellulose and hybrid materials.
Kim, Jaehwan; Yun, Sungryul; Mahadeva, Suresha K; Yun, Kiju; Yang, Sang Yeol; Maniruzzaman, Mohammad
2010-01-01
Recently, cellulose has been re-discovered as a smart material that can be used as sensor and actuator materials, which is termed electro-active paper (EAPap). This paper reports recent advances in paper actuators made with cellulose and hybrid materials such as multi-walled carbon nanotubes, conducting polymers and ionic liquids. Two distinct actuator principles in EAPap actuators are demonstrated: piezoelectric effect and ion migration effect in cellulose. Piezoelectricity of cellulose EAPap is quite comparable with other piezoelectric polymers. But, it is biodegradable, biocompatible, mechanically strong and thermally stable. To enhance ion migration effect in the cellulose, polypyrrole conducting polymer and ionic liquids were nanocoated on the cellulose film. This hybrid cellulose EAPap nanocomposite exhibits durable bending actuation in an ambient humidity and temperature condition. Fabrication, characteristics and performance of the cellulose EAPap and its hybrid EAPap materials are illustrated. Also, its possibility for remotely microwave-driven paper actuator is demonstrated.
Ectopic lignification in primary cellulose-deficient cell walls of maize cell suspension cultures.
Mélida, Hugo; Largo-Gosens, Asier; Novo-Uzal, Esther; Santiago, Rogelio; Pomar, Federico; García, Pedro; García-Angulo, Penélope; Acebes, José Luis; Álvarez, Jesús; Encina, Antonio
2015-04-01
Maize (Zea mays L.) suspension-cultured cells with up to 70% less cellulose were obtained by stepwise habituation to dichlobenil (DCB), a cellulose biosynthesis inhibitor. Cellulose deficiency was accompanied by marked changes in cell wall matrix polysaccharides and phenolics as revealed by Fourier transform infrared (FTIR) spectroscopy. Cell wall compositional analysis indicated that the cellulose-deficient cell walls showed an enhancement of highly branched and cross-linked arabinoxylans, as well as an increased content in ferulic acid, diferulates and p-coumaric acid, and the presence of a polymer that stained positive for phloroglucinol. In accordance with this, cellulose-deficient cell walls showed a fivefold increase in Klason-type lignin. Thioacidolysis/GC-MS analysis of cellulose-deficient cell walls indicated the presence of a lignin-like polymer with a Syringyl/Guaiacyl ratio of 1.45, which differed from the sensu stricto stress-related lignin that arose in response to short-term DCB-treatments. Gene expression analysis of these cells indicated an overexpression of genes specific for the biosynthesis of monolignol units of lignin. A study of stress signaling pathways revealed an overexpression of some of the jasmonate signaling pathway genes, which might trigger ectopic lignification in response to cell wall integrity disruptions. In summary, the structural plasticity of primary cell walls is proven, since a lignification process is possible in response to cellulose impoverishment. © 2015 Institute of Botany, Chinese Academy of Sciences.
Nanomechanics of cellulose crystals and cellulose-based polymer composites
NASA Astrophysics Data System (ADS)
Pakzad, Anahita
Cellulose-polymer composites have potential applications in aerospace and transportation areas where lightweight materials with high mechanical properties are needed. In addition, these economical and biodegradable composites have been shown to be useful as polymer electrolytes, packaging structures, optoelectronic devices, and medical implants such as wound dressing and bone scaffolds. In spite of the above mentioned advantages and potential applications, due to the difficulties associated with synthesis and processing techniques, application of cellulose crystals (micro and nano sized) for preparation of new composite systems is limited. Cellulose is hydrophilic and polar as opposed to most of common thermoplastics, which are non-polar. This results in complications in addition of cellulose crystals to polymer matrices, and as a result in achieving sufficient dispersion levels, which directly affects the mechanical properties of the composites. As in other composite materials, the properties of cellulose-polymer composites depend on the volume fraction and the properties of individual phases (the reinforcement and the polymer matrix), the dispersion quality of the reinforcement through the matrix and the interaction between CNCs themselves and CNC and the matrix (interphase). In order to develop economical cellulose-polymer composites with superior qualities, the properties of individual cellulose crystals, as well as the effect of dispersion of reinforcements and the interphase on the properties of the final composites should be understood. In this research, the mechanical properties of CNC polymer composites were characterized at the macro and nano scales. A direct correlation was made between: - Dispersion quality and macro-mechanical properties - Nanomechanical properties at the surface and tensile properties - CNC diameter and interphase thickness. Lastly, individual CNCs from different sources were characterized and for the first time size-scale effect on their nanomechanical properties were reported. Then the effect of CNC surface modification on the mechanical properties was studied and correlated to the crystalline structure of these materials.
Composite polymer electrolytes based on MG49 and carboxymethyl cellulose from kenaf
NASA Astrophysics Data System (ADS)
Jafirin, Serawati; Ahmad, Ishak; Ahmad, Azizan
2013-11-01
The development of 49% poly(methyl methacrylate)-grafted natural rubber (MG49) and carboxymethyl cellulose as a composite polymer electrolyte film incorporating LiCF3SO3 were explored. Carboxymethyl cellulose was synthesized from kenaf bast fibres via carboxymethylation process by alkali catalyzed reaction of cellulose with sodium chloroacetate. Reflection fourier transform infrared (ATR-FTIR) spectroscopy showed the presence of carboxyl peak after modification of cellulose with sodium chloroacetate. X-ray diffraction (XRD) analysis revealed that the crystallinity of cellulose was decrease after synthesis. High performance composite polymer electrolytes were prepared with various composition of carboxymethyl cellulose (2-10 wt%) via solution-casting method. The conductivity was increased with carboxymethyl cellulose loading. The highest conductivity value achieved was 3.3 × 10-7 Scm-1 upon addition of 6% wt carboxymethyl cellulose. 6% wt carboxymethyl cellulose composition showed the highest tensile strength value of 7.9 MPa and 273 MPa of modulus value which demonstrated high mechanical performance with accepatable level of ionic conductivity.
DNA immobilization and detection on cellulose paper using a surface grown cationic polymer via ATRP.
Aied, Ahmed; Zheng, Yu; Pandit, Abhay; Wang, Wenxin
2012-02-01
Cationic polymers with various structures have been widely investigated in the areas of medical diagnostics and molecular biology because of their unique binding properties and capability to interact with biological molecules in complex biological environments. In this work, we report the grafting of a linear cationic polymer from an atom transfer radical polymerization (ATRP) initiator bound to cellulose paper surface. We show successful binding of ATRP initiator onto cellulose paper and grafting of polymer chains from the immobilized initiator with ATRP. The cellulose paper grafted polymer was used in combination with PicoGreen (PG) to demonstrate detection of nucleic acids in the nanogram range in homogeneous solution and in a biological sample (serum). The results showed specific identification of hybridized DNA after addition of PG in both solutions.
Chemical Modification of Cellulose Esters for Oral Drug Delivery
NASA Astrophysics Data System (ADS)
Meng, Xiangtao
Polymer functional groups have critical impacts upon physical, chemical and mechanical properties, and thus affect the specific applications of the polymer. Functionalization of cellulose esters and ethers has been under extensive investigation for applications including drug delivery, cosmetics, food ingredients, and automobile coating. In oral delivery of poorly water-soluble drugs, amorphous solid dispersion (ASD) formulations have been used, prepared by forming miscible blends of polymers and drugs to inhibit crystallization and enhance bioavailability of the drug. The Edgar and Taylor groups have revealed that some cellulose o-carboxyalkanoates were highly effective as ASD polymers, with the pendant carboxylic acid groups providing both specific polymer-drug interactions and pHtriggered release through swelling of the ionized polymer matrix. While a variety of functional groups such as hydroxyl and amide groups are also of interest, cellulose functionalization has relied heavily on classical methods such as esterification and etherification for appending functional groups. These methods, although they have been very useful, are limited in two respects. First, they typically employ harsh reaction conditions. Secondly, each synthetic pathway is only applicable for one or a narrow group of functionalities due to restrictions imposed by the required reaction conditions. To this end, there is a great impetus to identify novel reactions in cellulose modification that are mild, efficient and ideally modular. In the initial effort to design and synthesize cellulose esters for oral drug delivery, we developed several new methods in cellulose functionalization, which can overcome drawbacks of conventional synthetic pathways, provide novel cellulose derivatives that are otherwise inaccessible, and present a platform for structure-property relationship study. Cellulose o-hydroxyalkanoates were previously difficult to access as the hydroxyl groups, if not protected, react with carboxylic acid/carbonyl during a typical esterification reaction or ring opening of lactones, producing cellulose-g-polyester and homopolyester. We demonstrated the viability of chemoselective olefin hydroboration-oxidation in the synthesis of cellulose o-hydroxyesters in the presence of ester groups. Cellulose esters with terminally olefinic side chains were transformed to the target products by two-step, one-pot hydroborationoxidation reactions, using 9-borabicyclo[3.3.1]nonane (9-BBN) as hydroboration agent, followed by oxidizing the organoborane intermediate to a primary alcohol using mildly alkaline H2O2. The use of 9-BBN as hydroboration agent and sodium acetate as base catalyst in oxidation successfully avoided cleavage of ester linkages by borane reduction and base catalyzed hydrolysis. With the impetus of modular and efficient synthesis, we introduced olefin crossmetathesis (CM) in polysaccharide functionalization. Using Grubbs type catalyst, cellulose esters with terminally olefinic side chains were reacted with various CM partners including acrylic acid, acrylates and acrylamides to afford families of functionalized cellulose esters. Molar excesses of CM partners were used in order to suppress potential crosslinking caused by self-metathesis between terminally olefinic side chains. Amide CM partners can chelate with the ruthenium catalyst and cause low conversions in conventional solvents such as THF. While the inherent reactivity toward CM and tendency of acrylamides to chelate Ru is influenced by the acrylamide N-substituents, employing acetic acid as a solvent significantly improved the conversion of certain acrylamides. We observed that the CM products are prone to crosslinking during storage, and found that the crosslinking is likely caused by free radical abstraction of gamma-hydrogen of the alpha,beta-unsaturation and subsequent recombination. We further demonstrated successful hydrogenation of these alpha,beta-unsaturated acids, esters, and amides, thereby eliminating the potential for radical-induced crosslinking during storage. The alpha,beta-unsaturation on CM products can cause crosslinking due to gamma-H abstraction and recombination if not reduced immediately after reaction. Instead of eliminating the double bond by hydrogenation, we described a method to make use of these reactive conjugated olefins by post-CM thiol-Michael addition. Under amine catalysis, different CM products and thiols were combined and reacted. Using proper thiols and catalyst, complete conversion can be achieved under mild reaction conditions. The combination of the two modular reactions creates versatile access to multi-functionalized cellulose derivatives. Compared with conventional reactions, these reactions enable click or click-like conjugation of functional groups onto cellulose backbone. The modular profile of the reactions enables clean and informative structure-property relationship studies for ASD. These approaches also provide opportunities for the synthesis of chemically and architecturally diverse cellulosic polymers that are otherwise difficult to access, opening doors for many other applications such as antimicrobial, antifouling, in vivo drug delivery, and bioconjugation. We believe that the cellulose functionalization approaches we pioneered can be expanded to the modification of other polysaccharides and polymers, and that these reactions will become useful tools in the toolbox of polymer/polysaccharide chemists.
Janko, Marek; Jocher, Michael; Boehm, Alexander; Babel, Laura; Bump, Steven; Biesalski, Markus; Meckel, Tobias; Stark, Robert W
2015-07-13
The properties of paper sheets can be tuned by adjusting the surface or bulk chemistry using functional polymers that are applied during (online) or after (offline) papermaking processes. In particular, polymers are widely used to enhance the mechanical strength of the wet state of paper sheets. However, the mechanical strength depends not only on the chemical nature of the polymeric additives but also on the distribution of the polymer on and in the lignocellulosic paper. Here, we analyze the photochemical attachment and distribution of hydrophilic polydimethylacrylamide-co-methacrylate-benzophenone P(DMAA-co-MABP) copolymers with defined amounts of photoreactive benzophenone moieties in model paper sheets. Raman microscopy was used for the unambiguous identification of P(DMAA-co-MABP) and cellulose specific bands and thus the copolymer distribution within the cellulose matrix. Two-dimensional Raman spectral maps at the intersections of overlapping cellulose fibers document that the macromolecules only partially surround the cellulose fibers, favor to attach to the fiber surface, and connect the cellulose fibers at crossings. Moreover, the copolymer appears to accumulate preferentially in holes, vacancies, and dips on the cellulose fiber surface. Correlative brightfield, Raman, and confocal laser scanning microscopy finally reveal a reticular three-dimensional distribution of the polymer and show that the polymer is predominately deposited in regions of high capillarity (i.e., in proximity to fine cellulose fibrils). These data provide deeper insights into the effects of paper functionalization with a copolymer and aid in understanding how these agents ultimately influence the local and overall properties of paper.
Development of a solvent processed insensitive propellant
NASA Technical Reports Server (NTRS)
Trask, R.; Costa, E.; Beardell, A. J.
1980-01-01
Two types of low vulnerability propellants are studied which are distinguished by whether the binder is a rubber, such as polyurethane or CTBN, or a plasticizable polymer such as ethyl cellulose or cellulose acetate. The former propellants are made by a partial cure extrusion process while the latter are made by the conventional solvent process. Emphasis is given to a cellulose binder (plasticizer) RDX composition. The type of binder used, the particle size of the RDX and the presence of small quantities of nitrocellulose in the solvent processed compositions have important influences on the mechanical and combustion characteristics of the propellant. The low temperature combustion is of particular concern because of potential breakup of the grains that can lead to instability.
Yu, Juan; Lu, Chuanwei; Wang, Chunpeng; Wang, Jifu; Fan, Yimin; Chu, Fuxiang
2017-11-15
Cellulose-based thermoplastic elastomers (TPEs) have attracted considerable attention because of their rigid backbone, good mechanical properties, renewable nature and abundance. In the present study, sustainable TPEs based on ethyl cellulose (EC), fatty acid and furfural were generated by the combination of ATRP and "click chemistry". To fabricate sustainable TPEs with higher toughness, a range of polymers, including mono random-copolymer poly(tetrahydrofurfuryl methacrylate-co-lauryl methacrylate) (P(THFMA-co-LMA), dual polymer side chains PTHFMA and PLMA, and mono-block copolymer PTHFMA-b-PLMA, were designed as side chains to fabricate EC brush copolymers with random, dual or block side chain architectures using the "grafting from" and "grafting onto" methods. The multi-armed structures, chemical compositions and phase separation of these EC brush copolymers were confirmed by FT-IR, 1 H NMR, GPC, DSC, TEM and SEM. Overall, three types of EC brush copolymers all exhibited the desired mechanical properties of TPEs. In addition, the EC brush copolymers with dual/block side chain architectures showed higher tensile strength than that of the random polymers with similar compositions. Copyright © 2017. Published by Elsevier Ltd.
Nanocellulose in green food packaging.
Vilarinho, Fernanda; Sanches Silva, Ana; Vaz, M Fátima; Farinha, José Paulo
2018-06-13
The development of packaging materials with new functionalities and lower environmental impact is now an urgent need of our society. On one hand, the shelf-life extension of packaged products can be an answer to the exponential increase of worldwide demand for food. On the other hand, uncertainty of crude oil prices and reserves has imposed the necessity to find raw materials to replace oil-derived polymers. Additionally, consumers' awareness toward environmental issues increasingly pushes industries to look with renewed interest to "green" solutions. In response to these issues, numerous polymers have been exploited to develop biodegradable food packaging materials. Although the use of biopolymers has been limited due to their poor mechanical and barrier properties, these can be enhanced by adding reinforcing nanosized components to form nanocomposites. Cellulose is probably the most used and well-known renewable and sustainable raw material. The mechanical properties, reinforcing capabilities, abundance, low density, and biodegradability of nanosized cellulose make it an ideal candidate for polymer nanocomposites processing. Here we review the potential applications of cellulose based nanocomposites in food packaging materials, highlighting the several types of biopolymers with nanocellulose fillers that have been used to form bio-nanocomposite materials. The trends in nanocellulose packaging applications are also addressed.
Caitlin E. Meree; Gregory T. Schueneman; J. Carson Meredith; Meisha L. Shofner
2016-01-01
Recent emphasis on the pilot scale production of cellulosic nanomaterials has increased interest in the effective use of these materials as reinforcements for polymer composites. An important, enabling step to realizing the potential of cellulosic nanomaterials in their applications is the materials processing of CNC/polymer composites through multiple routes, i.e....
Wittgren, Bengt; Stefansson, Morgan; Porsch, Bedrich
2005-08-05
The novel approach described allows to characterise the surfactant-polymer interaction under several sodium dodecyl sulphate (SDS) concentrations (0-20 mM) using size exclusion chromatography (SEC) with online multi-angle light scattering (MALS) and refractometric (RI) detection. Three different cellulose derivatives, hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC) and hydroxyethyl cellulose (HEC), have been studied in solution containing 10 mM NaCl and various concentrations of sodium dodecyl sulphate. It is shown that this approach is well suited for successful application of both Hummel-Dreyer and multi-component light scattering principles and yields reliable molecular masses of both the polymer complex and the polymer itself within the complex, the amount of surfactant bound into the complex as well as appropriate values of the refractive index increment (dn/dc)micro, of both the complex and the polymer in question. The more hydrophobic derivatives HPC and HPMC adsorbed significantly more SDS than HEC. The inter-chain interactions close to critical aggregation concentration (cac) were clearly seen for HPC and HPMC as an almost two-fold average increase in polymer molecular mass contained in the complex.
Reinforcement of bacterial cellulose aerogels with biocompatible polymers.
Pircher, N; Veigel, S; Aigner, N; Nedelec, J M; Rosenau, T; Liebner, F
2014-10-13
Bacterial cellulose (BC) aerogels, which are fragile, ultra-lightweight, open-porous and transversally isotropic materials, have been reinforced with the biocompatible polymers polylactic acid (PLA), polycaprolactone (PCL), cellulose acetate (CA), and poly(methyl methacrylate) (PMMA), respectively, at varying BC/polymer ratios. Supercritical carbon dioxide anti-solvent precipitation and simultaneous extraction of the anti-solvent using scCO2 have been used as core techniques for incorporating the secondary polymer into the BC matrix and to convert the formed composite organogels into aerogels. Uniaxial compression tests revealed a considerable enhancement of the mechanical properties as compared to BC aerogels. Nitrogen sorption experiments at 77K and scanning electron micrographs confirmed the preservation (or even enhancement) of the surface-area-to-volume ratio for most of the samples. The formation of an open-porous, interpenetrating network of the second polymer has been demonstrated by treatment of BC/PMMA hybrid aerogels with EMIM acetate, which exclusively extracted cellulose, leaving behind self-supporting organogels. Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.
Reinforcement of bacterial cellulose aerogels with biocompatible polymers
Pircher, N.; Veigel, S.; Aigner, N.; Nedelec, J.M.; Rosenau, T.; Liebner, F.
2014-01-01
Bacterial cellulose (BC) aerogels, which are fragile, ultra-lightweight, open-porous and transversally isotropic materials, have been reinforced with the biocompatible polymers polylactic acid (PLA), polycaprolactone (PCL), cellulose acetate (CA), and poly(methyl methacrylate) (PMMA), respectively, at varying BC/polymer ratios. Supercritical carbon dioxide anti-solvent precipitation and simultaneous extraction of the anti-solvent using scCO2 have been used as core techniques for incorporating the secondary polymer into the BC matrix and to convert the formed composite organogels into aerogels. Uniaxial compression tests revealed a considerable enhancement of the mechanical properties as compared to BC aerogels. Nitrogen sorption experiments at 77 K and scanning electron micrographs confirmed the preservation (or even enhancement) of the surface-area-to-volume ratio for most of the samples. The formation of an open-porous, interpenetrating network of the second polymer has been demonstrated by treatment of BC/PMMA hybrid aerogels with EMIM acetate, which exclusively extracted cellulose, leaving behind self-supporting organogels. PMID:25037381
Secondary cell-wall assembly in flax phloem fibres: role of galactans.
Gorshkova, Tatyana; Morvan, Claudine
2006-01-01
Non-lignified fibre cells (named gelatinous fibres) are present in tension wood and the stems of fibre crops (such as flax and hemp). These cells develop a very thick S2 layer within the secondary cell wall, which is characterised by (1) cellulose microfibrils largely parallel to the longitudinal axis of the cell, and (2) a high proportion of galactose-containing polymers among the non-cellulosic polysaccharides. In this review, we focus on the role of these polymers in the assembly of gelatinous fibres of flax. At the different stages of fibre development, we analyse in detail data based on sugar composition, linkages of pectic polymers, and immunolocalisation of the beta-(1-->4)-galactans. These data indicate that high molecular-mass gelatinous galactans accumulate in specialised Golgi-derived vesicles during fibre cell-wall thickening. They consist of RG-I-like polymers with side chains of beta-(1-->4)-linked galactose. Most of them are short, but there are also long chains containing up to 28 galactosyl residues. At fibre maturity, two types of cross-linked galactans are identified, a C-L structure that resembles the part of soluble galactan with long side chains and a C-S structure with short chains. Different possibilities for soluble galactan to give rise to C-L and C-S are analysed. In addition, we discuss the prospect for the soluble galactan in preventing the newly formed cellulose chains from completing immediate crystallisation. This leads to a hypothesis that firstly the secretion of soluble galactans plays a role in the axial orientation of cellulose microfibrils, and secondly the remodelling and cross-linking of pectic galactans are linked to the dehydration and the assembly of S2 layer.
Micro-Nanostructures of Cellulose-Collagen for Critical Sized Bone Defect Healing.
Aravamudhan, Aja; Ramos, Daisy M; Nip, Jonathan; Kalajzic, Ivo; Kumbar, Sangamesh G
2018-02-01
Bone tissue engineering strategies utilize biodegradable polymeric matrices alone or in combination with cells and factors to provide mechanical support to bone, while promoting cell proliferation, differentiation, and tissue ingrowth. The performance of mechanically competent, micro-nanostructured polymeric matrices, in combination with bone marrow stromal cells (BMSCs), is evaluated in a critical sized bone defect. Cellulose acetate (CA) is used to fabricate a porous microstructured matrix. Type I collagen is then allowed to self-assemble on these microstructures to create a natural polymer-based, micro-nanostructured matrix (CAc). Poly (lactic-co-glycolic acid) matrices with identical microstructures serve as controls. Significantly higher number of implanted host cells are distributed in the natural polymer based micro-nanostructures with greater bone density and more uniform cell distribution. Additionally, a twofold increase in collagen content is observed with natural polymer based scaffolds. This study establishes the benefits of natural polymer derived micro-nanostructures in combination with donor derived BMSCs to repair and regenerate critical sized bone defects. Natural polymer based materials with mechanically competent micro-nanostructures may serve as an alternative material platform for bone regeneration. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Relative toxicity of pyrolysis products of some synthetic polymers
NASA Technical Reports Server (NTRS)
Hilado, C. J.; Slattengren, C. L.; Furst, A.; Kourtides, D. A.; Parker, J. A.
1976-01-01
Nineteen samples of synthetic polymers were evaluated for relative toxicity in the course of characterizing materials intended for aircraft interior applications. The generic polymers included ABS, chlorinated PVC, polycarbonate, polyphenylene oxide, polyphenylene sulfide, polysulfone, polyaryl sulfone, polyether sulfone, polybismaleimide, and polyvinyl fluoride. Test results are presented, and compared in relative rankings with similar results on cellulosic materials and other synthetic polymers. Under these test conditions, the samples of synthetic polymers were either comparable to or significantly less toxic than the samples of commercial cellulosic materials.
The Arabidopsis COBRA Protein Facilitates Cellulose Crystallization at the Plasma Membrane*
Sorek, Nadav; Sorek, Hagit; Kijac, Aleksandra; Szemenyei, Heidi J.; Bauer, Stefan; Hématy, Kian; Wemmer, David E.; Somerville, Chris R.
2014-01-01
Mutations in the Arabidopsis COBRA gene lead to defects in cellulose synthesis but the function of COBRA is unknown. Here we present evidence that COBRA localizes to discrete particles in the plasma membrane and is sensitive to inhibitors of cellulose synthesis, suggesting that COBRA and the cellulose synthase complex reside in close proximity on the plasma membrane. Live-cell imaging of cellulose synthesis indicated that, once initiated, cellulose synthesis appeared to proceed normally in the cobra mutant. Using isothermal calorimetry, COBRA was found to bind individual β1–4-linked glucan chains with a KD of 3.2 μm. Competition assays suggests that COBRA binds individual β1–4-linked glucan chains with higher affinity than crystalline cellulose. Solid-state nuclear magnetic resonance studies of the cell wall of the cobra mutant also indicated that, in addition to decreases in cellulose amount, the properties of the cellulose fibrils and other cell wall polymers differed from wild type by being less crystalline and having an increased number of reducing ends. We interpret the available evidence as suggesting that COBRA facilitates cellulose crystallization from the emerging β1–4-glucan chains by acting as a “polysaccharide chaperone.” PMID:25331944
Development of dialyzer with immobilized glycoconjugate polymers for removal of Shiga-toxin.
Miyagawa, Atsushi; Watanabe, Miho; Igai, Katsura; Kasuya, Maria Carmelita Z; Natori, Yasuhiro; Nishikawa, Kiyotaka; Hatanaka, Kenichi
2006-06-01
The dialyzer for Shiga-toxin elimination was developed and its performance was established. The dialyzer was prepared by immobilization of multivalent ligands. Glycoconjugate polymers having oligosaccharides and amino groups were synthesized to function as Shiga-toxin adsorbents. The amino group was utilized to immobilize the polymer inside the cellulose hollow fiber of the dialyzer. Cellulose hollow fibers packed in the dialyzer were carboxymethylated under moderate conditions. The glycoconjugate polymers were bound covalently to the hollow fibers of the dialyzer by condensation reaction between the amino group of the polymer and the carboxyl group of the cellulose hollow fiber. Shiga-toxin eliminabilities of the prepared dialyzers were evaluated at various conditions. Even at high concentration of protein such as FCS, the dialyzer showed an excellent performance for Shiga-toxin adsorption.
A Molecular Description of Cellulose Biosynthesis
McNamara, Joshua T.; Morgan, Jacob L.W.; Zimmer, Jochen
2016-01-01
Cellulose is the most abundant biopolymer on Earth, and certain organisms from bacteria to plants and animals synthesize cellulose as an extracellular polymer for various biological functions. Humans have used cellulose for millennia as a material and an energy source, and the advent of a lignocellulosic fuel industry will elevate it to the primary carbon source for the burgeoning renewable energy sector. Despite the biological and societal importance of cellulose, the molecular mechanism by which it is synthesized is now only beginning to emerge. On the basis of recent advances in structural and molecular biology on bacterial cellulose synthases, we review emerging concepts of how the enzymes polymerize glucose molecules, how the nascent polymer is transported across the plasma membrane, and how bacterial cellulose biosynthesis is regulated during biofilm formation. Additionally, we review evolutionary commonalities and differences between cellulose synthases that modulate the nature of the cellulose product formed. PMID:26034894
A solid-state NMR method to determine domain sizes in multi-component polymer formulations
NASA Astrophysics Data System (ADS)
Schlagnitweit, Judith; Tang, Mingxue; Baias, Maria; Richardson, Sara; Schantz, Staffan; Emsley, Lyndon
2015-12-01
Polymer domain sizes are related to many of the physical properties of polymers. Here we present a solid-state NMR experiment that is capable of measuring domain sizes in multi-component mixtures. The method combines selective excitation of carbon magnetization to isolate a specific component with proton spin diffusion to report on domain size. We demonstrate the method in the context of controlled release formulations, which represents one of today's challenges in pharmaceutical science. We show that we can measure domain sizes of interest in the different components of industrial pharmaceutical formulations at natural isotopic abundance containing various (modified) cellulose derivatives, such as microcrystalline cellulose matrixes that are film-coated with a mixture of ethyl cellulose (EC) and hydroxypropyl cellulose (HPC).
A Review on Grafting of Biofibers for Biocomposites
Wei, Liqing; McDonald, Armando G.
2016-01-01
A recent increase in the use of biofibers as low-cost and renewable reinforcement for the polymer biocomposites has been seen globally. Biofibers are classified into: lignocellulosic fibers (i.e., cellulose, wood and natural fibers), nanocellulose (i.e., cellulose nanocrystals and cellulose nanofibrils), and bacterial cellulose, while polymer matrix materials can be petroleum based or bio-based. Green biocomposites can be produced using both biobased fibers and polymers. Incompatibility between the hydrophilic biofibers and hydrophobic polymer matrix can cause performance failure of resulting biocomposites. Diverse efforts have focused on the modification of biofibers in order to improve the performances of biocomposites. “Grafting” copolymerization strategy can render the advantages of biofiber and impart polymer properties onto it and the performance of biocomposites can be tuned through changing grafting parameters. This review presents a short overview of various “grafting” methods which can be directly or potentially employed to enhance the interaction between biofibers and a polymer matrix for biocomposites. Major grafting techniques, including ring opening polymerization, grafting via coupling agent and free radical induced grafting, have been discussed. Improved properties such as mechanical, thermal, and water resistance have provided grafted biocomposites with new opportunities for applications in specific industries. PMID:28773429
Picard, Isabelle; Hollingsworth, Robert G; Salmieri, Stéphane; Lacroix, Monique
2012-08-01
Eight essential oils [0.125-1.0% (vol:vol) in acetone] were separately deposited on leaf disks to evaluate their potential to repel western flower thrips, Frankliniella occidentalis (Pergande) (Thysanoptera: Thripidae), adult females. Two of the best-performing essential oils were incorporated into polymer matrices of methyl cellulose or alginate [0.5 or 1% (wt:vol)] to verify the potential of the polymer to extend repellency of oils over time (24-120 h). Results showed that at a concentration of 0.5%, Thymus vulgaris L. (common thyme) and Satureja montana L. (winter savory) were the most repellent essential oils. For these two treatments, no western flower thrips were counted on treated leaf disks 60 min after the start of the test. T. serpyllum and O. compactum also showed repellency values > or = 90% at this concentration. With both the alginate and methyl cellulose polymers, the incorporation of polymers into treatment solutions containing 0.5% concentrations of S. montana and T. serpyllum resulted in higher repellency compared with treatment solutions lacking these polymers for a minimum of 3 d. For the alginate polymer, differences associated with polymer concentrations were most dramatic. High repellency was maintained for 4 d when a 0.5% concentration of the alginate was used in combination with a 0.5% concentration of S. montana. The use of repellent oils with polymers that extend their repellency may prove useful for both pre- and postharvest applications in flower crops.
Cellulose nanocrystals: synthesis, functional properties, and applications
George, Johnsy; Sabapathi, SN
2015-01-01
Cellulose nanocrystals are unique nanomaterials derived from the most abundant and almost inexhaustible natural polymer, cellulose. These nanomaterials have received significant interest due to their mechanical, optical, chemical, and rheological properties. Cellulose nanocrystals primarily obtained from naturally occurring cellulose fibers are biodegradable and renewable in nature and hence they serve as a sustainable and environmentally friendly material for most applications. These nanocrystals are basically hydrophilic in nature; however, they can be surface functionalized to meet various challenging requirements, such as the development of high-performance nanocomposites, using hydrophobic polymer matrices. Considering the ever-increasing interdisciplinary research being carried out on cellulose nanocrystals, this review aims to collate the knowledge available about the sources, chemical structure, and physical and chemical isolation procedures, as well as describes the mechanical, optical, and rheological properties, of cellulose nanocrystals. Innovative applications in diverse fields such as biomedical engineering, material sciences, electronics, catalysis, etc, wherein these cellulose nanocrystals can be used, are highlighted. PMID:26604715
Okunlola, Adenike; Adebayo, Amusa Sarafadeen; Adeyeye, Moji Christianah
2017-01-01
Tropical starches from Dioscorea dumetorum (bitter) and Dioscorea oppositifolia (Chinese) yams were acetylated with acetic anhydride in pyridine medium and utilized as polymers for the delivery of repaglinide in microsphere formulations in comparison to ethyl cellulose. Acetylated starches of bitter and Chinese yams with degrees of substitution of 2.56 and 2.70 respectively were obtained. Acetylation was confirmed by FTIR, 1 H NMR spectroscopy. A 3 2 factorial experimental design was performed using polymer type and drug-polymer ratio as independent variables. Particle size, swelling, entrapment and time for 50% drug release (t 50 ) were dependent variables. Contour plots showed the relationship between the independent factors and the response variables. All variables except swelling increased with drug: polymer ratio. Entrapment efficiency was generally in the rank of Bitter yam>Ethyl cellulose>Chinese yam. Repaglinide microspheres had size 50±4.00 to 350±18.10μm, entrapment efficiency 75.30±3.03 to 93.10±2.75% and t 50 3.20±0.42 to 7.20±0.55h. Bitter yam starch gave longer dissolution times than Chinese yam starch at all drug-polymer ratios. Drug release fitted Korsmeyer-Peppas and Hopfenberg models. Acetylated bitter and Chinese yam starches were found suitable as polymers to prolong release of repaglinide in microsphere formulations. Copyright © 2016 Elsevier B.V. All rights reserved.
Extraction of cellulose microcrystalline from galam wood for biopolymer
NASA Astrophysics Data System (ADS)
Ismail, Ika; Sa'adiyah, Devy; Rahajeng, Putri; Suprayitno, Abdi; Andiana, Rocky
2018-04-01
Consumption of plastic raw materials tends to increase, but until now the meet of the consumption of plastic raw are still low, even some are still imported. Nowadays, Indonesia's plastic needs are supported by petrochemicals where raw materials are still dependent abroad and petropolymer raw materials are derived from petroleum which will soon be depleted due to rising petroleum needs. Therefore, various studies have been conducted to develop natural fiber-based polymers that are biodegradable and abundant in nature. It is because the natural polymer production process is very efficient and very environmentally friendly. There have been many studies of biopolymers especially natural fiber-based polymers from plants, due to plants containing cellulose, hemicellulose and lignin. However, cellulose is the only one who has crystalline structures. Cellulose has a high crystality compared to amorphous lignin and hemicellulose. In this study, extracted cellulose as biopolymer and amplifier on composite. The cellulose is extracted from galam wood from East Kalimantan. Cellulose extraction will be obtained in nano / micro form through chemical and mechanical treatment processes. The chemical treatment of cellulose extraction is alkalinization process using NaOH solution, bleaching using NaClO2 and acid hydrolysis using sulfuric acid. After chemical treatment, ultrasonic mechanical treatment is made to make cellulose fibers into micro or nano size. Besides, cellulose results will be characterized. Characterization was performed to analyze molecules of cellulose compounds extracted from plants using Fourier Transformation Infra Red (FTIR) testing. XRD testing to analyze cellulose crystallinity. Scanning Electron Microscope (SEM) test to analyze morphology and fiber size.
Fox, Douglas M; Rodriguez, Rebeca S; Devilbiss, Mackenzie N; Woodcock, Jeremiah; Davis, Chelsea S; Sinko, Robert; Keten, Sinan; Gilman, Jeffrey W
2016-10-12
Cellulose nanocrystals (CNCs) have great potential as sustainable reinforcing materials for polymers, but there are a number of obstacles to commercialization that must first be overcome. High levels of water absorption, low thermal stabilities, poor miscibility with nonpolar polymers, and irreversible aggregation of the dried CNCs are among the greatest challenges to producing cellulose nanocrystal-polymer nanocomposites. A simple, scalable technique to modify sulfated cellulose nanocrystals (Na-CNCs) has been developed to address all of these issues. By using an ion exchange process to replace Na + with imidazolium or phosphonium cations, the surface energy is altered, the thermal stability is increased, and the miscibility of dried CNCs with a nonpolar polymer (epoxy and polystyrene) is enhanced. Characterization of the resulting ion exchanged CNCs (IE-CNCs) using potentiometry, inverse gas chromatography, dynamic vapor sorption, and laser scanning confocal microscopy reveals that the IE-CNCs have lower surface energies, adsorb less water, and have thermal stabilities of up to 100 °C higher than those of prepared protonated cellulose nanocrystals (H-CNCs) and 40 °C higher than that of neutralized Na-CNC. Methyl(triphenyl)phosphonium exchanged cellulose nanocrystals (MePh 3 P-CNC) adsorbed 30% less water than Na-CNC, retained less water during desorption, and were used to prepare well-dispersed epoxy composites without the aid of a solvent and well-dispersed polystyrene nanocomposites using a melt blending technique at 195 °C. Predictions of dispersion quality and glass transition temperatures from molecular modeling experiments match experimental observations. These fiber-reinforced polymers can be used as lightweight composites in transportation, infrastructure, and renewable energy applications.
Structural Investigations of Fibers and Films of Poly(p-phenylene benzobisthiazole). Volume 1
1982-05-01
differential scanning calorimetry, is unrelated to the diffuse scattered intensity [45]. Cellulose acetate which is known to be noncrystalline exhibits a high...Weidinger [45] found the diffuse scattered intensity increased with decreasing density and therefore, increasing void fraction, in air swollen cellulose ... Cellulose , and Poly(y-Benzyl-L-Glutamate)." J. Polym. Sci., Polym. Phys. Ed., 18, 663-682 (1980). 39. C.H. Kao and J.M. Ottino, personal communication
Microwave-assisted synthesis of noble nanostructures (Au, Pt, and Pd) using biodegradable polymer carboxymethyl cellulose (CMC) under microwave irradiation (MW) at 100 0C is reported. The reaction occurs within a few minutes, whereas at room temperature the reaction does not pro...
Liu, Cong; Li, Yanqing; Liao, Ruijin; Liao, Qiang; Tang, Chao
2018-01-01
Cellulose insulation polymer is an important component of oil-paper insulation, which is widely used in power transformer. The weight of the cellulose insulation polymer materials is as high as tens of tons in the larger converter transformer. Excellent performance of oil-paper insulation is very important for ensuring the safe operation of larger converter transformer. An effective way to improve the insulation and the physicochemical property of the oil impregnated insulation pressboard/paper is currently a popular research topic. In this paper, the polytetrafluoroethylene (PTFE) functional film was coated on the cellulose insulation pressboard by radio frequency (RF) magnetron sputtering to improve its breakdown voltage and the hydrophobicity properties. X-ray photoelectron spectroscopy (XPS) results show that the nano-structure PTFE functional film was successfully fabricated on the cellulose insulation pressboard surface. The scanning electron microscopy (SEM) and X-ray diffraction (XRD) present that the nanoscale size PTFE particles were attached to the pressboard surface and it exists in the amorphous form. Atomic force microscopy (AFM) shows that the sputtered pressboard surface is still rough. The rough PTFE functional film and the reduction of the hydrophilic hydroxyl of the surface due to the shielding effect of PTFE improve the breakdown and the hydrophobicity properties of the cellulose insulation pressboard obviously. This paper provides an innovative way to improve the performance of the cellulose insulation polymer. PMID:29883376
Hao, Jian; Liu, Cong; Li, Yanqing; Liao, Ruijin; Liao, Qiang; Tang, Chao
2018-05-21
Cellulose insulation polymer is an important component of oil-paper insulation, which is widely used in power transformer. The weight of the cellulose insulation polymer materials is as high as tens of tons in the larger converter transformer. Excellent performance of oil-paper insulation is very important for ensuring the safe operation of larger converter transformer. An effective way to improve the insulation and the physicochemical property of the oil impregnated insulation pressboard/paper is currently a popular research topic. In this paper, the polytetrafluoroethylene (PTFE) functional film was coated on the cellulose insulation pressboard by radio frequency (RF) magnetron sputtering to improve its breakdown voltage and the hydrophobicity properties. X-ray photoelectron spectroscopy (XPS) results show that the nano-structure PTFE functional film was successfully fabricated on the cellulose insulation pressboard surface. The scanning electron microscopy (SEM) and X-ray diffraction (XRD) present that the nanoscale size PTFE particles were attached to the pressboard surface and it exists in the amorphous form. Atomic force microscopy (AFM) shows that the sputtered pressboard surface is still rough. The rough PTFE functional film and the reduction of the hydrophilic hydroxyl of the surface due to the shielding effect of PTFE improve the breakdown and the hydrophobicity properties of the cellulose insulation pressboard obviously. This paper provides an innovative way to improve the performance of the cellulose insulation polymer.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jafirin, Serawati; Ahmad, Ishak; Ahmad, Azizan
The development of 49% poly(methyl methacrylate)-grafted natural rubber (MG49) and carboxymethyl cellulose as a composite polymer electrolyte film incorporating LiCF{sub 3}SO{sub 3} were explored. Carboxymethyl cellulose was synthesized from kenaf bast fibres via carboxymethylation process by alkali catalyzed reaction of cellulose with sodium chloroacetate. Reflection fourier transform infrared (ATR-FTIR) spectroscopy showed the presence of carboxyl peak after modification of cellulose with sodium chloroacetate. X-ray diffraction (XRD) analysis revealed that the crystallinity of cellulose was decrease after synthesis. High performance composite polymer electrolytes were prepared with various composition of carboxymethyl cellulose (2–10 wt%) via solution-casting method. The conductivity was increased withmore » carboxymethyl cellulose loading. The highest conductivity value achieved was 3.3 × 10{sup −7} Scm{sup −1} upon addition of 6% wt carboxymethyl cellulose. 6% wt carboxymethyl cellulose composition showed the highest tensile strength value of 7.9 MPa and 273 MPa of modulus value which demonstrated high mechanical performance with accepatable level of ionic conductivity.« less
Advanced Materials through Assembly of Nanocelluloses.
Kontturi, Eero; Laaksonen, Päivi; Linder, Markus B; Nonappa; Gröschel, André H; Rojas, Orlando J; Ikkala, Olli
2018-06-01
There is an emerging quest for lightweight materials with excellent mechanical properties and economic production, while still being sustainable and functionalizable. They could form the basis of the future bioeconomy for energy and material efficiency. Cellulose has long been recognized as an abundant polymer. Modified celluloses were, in fact, among the first polymers used in technical applications; however, they were later replaced by petroleum-based synthetic polymers. Currently, there is a resurgence of interest to utilize renewable resources, where cellulose is foreseen to make again a major impact, this time in the development of advanced materials. This is because of its availability and properties, as well as economic and sustainable production. Among cellulose-based structures, cellulose nanofibrils and nanocrystals display nanoscale lateral dimensions and lengths ranging from nanometers to micrometers. Their excellent mechanical properties are, in part, due to their crystalline assembly via hydrogen bonds. Owing to their abundant surface hydroxyl groups, they can be easily modified with nanoparticles, (bio)polymers, inorganics, or nanocarbons to form functional fibers, films, bulk matter, and porous aerogels and foams. Here, some of the recent progress in the development of advanced materials within this rapidly growing field is reviewed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
[Modern polymers in matrix tablets technology].
Zimmer, Łukasz; Kasperek, Regina; Poleszak, Ewa
2014-01-01
Matrix tablets are the most popular method of oral drug administration, and polymeric materials have been used broadly in matrix formulations to modify and modulate drug release rate. The main goal of the system is to extend drug release profiles to maintain a constant in vivo plasma drug concentration and a consistent pharmacological effect. Polymeric matrix tablets offer a great potential as oral controlled drug delivery systems. Cellulose derivatives, like hydroxypropyl methylcellulose (HPMC) are often used as matrix formers. However, also other types of polymers can be used for this purpose including: Kollidon SR, acrylic acid polymers such as Eudragits and Carbopols. Nevertheless, polymers of natural origin like: carragens, chitosan and alginates widely used in the food and cosmetics industry are now coming to the fore of pharmaceutical research and are used in matrix tablets technology. Modern polymers allow to obtain matrix tablets by 3D printing, which enables to develop new formulation types. In this paper, the polymers used in matrix tablets technology and examples of their applications were described.
Microwave-assisted (MW) synthesis of noble metals such as Au, Pt and Pd is reported using biodegradable polymer carboxymethyl cellulose (CMC) at 100°C within few seconds. The possible reduction entails the coupling of polar hydroxyl units in beta-glucopyranose units with micr...
Purushotham, Pallinti; Cho, Sung Hyun; Díaz-Moreno, Sara M.; Kumar, Manish; Nixon, B. Tracy; Bulone, Vincent; Zimmer, Jochen
2016-01-01
Plant cell walls are a composite material of polysaccharides, proteins, and other noncarbohydrate polymers. In the majority of plant tissues, the most abundant polysaccharide is cellulose, a linear polymer of glucose molecules. As the load-bearing component of the cell wall, individual cellulose chains are frequently bundled into micro and macrofibrils and are wrapped around the cell. Cellulose is synthesized by membrane-integrated and processive glycosyltransferases that polymerize UDP-activated glucose and secrete the nascent polymer through a channel formed by their own transmembrane regions. Plants express several different cellulose synthase isoforms during primary and secondary cell wall formation; however, so far, none has been functionally reconstituted in vitro for detailed biochemical analyses. Here we report the heterologous expression, purification, and functional reconstitution of Populus tremula x tremuloides CesA8 (PttCesA8), implicated in secondary cell wall formation. The recombinant enzyme polymerizes UDP-activated glucose to cellulose, as determined by enzyme degradation, permethylation glycosyl linkage analysis, electron microscopy, and mutagenesis studies. Catalytic activity is dependent on the presence of a lipid bilayer environment and divalent manganese cations. Further, electron microscopy analyses reveal that PttCesA8 produces cellulose fibers several micrometers long that occasionally are capped by globular particles, likely representing PttCesA8 complexes. Deletion of the enzyme’s N-terminal RING-finger domain almost completely abolishes fiber formation but not cellulose biosynthetic activity. Our results demonstrate that reconstituted PttCesA8 is not only sufficient for cellulose biosynthesis in vitro but also suffices to bundle individual glucan chains into cellulose microfibrils. PMID:27647898
Purushotham, Pallinti; Cho, Sung Hyun; Díaz-Moreno, Sara M; Kumar, Manish; Nixon, B Tracy; Bulone, Vincent; Zimmer, Jochen
2016-10-04
Plant cell walls are a composite material of polysaccharides, proteins, and other noncarbohydrate polymers. In the majority of plant tissues, the most abundant polysaccharide is cellulose, a linear polymer of glucose molecules. As the load-bearing component of the cell wall, individual cellulose chains are frequently bundled into micro and macrofibrils and are wrapped around the cell. Cellulose is synthesized by membrane-integrated and processive glycosyltransferases that polymerize UDP-activated glucose and secrete the nascent polymer through a channel formed by their own transmembrane regions. Plants express several different cellulose synthase isoforms during primary and secondary cell wall formation; however, so far, none has been functionally reconstituted in vitro for detailed biochemical analyses. Here we report the heterologous expression, purification, and functional reconstitution of Populus tremula x tremuloides CesA8 (PttCesA8), implicated in secondary cell wall formation. The recombinant enzyme polymerizes UDP-activated glucose to cellulose, as determined by enzyme degradation, permethylation glycosyl linkage analysis, electron microscopy, and mutagenesis studies. Catalytic activity is dependent on the presence of a lipid bilayer environment and divalent manganese cations. Further, electron microscopy analyses reveal that PttCesA8 produces cellulose fibers several micrometers long that occasionally are capped by globular particles, likely representing PttCesA8 complexes. Deletion of the enzyme's N-terminal RING-finger domain almost completely abolishes fiber formation but not cellulose biosynthetic activity. Our results demonstrate that reconstituted PttCesA8 is not only sufficient for cellulose biosynthesis in vitro but also suffices to bundle individual glucan chains into cellulose microfibrils.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gross, R.A.
1993-08-30
In this Final Report, work carried out under ARO grant C-DAAL03-G-0111 is described. The investigations performed include the following: (1) isolation, purification and characterization of a poly(3-hydroxybutyrate) depolymerase enzyme from Penicillium funiculosum, (2) determination that the depolymerase is a serine esterase, (3) study of the effect of polymer stereochemistry and crystalline order in a semi-crystalline polymer film substrate on enzyme specificity and activity, (3) isolation, purification and characterization of cellulose acetate degrading microorganisms and (4) determination of the biodegradability of cellulose acetate with degrees of substitution up to 2.5 under aerobic thermophilic conditions. Poly(3-hydroxybutyrate) biodegradation, Poly(3-hydroxybutyrate) depolymerase enzyme, Depolymerase frommore » Penicillium funiculosum, Cellulose acetate degrading microorganisms, Composting polymer biodegradable.« less
Dasan, Y K; Bhat, A H; Ahmad, Faiz
2017-02-10
The current research discusses the development of poly (lactic acid) (PLA) and poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) reinforced nanocrystalline cellulose bionanocomposites. The nanocrystalline cellulose was derived from waste oil palm empty fruit bunch fiber by acid hydrolysis process. The resulting nanocrystalline cellulose suspension was then surface functionalized by TEMPO-mediated oxidation and solvent exchange process. Furthermore, the PLA/PHBV/nanocrystalline cellulose bionanocomposites were produced by solvent casting method. The effect of the addition of nanocrystalline cellulose on structural, morphology, mechanical and barrier properties of bionanocomposites was investigated. The results revealed that the developed bionanocomposites showed improved mechanical properties and decrease in oxygen permeability rate. Therefore, the developed bio-based composite incorporated with an optimal composition of nanocrystalline cellulose exhibits properties as compared to the polymer blend. Copyright © 2016 Elsevier Ltd. All rights reserved.
Lee, Woong Gi; Kim, Do Hyeong; Jeon, Woo Cheol; Kwak, Sang Kyu; Kang, Seok Ju; Kang, Sang Wook
2017-04-28
We succeed in fabricating nearly straight nanopores in cellulose acetate (CA) polymers for use as battery gel separators by utilizing an inorganic hexahydrate (Ni(NO 3 ) 2 ·6H 2 O) complex and isostatic water pressure treatment. The continuous nanopores are generated when the polymer film is exposed to isostatic water pressure after complexing the nickel(II) nitrate hexahydrate (Ni(NO 3 ) 2 ·6H 2 O) with the CA. These results can be attributed to the manner in which the polymer chains are weakened because of the plasticization effect of the Ni(NO 3 ) 2 ·6H 2 O that is incorporated into the CA. Furthermore, we performed extensive molecular dynamics simulation for confirming the interaction between electrolyte and CA separator. The well controlled CA membrane after water pressure treatment enables fabrication of highly reliable cell by utilizing 2032-type coin cell structure. The resulting cell performance exhibits not only the effect of the physical morphology of CA separator, but also the chemical interaction of electrolyte with CA polymer which facilitates the Li-ion in the cell.
USDA-ARS?s Scientific Manuscript database
A novel biodegradable polymer based on glycerol, succinic anhydride and maleic anhydride, poly(glycerol succinate-co-maleate), poly(GlySAMA), was synthesized by melt polycondensation and tested as a matrix for composites with cellulose nanowhiskers. This glycerol-based polymer is thermally stable as...
Bali, Garima; Khunsupat, Ratayakorn; Akinosho, Hannah; ...
2016-09-10
Here, the recalcitrant nature of lignocellulosic biomass is a combined effect of several factors such as high crystallinity and high degree of polymerization of cellulose, lignin content and structure, and the available surface area for enzymatic degradation (i.e., accessibility). Genetic improvement of feedstock cell wall properties is a path to reducing recalcitrance of lignocellulosic biomass and improving conversion to various biofuels. An advanced understanding of the cellulose biosynthesis pathway is essential to precisely modify cellulose properties of plant cell walls. Here we report on the impact of modified expression of candidate cellulose biosynthesis pathway genes on the ultra-structure of cellulose,more » a key carbohydrate polymer of Populus cell wall using advanced nuclear magnetic resonance approaches. Noteworthy changes were observed in the cell wall characteristics of downregulated KORRIGAN 1 (KOR) and KOR 2 transgenic plants in comparison to the wild-type control. It was observed that all of the transgenic lines showed variation in cellulose ultrastructure, increase in cellulose crystallinity and decrease in the cellulose degree of polymerization. Additionally, the properties of cellulose allomorph abundance and accessibility were found to be variable. Application of such cellulose characterization techniques beyond the traditional measurement of cellulose abundance to comprehensive studies of cellulose properties in larger transgenic and naturally variable populations is expected to provide deeper insights into the complex nature of lignocellulosic material, which can significantly contribute to the development of precisely tailored plants for enhanced biofuels production.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bali, Garima; Khunsupat, Ratayakorn; Akinosho, Hannah
Here, the recalcitrant nature of lignocellulosic biomass is a combined effect of several factors such as high crystallinity and high degree of polymerization of cellulose, lignin content and structure, and the available surface area for enzymatic degradation (i.e., accessibility). Genetic improvement of feedstock cell wall properties is a path to reducing recalcitrance of lignocellulosic biomass and improving conversion to various biofuels. An advanced understanding of the cellulose biosynthesis pathway is essential to precisely modify cellulose properties of plant cell walls. Here we report on the impact of modified expression of candidate cellulose biosynthesis pathway genes on the ultra-structure of cellulose,more » a key carbohydrate polymer of Populus cell wall using advanced nuclear magnetic resonance approaches. Noteworthy changes were observed in the cell wall characteristics of downregulated KORRIGAN 1 (KOR) and KOR 2 transgenic plants in comparison to the wild-type control. It was observed that all of the transgenic lines showed variation in cellulose ultrastructure, increase in cellulose crystallinity and decrease in the cellulose degree of polymerization. Additionally, the properties of cellulose allomorph abundance and accessibility were found to be variable. Application of such cellulose characterization techniques beyond the traditional measurement of cellulose abundance to comprehensive studies of cellulose properties in larger transgenic and naturally variable populations is expected to provide deeper insights into the complex nature of lignocellulosic material, which can significantly contribute to the development of precisely tailored plants for enhanced biofuels production.« less
Disposable chemical sensors and biosensors made on cellulose paper.
Kim, Joo-Hyung; Mun, Seongcheol; Ko, Hyun-U; Yun, Gyu-Young; Kim, Jaehwan
2014-03-07
Most sensors are based on ceramic or semiconducting substrates, which have no flexibility or biocompatibility. Polymer-based sensors have been the subject of much attention due to their ability to collect molecules on their sensing surface with flexibility. Beyond polymer-based sensors, the recent discovery of cellulose as a smart material paved the way to the use of cellulose paper as a potential candidate for mechanical as well as electronic applications such as actuators and sensors. Several different paper-based sensors have been investigated and suggested. In this paper, we review the potential of cellulose materials for paper-based application devices, and suggest their feasibility for chemical and biosensor applications.
Im, Jisun; Sterner, Elizabeth S.; Swager, Timothy M.
2016-01-01
An integrated cellulose polymer concentrator/single-walled carbon nanotube (SWCNT) sensing system is demonstrated to detect benzene, toluene, and xylenes (BTX) vapors. The sensing system consists of functionalized cellulose as a selective concentrator disposed directly on top of a conductive SWCNT sensing layer. Functionalized cellulose concentrator (top layer) selectively adsorbs the target analyte and delivers the concentrated analyte as near as possible to the SWCNT sensing layer (bottom layer), which enables the simultaneous concentrating and sensing within a few seconds. The selectivity can be achieved by functionalizing cellulose acetate with a pentafluorophenylacetyl selector that interacts strongly with the target BTX analytes. A new design of the integrated cellulose concentrator/SWCNT sensing system allows high sensitivity with limits of detection for benzene, toluene, and m-xylene vapors of 55 ppm, 19 ppm, and 14 ppm, respectively, selectivity, and fast responses (<10 s to reach equilibrium), exhibiting the potential ability for on-site, real-time sensing applications. The sensing mechanism involves the selective adsorption of analytes in the concentrator film, which in turn mediates changes in the electronic potentials at the polymer-SWCNT interface and potentially changes in the tunneling barriers between nanotubes. PMID:26848660
Influence of Cellulose Nanofillers on the Rheological Properties of Polymer Electrolytes
NASA Astrophysics Data System (ADS)
El Kissi, Nadia; Alloin, Fannie; Dufresne, Alain; Sanchez, Jean-Yves; Bossard, Frédéric; D'Aprea, Alessandra; Leroy, Séverine
2008-07-01
In this study, nanocomposite polymer electrolytes, based on high molecular weight PEO were prepared from high aspect ratio natural cellulosic nanofillers. The thermomechanical behaviour of the resulting nanocomposites was investigated using differential scanning calorimetry, dynamic mechanical analysis and rheometrical measurements. The influence of entanglements versus percolation mechanism on the determination of the mechanical properties of the composite was also investigated. Shear rheometry of the unfilled PEO and related nanocomposites shows that the shear viscosity first decreases when the concentration in cellulose increases. Then typical suspension behaviour is obtained and the viscosity increases with the concentration. This observation is in agreement with DSC and DMA results and is explained in terms of polymer-filler interactions. Interactions between cellulose fillers, are responsible for the reinforcing effect above the melting temperature of the matrix, through the formation of a stiff network that is well predicted by a percolation concept.
Anisotropic membranes for gas separation
Gollan, A.Z.
1987-07-21
A gas separation membrane has a dense separating layer about 10,000 Angstroms or less thick and a porous support layer 10 to 400 microns thick that is an integral unit with gradually and continuously decreasing pore size from the base of the support layer to the surface of the thin separating layer and is made from a casting solution comprising ethyl cellulose and ethyl cellulose-based blends, typically greater than 47.5 ethoxyl content ethyl cellulose blended with compatible second polymers, such as nitrocellulose. The polymer content of the casting solution is from about 10% to about 35% by weight of the total solution with up to about 50% of this polymer weight a compatible second polymer to the ethyl cellulose in a volatile solvent such as isopropanol, methylacetate, methanol, ethanol, and acetone. Typical nonsolvents for the casting solutions include water and formamide. The casting solution is cast in air from about zero to 10 seconds to allow the volatile solvent to evaporate and then quenched in a coagulation bath, typically water, at a temperature of 7--25 C and then air dried at ambient temperature, typically 10--30 C. 2 figs.
NASA Astrophysics Data System (ADS)
Guo, Melinda
The surface of cellulose nanocrystals (CNCs) was successfully functionalized with metal chelating diblock copolymers via HyNic-4FB conjugation. Two types of PEG-metal-chelating block polymers with hydrazinonicotinate acetone hydrazine (HyNic) end groups were synthesized: mPEG-PGlu(DTPA) 18-HyNic and mPEG-PGlu(DTPA)25-HyNic. These two polymers both had a methoxy PEG (M ˜ 2000 Da) block that differed in the mean degree of polymerization of the metal-chelating block. They were characterized by 1H NMR spectroscopy and gel-permeation chromatography (GPC). 4-Formylbenzamide (4FB) groups were introduced onto the surface of CNCs and quantified through their reaction with 2-hydrazinopyridine. The polymers were grafted onto the surface of CNCs via bis-aryl hydrazone bond formation, and the kinetics of this reaction was explored by UV/Vis spectroscopy. The CNCs were also labeled with rhodamine and Alexa FluorRTM 488 dyes. Students in our collaborator's group in Pharmacy are examining applications of these materials as radiotherapeutic agents for cancer treatment.
Samuel L. Zelinka; Michael J. Lambrecht; Samuel V. Glass; Alex C. Wiedenhoeft; Daniel J. Yelle
2012-01-01
This paper examines phase transformations of water in wood and isolated wood cell wall components using differential scanning calorimetry with the purpose of better understanding "Type II water" or "freezable bound water" that has been reported for cellulose and other hydrophilic polymers. Solid loblolly pine (Pinus taeda...
Utilization of ethyl cellulose polymer and waste materials for roofing tile production
NASA Astrophysics Data System (ADS)
Sam, Suubitaa Spencer; Ng, ChoonAun; Chee, Swee Yong; Habib, NoorZainab; Nadeem, Humayon; Teoh, Wei Ping
2017-05-01
The aim of this study was to utilize ethyl cellulose, mixture of waste engine oil and waste vegetable oil as a binder in the environmental friendly roofing tile production. The waste engine-vegetable oil wasmix together with ethyl cellulose, fly ash, coarse aggregates, fine aggregatesand a catalyst. The Fourier Transform Infrared (FTIR) analysis showed that the oil mixture added with ethyl cellulose has the relatively high binding effect due to the presence of strong carbonyl group especially after being heat cured at 1900C for 24 hours. The mixed proportion of materials with different amount of ethyl cellulose used was studied in the production of tile specimen. The results showed that the ethyl cellulose composed roofing tile specimens passed the transverse breaking strength, durability, permeabilityand the ultraviolet accelerated test. The shrinkage on the tile can be overcome by adding temperature resistance polymer on the exterior of the tile.
Cellulose Fibre-Reinforced Biofoam for Structural Applications
Obradovic, Jasmina; Voutilainen, Mikko; Virtanen, Pasi; Lassila, Lippo; Fardim, Pedro
2017-01-01
Traditionally, polymers and macromolecular components used in the foam industry are mostly derived from petroleum. The current transition to a bio-economy creates demand for the use of more renewable feedstocks. Soybean oil is a vegetable oil, composed mainly of triglycerides, that is suitable material for foam production. In this study, acrylated epoxidized soybean oil and variable amounts of cellulose fibres were used in the production of bio-based foam. The developed macroporous bio-based architectures were characterised by several techniques, including porosity measurements, nanoindentation testing, scanning electron microscopy, and thermogravimetric analysis. It was found that the introduction of cellulose fibres during the foaming process was necessary to create the three-dimensional polymer foams. Using cellulose fibres has potential as a foam stabiliser because it obstructs the drainage of liquid from the film region in these gas-oil interfaces while simultaneously acting as a reinforcing agent in the polymer foam. The resulting foams possessed a porosity of approximately 56%, and the incorporation of cellulose fibres did not affect thermal behaviour. Scanning electron micrographs showed randomly oriented pores with irregular shapes and non-uniform pore size throughout the samples. PMID:28772981
Dynamic and Structure of Polymer-Cellulose Composite Electrolyte for Li-ion Battery
NASA Astrophysics Data System (ADS)
Zhan, Pengfei; Maranas, Janna
Crystalline PEO6LiX complex is a tunnel-like polymer/salt structure that promotes fast Li motion. The application is limited because high ion conductivity is only observed with short molecular weight PEO, as the molecular weight increase, tunnels are misaligned and the conductivity is decreased. High aspect ratio nanofillers based on cellulose nanowhiskers are hypothesized to promote the formation of tunnel structures. Compared with unfilled electrolyte, the room temperature ion conductivity increased as much as 1100% in filled electrolyte. With wide angle x-ray scattering (WAXS), we observe that the structure transitions from amorphous phase to crystalline phase as we add cellulose nanowhiskers and this is because the interaction between cellulose surface and polymer chain enhances the crystallization. From the temperature dependence of conductivity, the calculated Li+ hopping activation energy is shown to be lower in acidic cellulose nanowhisker filled samples. Our quasi-elastic neutron scattering (QENS) indicates with acidic surface, the rotation of PEO6 channels are more stabilized and this could be the origin of the low activation energy and high conductivity
Xuezhu Xu; Haoran Wang; Long Jiang; Xinnan Wang; Scott A. Payne; J.Y. Zhu; Ruipeng Li
2014-01-01
Poly(ethylene oxide) (PEO) nanofiber mats were produced by electrospinning. Biobased cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) as reinforcement nanofillers were also added to the polymer to produce composite nanofiber mats. The effects of the two cellulose nanofillers on the rheological properties of the PEO solutions and the microstructure,...
Electro-mechanical properties of hydrogel composites with micro- and nano-cellulose fillers
NASA Astrophysics Data System (ADS)
N, Mohamed Shahid U.; Deshpande, Abhijit P.; Lakshmana Rao, C.
2015-09-01
Stimuli responsive cross-linked hydrogels are of great interest for applications in diverse fields such as sensors and biomaterials. In this study, we investigate polymer composites filled with cellulose fillers. The celluloses used in making the composites were a microcrystalline cellulose of commercial grade and cellulose nano-whiskers obtained through acid hydrolysis of microcrystalline cellulose. The filler concentration was varied and corresponding physical, mechanical and electro-mechanical characterization was carried out. The electro-mechanical properties were determined using a quasi-static method. The fillers not only enhance the mechanical properties of the composite by providing better reinforcement but also provide a quantitative electric potential in the composite. The measurements reveal that the polymer composites prepared from two different cellulose fillers possess a quantitative electric potential which can be utilized in biomedical applications. It is argued that the mechanism behind the quantitative electric potential in the composites is due to streaming potentials arising due to electrical double layer formation.
Bacterial cellulose biosynthesis: diversity of operons, subunits, products, and functions.
Römling, Ute; Galperin, Michael Y
2015-09-01
Recent studies of bacterial cellulose biosynthesis, including structural characterization of a functional cellulose synthase complex, provided the first mechanistic insight into this fascinating process. In most studied bacteria, just two subunits, BcsA and BcsB, are necessary and sufficient for the formation of the polysaccharide chain in vitro. Other subunits - which differ among various taxa - affect the enzymatic activity and product yield in vivo by modulating (i) the expression of the biosynthesis apparatus, (ii) the export of the nascent β-D-glucan polymer to the cell surface, and (iii) the organization of cellulose fibers into a higher-order structure. These auxiliary subunits play key roles in determining the quantity and structure of resulting biofilms, which is particularly important for the interactions of bacteria with higher organisms - leading to rhizosphere colonization and modulating the virulence of cellulose-producing bacterial pathogens inside and outside of host cells. We review the organization of four principal types of cellulose synthase operon found in various bacterial genomes, identify additional bcs genes that encode components of the cellulose biosynthesis and secretion machinery, and propose a unified nomenclature for these genes and subunits. We also discuss the role of cellulose as a key component of biofilms and in the choice between acute infection and persistence in the host. Copyright © 2015 Elsevier Ltd. All rights reserved.
Karlsson, Rose-Marie Pernilla; Larsson, Per Tomas; Yu, Shun; Pendergraph, Samuel Allen; Pettersson, Torbjörn; Hellwig, Johannes; Wågberg, Lars
2018-06-01
Macroscopic beads of water-based gels consisting of uncharged and partially charged β-(1,4)-d-glucan polymers were developed to be used as a novel model material for studying the water induced swelling of the delignified plant fiber walls. The gel beads were prepared by drop-wise precipitation of solutions of dissolving grade fibers carboxymethylated to different degrees. The internal structure was analyzed using Solid State Cross-Polarization Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance and Small Angle X-ray Scattering showing that the internal structure could be considered a homogeneous, non-crystalline and molecularly dispersed polymer network. When beads with different charge densities were equilibrated with aqueous solutions of different ionic strengths and/or pH, the change in water uptake followed the trends expected for weak polyelectrolyte gels and the trends found for cellulose-rich fibers. When dried and subsequently immersed in water the beads also showed an irreversible loss of swelling depending on the charge and type of counter-ion which is commonly also found for cellulose-rich fibers. Taken all these results together it is clear that the model cellulose-based beads constitute an excellent tool for studying the fundamentals of swelling of cellulose rich plant fibers, aiding in the elucidation of the different molecular and supramolecular contributions to the swelling. Copyright © 2018 Elsevier Inc. All rights reserved.
Cellulose nanowhiskers and nanofibers from biomass for composite applications
NASA Astrophysics Data System (ADS)
Wang, Tao
2011-12-01
Biological nanocomposites such as plant cell wall exhibit high mechanical properties at a light weight. The secret of the rigidity and strength of the cell wall lies in its main structural component -- cellulose. Native cellulose exists as highly-ordered microfibrils, which are just a few nanometers wide and have been found to be stiffer than many synthetic fibers. In the quest for sustainable development around the world, using cellulose microfibrils from plant materials as renewable alternatives to conventional reinforcement materials such as glass fibers and carbon fibers is generating particular interest. In this research, by mechanical disintegration and by controlled chemical hydrolysis, both cellulose nanofibers and nanowhiskers were extracted from the cell wall of an agricultural waste, wheat straw. The reinforcement performances of the two nanofillers were then studied and compared using the water-soluble polyvinyl alcohol (PVOH) as a matrix material. It was found that while both of these nanofillers could impart higher stiffness to the polymer, the nanofibers from biomass were more effective in composite reinforcement than the cellulose crystals thanks to their large aspect ratio and their ability to form interconnected network structures through hydrogen bonding. One of the biggest challenges in the development of cellulose nanocomposites is achieving good dispersion. Because of the high density of hydroxyl groups on the surface of cellulose, it remains a difficult task to disperse cellulose nanofibers in many commonly used polymer matrices. The present work addresses this issue by developing a water-based route taking advantage of polymer colloidal suspensions. Combining cellulose nanofibers with one of the most important biopolymers, poly(lactic acid) (PLA), we have prepared nanocomposites with excellent fiber dispersion and improved modulus and strength. The bio-based nanocomposites have a great potential to serve as light-weight structural materials for automotive, medical, and other applications.
Streubel, A; Siepmann, J; Bodmeier, R
2003-01-01
The aim of this study was to develop and physicochemically characterize single unit, floating controlled drug delivery systems consisting of (i). polypropylene foam powder, (ii). matrix-forming polymer(s), (iii). drug, and (iv). filler (optional). The highly porous foam powder provided low density and, thus, excellent in vitro floating behavior of the tablets. All foam powder-containing tablets remained floating for at least 8 h in 0.1 N HCl at 37 degrees C. Different types of matrix-forming polymers were studied: hydroxypropyl methylcellulose (HPMC), polyacrylates, sodium alginate, corn starch, carrageenan, gum guar and gum arabic. The tablets eroded upon contact with the release medium, and the relative importance of drug diffusion, polymer swelling and tablet erosion for the resulting release patterns varied significantly with the type of matrix former. The release rate could effectively be modified by varying the "matrix-forming polymer/foam powder" ratio, the initial drug loading, the tablet geometry (radius and height), the type of matrix-forming polymer, the use of polymer blends and the addition of water-soluble or water-insoluble fillers (such as lactose or microcrystalline cellulose). The floating behavior of the low density drug delivery systems could successfully be combined with accurate control of the drug release patterns.
Anisotropic membranes for gas separation
Gollan, Arye Z.
1987-01-01
A gas separation membrane has a dense separating layer about 10,000 Angstroms or less thick and a porous support layer 10 to 400 microns thick that is an integral unit with gradually and continuously decreasing pore size from the base of the support layer to the surface of the thin separating layer and is made from a casting solution comprising ethyl cellulose and ethyl cellulose-based blends, typically greater than 47.5 ethoxyl content ethyl cellulose blended with compatible second polymers, such as nitrocellulose. The polymer content of the casting solution is from about 10% to about 35% by weight of the total solution with up to about 50% of this polymer weight a compatible second polymer to the ethyl cellulose in a volatile solvent such as isopropanol, methylacetate, methanol, ethanol, and acetone. Typical nonsolvents for the casting solutions include water and formamide. The casting solution is cast in air from about zero to 10 seconds to allow the volatile solvent to evaporate and then quenched in a coagulation bath, typically water, at a temperature of 7.degree.-25.degree. C. and then air dried at ambient temperature, typically 10.degree.-30.degree. C.
Kha, Hung; Tuble, Sigrid C; Kalyanasundaram, Shankar; Williamson, Richard E
2010-02-01
We understand few details about how the arrangement and interactions of cell wall polymers produce the mechanical properties of primary cell walls. Consequently, we cannot quantitatively assess if proposed wall structures are mechanically reasonable or assess the effectiveness of proposed mechanisms to change mechanical properties. As a step to remedying this, we developed WallGen, a Fortran program (available on request) building virtual cellulose-hemicellulose networks by stochastic self-assembly whose mechanical properties can be predicted by finite element analysis. The thousands of mechanical elements in the virtual wall are intended to have one-to-one spatial and mechanical correspondence with their real wall counterparts of cellulose microfibrils and hemicellulose chains. User-defined inputs set the properties of the two polymer types (elastic moduli, dimensions of microfibrils and hemicellulose chains, hemicellulose molecular weight) and their population properties (microfibril alignment and volume fraction, polymer weight percentages in the network). This allows exploration of the mechanical consequences of variations in nanostructure that might occur in vivo and provides estimates of how uncertainties regarding certain inputs will affect WallGen's mechanical predictions. We summarize WallGen's operation and the choice of values for user-defined inputs and show that predicted values for the elastic moduli of multinet walls subject to small displacements overlap measured values. "Design of experiment" methods provide systematic exploration of how changed input values affect mechanical properties and suggest that changing microfibril orientation and/or the number of hemicellulose cross-bridges could change wall mechanical anisotropy.
Host-guest chemistry of cyclodextrin carbamates and cellulose derivatives in aqueous solution.
Guo, Xin; Jia, Xiangxiang; Du, Jiaojiao; Xiao, Longqiang; Li, Feifei; Liao, Liqiong; Liu, Lijian
2013-10-15
Supramolecular polymer micelles were prepared on basis of the inclusion complexation between cyclodextrin carbamates and cellulose derivatives in aqueous media. Cyclodextrin carbamates were synthesized by microwave-assisted method from cyclodextrin and urea. The urea modified cyclodextrin shows the higher yield than the physical mixture of urea/cyclodextrin in the micellization with cellulose derivatives. The supramolecular structure of the core-shell micelles was demonstrated by (1)H NMR spectra, TEM images, and fluorescence spectra. The drug release behavior of the supramolecular polymer micelles was evaluated using prednisone acetate as a model drug. The drug loaded micelles showed steady and long time drug release behavior. With these properties, the supramolecular polymer micelles are attractive as drug carriers for pharmaceutical applications. Copyright © 2013 Elsevier Ltd. All rights reserved.
Water purification by reverse osmosis using heterocyclic polymer membranes
NASA Technical Reports Server (NTRS)
Scott, H.
1972-01-01
Pyrrone (polyimidazopyrrolone) polymers are a new class of thermally stable, radiation and chemical resistant aromatic-heterocyclic polymers featuring a greater chemical and mechanical durability than cellulose acetate.
NASA Astrophysics Data System (ADS)
Smyslov, R. Yu; Ezdakova, K. V.; Kopitsa, G. P.; Khripunov, A. K.; Bugrov, A. N.; Tkachenko, A. A.; Angelov, B.; Pipich, V.; Szekely, N. K.; Baranchikov, A. E.; Latysheva, E.; Chetverikov, Yu O.; Haramus, V.
2017-05-01
Scanning electron microscopy, ultra-small-angle neutron scattering (USANS), small-angle neutron and X-ray scattering (SANS and SAXS), as well as low-temperature nitrogen adsorption, were used in the studies of micro- and mesostructure of polymer matrix prepared from air-dry preliminarily disintegrated cellulose nano-gel film (synthesized by Gluconacetobacter xylinus) and the composites based on this bacterial cellulose. The composites included ZrO2 nanoparticles, Tb3+ in the form of low molecular weight salt and of metal-polymer complex with poly(vinylpyrrolydone)-poly(methacryloyl-o-aminobenzoic acid) copolymer. The combined analysis of the data obtained allowed revealing three levels of fractal organization in mesostructure of G. xylinus cellulose and its composites. It was shown that both the composition and an aggregation state of dopants have a significant impact on the structural characteristics of the organic-inorganic composites. The composites containing Tb3+ ions demonstrate efficient luminescence; its intensity is an order of magnitude higher in the case of the composites with the metal-polymer complex. It was found that there is the optimal content of ZrO2 nanoparticles in composites resulting in increased Tb3+ luminescence.
Wound dressings from naturally-occurring polymers: A review on homopolysaccharide-based composites.
Naseri-Nosar, Mahdi; Ziora, Zyta Maria
2018-06-01
Wound dressings are designed to support the wound bed and protect it from the factors that may delay or impede its healing such as contaminations and moisture-loss, thereby facilitating and accelerating the healing process. The materials used to prepare wound dressings include natural and synthetic polymers, as well as their combinations, in the forms of films, sponges and hydrogels. Polysaccharides are naturally-occurring polymers that have been extensively used as wound dressing materials. Homopolysaccharides are a class of polysaccharides consist of only one type of monosaccharide. The current review intends to overview the studies in which wound dressings from naturally-occurring polymers, based on homopolysaccharides, were prepared and evaluated. Homopolysaccharides such as cellulose, chitosan, chitin, pullulan, starch and β-glucan were considered. Copyright © 2018 Elsevier Ltd. All rights reserved.
Functional reconstitution of cellulose synthase in Escherichia coli.
Imai, Tomoya; Sun, Shi-Jing; Horikawa, Yoshiki; Wada, Masahisa; Sugiyama, Junji
2014-11-10
Cellulose is a high molecular weight polysaccharide of β1 → 4-d-glucan widely distributed in nature-from plant cell walls to extracellular polysaccharide in bacteria. Cellulose synthase, together with other auxiliary subunit(s) in the cell membrane, facilitates the fibrillar assembly of cellulose polymer chains into a microfibril. The gene encoding the catalytic subunit of cellulose synthase is cesA and has been identified in many cellulose-producing organisms. Very few studies, however, have shown that recombinant CesA protein synthesizes cellulose polymer, but the mechanism by which CesA protein synthesizes cellulose microfibrils is not known. Here we show that cellulose-synthesizing activity is successfully reconstituted in Escherichia coli by expressing the bacterial cellulose synthase complex of Gluconacetobacter xylinus: CesA and CesB (formerly BcsA and BcsB, respectively). Cellulose synthase activity was, however, only detected when CesA and CesB were coexpressed with diguanyl cyclase (DGC), which synthesizes cyclic-di-GMP (c-di-GMP), which in turn activates cellulose-synthesizing activity in bacteria. Direct observation by electron microscopy revealed extremely thin fibrillar structures outside E. coli cells, which were removed by cellulase treatment. This fiber structure is not likely to be the native crystallographic form of cellulose I, given that it was converted to cellulose II by a chemical treatment milder than ever described. We thus putatively conclude that this fine fiber is an unprecedented structure of cellulose. Despite the inability of the recombinant enzyme to synthesize the native structure of cellulose, the system described in this study, named "CESEC (CEllulose-Synthesizing E. Coli)", represents a useful tool for functional analyses of cellulose synthase and for seeding new nanomaterials.
Hutchens, Stacy A [Knoxville, TN; Woodward, Jonathan [Solihull, GB; Evans, Barbara R [Oak Ridge, TN; O'Neill, Hugh M [Knoxville, TN
2012-02-07
A composite biocompatible hydrogel material includes a porous polymer matrix, the polymer matrix including a plurality of pores and providing a Young's modulus of at least 10 GPa. A calcium comprising salt is disposed in at least some of the pores. The porous polymer matrix can comprise cellulose, including bacterial cellulose. The composite can be used as a bone graft material. A method of tissue repair within the body of animals includes the steps of providing a composite biocompatible hydrogel material including a porous polymer matrix, the polymer matrix including a plurality of pores and providing a Young's modulus of at least 10 GPa, and inserting the hydrogel material into cartilage or bone tissue of an animal, wherein the hydrogel material supports cell colonization in vitro for autologous cell seeding.
Mechanical Properties versus Morphology of Ordered Polymers
1980-05-01
for a similar banding observed in PPTA 30 fibers. The dark field results suggest each microfibril ribbon consists of a succession of narrow...transmission electron microscopy may be obtained by surface tension aided microfibril dispersion. The longitudinal sections of fibers obtained by...the value of c ( 0.08) obtained for native and regenerated cellulose , another class of stiff chain polymers16). (Deriva- tives of cellulose can be spun
Si Chen; Greg Schueneman; R. Byron Pipes; Jeffrey Youngblood; Robert J. Moon
2014-01-01
This work presents the development of dry spun cellulose acetate (CA) fibers using cellulose nanocrystals (CNCs) as reinforcements. Increasing amounts of CNCs were dispersed into CA fibers in efforts to improve the tensile strength and elastic modulus of the fiber. A systematic characterization of dispersion of CNCs in the polymer fiber and their effect on the...
Physical and mechanical testing of essential oil-embedded cellulose ester films
USDA-ARS?s Scientific Manuscript database
Polymer films made from cellulose esters are useful for embedding plant essential oils, either for food packaging or air freshener applications. Studies and testing were done on the physical and mechanical properties of cellulose ester-based films incorporating essential oils (EO) from lemongrass (C...
USDA-ARS?s Scientific Manuscript database
In recent years, the preparation of cellulosic composites and nanocomposites has become an important approach because of the wide abundance of cellulose, its biodegradability, renewability, and the ability to effectively reinforce a polymer matrix in an environmentally benign nature. The main object...
Bacterial cellulose biosynthesis: diversity of operons, subunits, products and functions
Römling, Ute; Galperin, Michael Y.
2015-01-01
Summary Recent studies of bacterial cellulose biosynthesis, including structural characterization of a functional cellulose synthase complex, provided the first mechanistic insight into this fascinating process. In most studied bacteria, just two subunits, BcsA and BcsB, are necessary and sufficient for the formation of the polysaccharide chain in vitro. Other subunits – which differ among various taxa – affect the enzymatic activity and product yield in vivo by modulating expression of biosynthesis apparatus, export of the nascent β-D-glucan polymer to the cell surface, and the organization of cellulose fibers into a higher-order structure. These auxiliary subunits play key roles in determining the quantity and structure of the resulting biofilm, which is particularly important for interactions of bacteria with higher organisms that lead to rhizosphere colonization and modulate virulence of cellulose-producing bacterial pathogens inside and outside of host cells. Here we review the organization of four principal types of cellulose synthase operons found in various bacterial genomes, identify additional bcs genes that encode likely components of the cellulose biosynthesis and secretion machinery, and propose a unified nomenclature for these genes and subunits. We also discuss the role of cellulose as a key component of biofilms formed by a variety of free-living and pathogenic bacteria and, for the latter, in the choice between acute infection and persistence in the host. PMID:26077867
Conformations of low-molecular-weight lignin polymers in water
Petridis, Loukas; Smith, Jeremy C.
2016-01-13
Low-molecular-weight lignin binds to cellulose during the thermochemical pretreatment of biomass for biofuel production, which prevents the efficient hydrolysis of the cellulose to sugars. The binding properties of lignin are influenced strongly by the conformations it adopts. Here, we use molecular dynamics simulations in aqueous solution to investigate the dependence of the shape of lignin polymers on chain length and temperature. Lignin is found to adopt collapsed conformations in water at 300 and 500 K. However, at 300 K, a discontinuous transition is found in the shape of the polymer as a function of the chain length. Below a criticalmore » degree of polymerization, N c=15, the polymer adopts less spherical conformations than above N c. The transition disappears at high temperatures (500 K) at which only spherical shapes are adopted. As a result, an implication relevant to cellulosic biofuel production is that lignin will self-aggregate even at high pretreatment temperatures.« less
Conformations of Low-Molecular-Weight Lignin Polymers in Water.
Petridis, Loukas; Smith, Jeremy C
2016-02-08
Low-molecular-weight lignin binds to cellulose during the thermochemical pretreatment of biomass for biofuel production, which prevents the efficient hydrolysis of the cellulose to sugars. The binding properties of lignin are influenced strongly by the conformations it adopts. Here, we use molecular dynamics simulations in aqueous solution to investigate the dependence of the shape of lignin polymers on chain length and temperature. Lignin is found to adopt collapsed conformations in water at 300 and 500 K. However, at 300 K, a discontinuous transition is found in the shape of the polymer as a function of the chain length. Below a critical degree of polymerization, Nc =15, the polymer adopts less spherical conformations than above Nc. The transition disappears at high temperatures (500 K) at which only spherical shapes are adopted. An implication relevant to cellulosic biofuel production is that lignin will self-aggregate even at high pretreatment temperatures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Lai-Kee-Him, Joséphine; Chanzy, Henri; Müller, Martin; Putaux, Jean-Luc; Imai, Tomoya; Bulone, Vincent
2002-10-04
Detergent extracts of microsomal fractions from suspension cultured cells of Rubus fruticosus (blackberry) were tested for their ability to synthesize in vitro sizable quantities of cellulose from UDP-glucose. Both Brij 58 and taurocholate were effective and yielded a substantial percentage of cellulose microfibrils together with (1-->3)-beta-d-glucan (callose). The taurocholate extracts, which did not require the addition of Mg(2+), were the most efficient, yielding roughly 20% of cellulose. This cellulose was characterized after callose removal by methylation analysis, electron microscopy, and electron and x-ray synchrotron diffractions; its resistance toward the acid Updegraff reagent was also evaluated. The cellulose microfibrils synthesized in vitro had the same diameter as the endogenous microfibrils isolated from primary cell walls. Both polymers diffracted as cellulose IV(I), a disorganized form of cellulose I. Besides these similarities, the in vitro microfibrils had a higher perfection and crystallinity as well as a better resistance toward the Updegraff reagent. These differences can be attributed to the mode of synthesis of the in vitro microfibrils that are able to grow independently in a neighbor-free environment, as opposed to the cellulose in the parent cell walls where new microfibrils have to interweave with the already laid polymers, with the result of a number of structural defects.
Jang, Suk-Yong; Han, Sien-Ho
2016-12-19
Currently, Si as an active material for LIBs has been attracting much attention due to its high theoretical specific capacity (3572 mAh g -1 ). However, a disadvantage when using a Si negative electrode for LIBs is the abrupt drop of its capabilities during the cycling process. Therefore, there have been a few studies of polymers such as poly(vinylidene fluoride) (PVdF), carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR) and polyacrylic acid (PAA) given that the robust structure of a polymeric binder to LIBs anodes is a promising means by which to enhance the performance of high-capacity anodes. These studies essentially focused mainly on modifying of the linear-polymer component or on copolymers dissolved in solvents. Cross-linking polymers as a binder may be preferred due to their good scratch resistance, excellent chemical resistance and high levels of adhesion and resilience. However, because these types of polymers (with a rigid structure and cross-linking points) are also insoluble in general organic solvents, applying these types in this capacity is virtually impossible.
Bioerodible System for Sequential Release of Multiple Drugs
Sundararaj, Sharath C.; Thomas, Mark V.; Dziubla, Thomas D.; Puleo, David A.
2013-01-01
Because many complex physiological processes are controlled by multiple biomolecules, comprehensive treatment of certain disease conditions may be more effectively achieved by administration of more than one type of drug. Thus, the objective of the present research was to develop a multilayered, polymer-based system for sequential delivery of multiple drugs. The polymers used were cellulose acetate phthalate (CAP) complexed with Pluronic F-127 (P). After evaluating morphology of the resulting CAPP system, in vitro release of small molecule drugs and a model protein was studied from both single and multilayered devices. Drug release from single-layered CAPP films followed zero-order kinetics related to surface erosion of the association polymer. Release studies from multilayered CAPP devices showed the possibility of achieving intermittent release of one type of drug as well as sequential release of more than one type of drug. Mathematical modeling accurately predicted the release profiles for both single layer and multilayered devices. The present CAPP association polymer-based multilayer devices can be used for localized, sequential delivery of multiple drugs for the possible treatment of complex disease conditions, and perhaps for tissue engineering applications, that require delivery of more than one type of biomolecule. PMID:24096151
Effect of cellulose nanocrystals on crystallization kinetics of polycaprolactone
NASA Astrophysics Data System (ADS)
Migler, Kalman; Roy, Debjani; Kotula, Anthony; Natarajan, Bharath; Gilman, Jeffrey; Fox, Douglas
The development of biocompatible polymer composites that enhance mechanical properties while maintaining thermoplastic processability is a longstanding goal in sustainable materials. Here we compatibilize a crystallizable polymer and a nano-fiber via surface modification and study the properties and crystallization kinetics of the resulting composite. First we demonstrate that polycaprolactone (PCL) and cellulose nanocrystals (CNCs) can be well-compatibilized by replacing the Na+ of sulfated cellulose nanocrystals (Na-CNCs) with tertiary butyl ammonium cations and then melt mixing via twin-screw extrusion. Transmission electron microscope and high temperature melt rheology show that the modified CNCs were dispersed in the polymer matrix. We find the crystallization kinetics are substantially affected by the CNC as indicated by the simultaneous measures of modulus and conformational states; higher loadings of CNCs accelerated the kinetics. We further correlate the crystallization kinetics, mechanical properties and stability.
Screening and characterization of plant cell walls using carbohydrate microarrays.
Sørensen, Iben; Willats, William G T
2011-01-01
Plant cells are surrounded by cell walls built largely from complex carbohydrates. The primary walls of growing plant cells consist of interdependent networks of three polysaccharide classes: cellulose, cross-linking glycans (also known as hemicelluloses), and pectins. Cellulose microfibrils are tethered together by cross-linking glycans, and this assembly forms the major load-bearing component of primary walls, which is infiltrated with pectic polymers. In the secondary walls of woody tissues, pectins are much reduced and walls are reinforced with the phenolic polymer lignin. Plant cell walls are essential for plant life and also have numerous industrial applications, ranging from wood to nutraceuticals. Enhancing our knowledge of cell wall biology and the effective use of cell wall materials is dependent to a large extent on being able to analyse their fine structures. We have developed a suite of techniques based on microarrays probed with monoclonal antibodies with specificity for cell wall components, and here we present practical protocols for this type of analysis.
Fornalé, Silvia; Capellades, Montserrat; Encina, Antonio; Wang, Kan; Irar, Sami; Lapierre, Catherine; Ruel, Katia; Joseleau, Jean-Paul; Berenguer, Jordi; Puigdomènech, Pere; Rigau, Joan; Caparrós-Ruiz, David
2012-07-01
Cinnamyl alcohol dehydrogenase (CAD) is a key enzyme involved in the last step of monolignol biosynthesis. The effect of CAD down-regulation on lignin production was investigated through a transgenic approach in maize. Transgenic CAD-RNAi plants show a different degree of enzymatic reduction depending on the analyzed tissue and show alterations in cell wall composition. Cell walls of CAD-RNAi stems contain a lignin polymer with a slight reduction in the S-to-G ratio without affecting the total lignin content. In addition, these cell walls accumulate higher levels of cellulose and arabinoxylans. In contrast, cell walls of CAD-RNAi midribs present a reduction in the total lignin content and of cell wall polysaccharides. In vitro degradability assays showed that, although to a different extent, the changes induced by the repression of CAD activity produced midribs and stems more degradable than wild-type plants. CAD-RNAi plants grown in the field presented a wild-type phenotype and produced higher amounts of dry biomass. Cellulosic bioethanol assays revealed that CAD-RNAi biomass produced higher levels of ethanol compared to wild-type, making CAD a good target to improve both the nutritional and energetic values of maize lignocellulosic biomass.
Fiber lubrication: A molecular dynamics simulation study
NASA Astrophysics Data System (ADS)
Liu, Hongyi
Molecular and mesoscopic level description of friction and lubrication remains a challenge because of difficulties in the phenomenological understanding of to the behaviors of solid-liquid interfaces during sliding. Fortunately, there is the computational simulation approach opens an opportunity to predict and analyze interfacial phenomena, which were studied with molecular dynamics (MD) and mesoscopic dynamics (MesoDyn) simulations. Polypropylene (PP) and cellulose are two of most common polymers in textile fibers. Confined amorphous surface layers of PP and cellulose were built successfully with xenon crystals which were used to compact the polymers. The physical and surface properties of the PP and cellulose surface layers were investigated by MD simulations, including the density, cohesive energy, volumetric thermal expansion, and contact angle with water. The topology method was employed to predict the properties of poly(alkylene glycol) (PAG) diblock copolymers and Pluronic triblock copolymers used as lubricants on surfaces. Density, zero shear viscosity, shear module, cohesive energy and solubility parameter were predicted with each block copolymer. Molecular dynamics simulations were used to study the interaction energy per unit contact area of block copolymer melts with PP and cellulose surfaces. The interaction energy is defined as the ratio of interfacial interaction energy to the contact area. Both poly(proplene oxide) (PPO) and poly(ethylene oxide) (PEO) segments provided a lipophilic character to both PP and cellulose surfaces. The PPO/PEO ratio and the molecular weight were found to impact the interaction energy on both PP and cellulose surfaces. In aqueous solutions, the interaction energy is complicated due to the presence of water and the cross interactions between the multiple molecular components. The polymer-water-surface (PWS) calculation method was proposed to calculate such complex systems. In a contrast with a vacuum condition, the presence of water increases the attractive interaction energy of the diblock copolymer on the cellulose surface, compared with that on the PP surface. Water decreases the interaction energy of the triblock copolymer on the cellulose surface, compared with that on the PP surface. MesoDyn was adopted to investigate the self-assembled morphology of the triblock copolymer, in aqueous solution, confined and sheared at solid-liquid interfaces. In a bulk aqueous solution, when the polymer concentration reached 10% v/v, micelles were observed with PPO blocks in the core and PEO blocks in the shell of the micelles. At the concentrations of 25% and 50%, worm-like micelles and irregular cylinders were observed in solutions, respectively. The micelles were formed faster in aqueous solutions confined by cellulose surfaces than that in the bulk. The formed micelles were broken under shearing, which led to a depletion of polymers at the interfaces. During the shearing on the PP surfaces, the polymers were adsorbed on the surfaces protecting the PP surfaces. This simulation study in the fiber lubrication was in good agreement with the experimental results and so provided an approach to visualize the polymer configuration at the liquid-solid interface, predict the lubricant-surface systems, and theoretically guide the experiments of designing new/efficient lubricants for fibers.
Method of tissue repair using a composite material
Hutchens, Stacy A.; Woodward, Jonathan; Evans, Barbara R.; O'Neill, Hugh M.
2016-03-01
A composite biocompatible hydrogel material includes a porous polymer matrix, the polymer matrix including a plurality of pores and providing a Young's modulus of at least 10 GPa. A calcium comprising salt is disposed in at least some of the pores. The porous polymer matrix can comprise cellulose, including bacterial cellulose. The composite can be used as a bone graft material. A method of tissue repair within the body of animals includes the steps of providing a composite biocompatible hydrogel material including a porous polymer matrix, the polymer matrix including a plurality of pores and providing a Young's modulus of at least 10 GPa, and inserting the hydrogel material into cartilage or bone tissue of an animal, wherein the hydrogel material supports cell colonization in vitro for autologous cell seeding.
Method of tissue repair using a composite material
Hutchens, Stacy A; Woodward, Jonathan; Evans, Barbara R; O'Neill, Hugh M
2014-03-18
A composite biocompatible hydrogel material includes a porous polymer matrix, the polymer matrix including a plurality of pores and providing a Young's modulus of at least 10 GPa. A calcium comprising salt is disposed in at least some of the pores. The porous polymer matrix can comprise cellulose, including bacterial cellulose. The composite can be used as a bone graft material. A method of tissue repair within the body of animals includes the steps of providing a composite biocompatible hydrogel material including a porous polymer matrix, the polymer matrix including a plurality of pores and providing a Young's modulus of at least 10 GPa, and inserting the hydrogel material into cartilage or bone tissue of an animal, wherein the hydrogel material supports cell colonization in vitro for autologous cell seeding.
Biopolymer-based nanocomposites: effect of lignin acetylation in cellulose triacetate films
Nevárez, Laura Alicia Manjarrez; Casarrubias, Lourdes Ballinas; Celzard, Alain; Fierro, Vanessa; Muñoz, Vinicio Torres; Davila, Alejandro Camacho; Lubian, José Román Torres; Sánchez, Guillermo González
2011-01-01
We have prepared all-biopolymer nanocomposite films using lignin as a filler and cellulose triacetate (CTA) as a polymer matrix, and characterized them by several analytical methods. Three types of lignin were tested: organosolv, hydrolytic and kraft, with or without acetylation. They were used in the form of nanoparticles incorporated at 1 wt% in CTA. Self-supported films were prepared by vapor-induced phase separation at controlled temperature (35–55 °C) and relative humidity (10–70%). The efficiency of acetylation of each type of lignin was studied and discussed, as well as its effects on film structure, homogeneity and mechanical properties. The obtained results are explained in terms of intermolecular filler-matrix interaction at the nanometer scale, for which the highest mechanical resistance was reached using hydrolytic lignin in the nanocomposite. PMID:27877425
NASA Astrophysics Data System (ADS)
Winter, Armin; Mundigler, Norbert; Holzweber, Julian; Veigel, Stefan; Müller, Ulrich; Kovalcik, Adriana; Gindl-Altmutter, Wolfgang
2017-12-01
Microfibrillated cellulose (MFC) is a fascinating material with an obvious potential for composite reinforcement due to its excellent mechanics together with high specific surface area. However, in order to use this potential, commercially viable solutions to important technological challenges have to be found. Notably, the distinct hydrophilicity of MFC prevents efficient drying without loss in specific surface area, necessitating storage and processing in wet condition. This greatly hinders compounding with important technical polymers immiscible with water. Differently from cellulose, the chemistry of the major wood polymers lignin and hemicellulose is much more diverse in terms of functional groups. Specifically, the aromatic moieties present in lignin and acetyl groups in hemicellulose provide distinctly less polar surface-chemical functionality compared to hydroxyl groups which dominate the surface-chemical character of cellulose. It is shown that considerable advantages in the production of MFC-filled poly(lactic acid) filaments for three-dimensional printing can be obtained through the use of MFC containing residual lignin and hemicellulose due to their advantageous surface-chemical characteristics. Specifically, considerably reduced agglomerations of MFC in the filaments in combination with improved printability and improved toughness of printed objects are achieved. This article is part of a discussion meeting issue `New horizons for cellulose nanotechnology'.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hogen-Esch, T.E.
1984-01-01
Accomplishments for the past year are discussed for grafting of acrylamide to: (1) starch and related polysaccharides; and (2) cellulose solutions. In grafting acrylamide to various polysaccharide substrates such as okra polysaccharide, yellow dextrin, waxy corn starch, potato amylose, gum arabic, the efficiency of Ce/sup 4 +/ as initiator was found to vary from 0.02 to 0.89, depending on reaction conditions. Okra polysaccharide was isolated, characterized, and evaluated for use in enhanced oil recovery. A series of experiments designed to increase the viscosifying power of certain polymers by chain extension techniques has also been conducted. Characterization of the polymers bymore » ultracentrifugation, size exclusion chromatography, membrane filtration, multi-cell equilibrium dialysis, and rheological studies has also been done. In grafting of acrylamide to cellulose solutions the following two courses were taken: (1) dissolution of cellulose in 70% aqueous zinc chloride, followed by Ce/sup 4 +/ initiated grafting of acrylamide, and (2) introduction of a 1,2-diol substituent onto the anhydroglucose units of the cellulose chain via dissolution of cellulose in concentrated aqueous NaOH, followed by treatment with glyceryl chlorohydrin. Considerable progress has been made via both approaches. 11 refs., 1 fig., 1 tab.« less
Winter, Armin; Mundigler, Norbert; Holzweber, Julian; Veigel, Stefan; Müller, Ulrich; Kovalcik, Adriana; Gindl-Altmutter, Wolfgang
2018-02-13
Microfibrillated cellulose (MFC) is a fascinating material with an obvious potential for composite reinforcement due to its excellent mechanics together with high specific surface area. However, in order to use this potential, commercially viable solutions to important technological challenges have to be found. Notably, the distinct hydrophilicity of MFC prevents efficient drying without loss in specific surface area, necessitating storage and processing in wet condition. This greatly hinders compounding with important technical polymers immiscible with water. Differently from cellulose, the chemistry of the major wood polymers lignin and hemicellulose is much more diverse in terms of functional groups. Specifically, the aromatic moieties present in lignin and acetyl groups in hemicellulose provide distinctly less polar surface-chemical functionality compared to hydroxyl groups which dominate the surface-chemical character of cellulose. It is shown that considerable advantages in the production of MFC-filled poly(lactic acid) filaments for three-dimensional printing can be obtained through the use of MFC containing residual lignin and hemicellulose due to their advantageous surface-chemical characteristics. Specifically, considerably reduced agglomerations of MFC in the filaments in combination with improved printability and improved toughness of printed objects are achieved.This article is part of a discussion meeting issue 'New horizons for cellulose nanotechnology'. © 2017 The Author(s).
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang, L.; Zhou, J.; Huang, J.
1999-11-01
Interpenetrating polymer network (IPN) coatings synthesized from castor-oil-based polyurethane (PU) with chitosan, nitrocellulose, or elaeostearin were coated on regenerated cellulose (RC) film for curing at 80--100 C for 2--5 min, providing biodegradable, water-resistant cellulose films coded, respectively, as RCCH, RCNC, and RCEs. The coated films were buried in natural soil for decaying and inoculated with a spore suspension of fungi on the agar medium, respectively, to test biodegradability. The viscosity-average molecular weight, M{sub {eta}}, and the weight of the degraded films decreased sharply with the progress of degradation. The degradation half-lifes, t{sub 1/2}, of the films in soil at 30more » C were found to be 19 days for RC, 25 days for RCNC, 32 days for RCCH, and 45 days for the RCEs films. Scanning electron microscopy (SEM) showed that the extent of decay followed in the order RC {gt} RCNC {gt} RCCH {gt} RCEs. SEM, infrared (IR), high-performance liquid chromatography (HPLC), and CO{sub 2} evolution results indicated that the microorganisms directly attacked the water-resistant coating layer and then penetrated into the cellulose to speedily metabolize, while accompanying with producing CO{sub 2}, H{sub 2}O, glucose cleaved from cellulose, and small molecules decomposed from the coatings.« less
High throughput workflow for coacervate formation and characterization in shampoo systems.
Kalantar, T H; Tucker, C J; Zalusky, A S; Boomgaard, T A; Wilson, B E; Ladika, M; Jordan, S L; Li, W K; Zhang, X; Goh, C G
2007-01-01
Cationic cellulosic polymers find wide utility as benefit agents in shampoo. Deposition of these polymers onto hair has been shown to mend split-ends, improve appearance and wet combing, as well as provide controlled delivery of insoluble actives. The deposition is thought to be enhanced by the formation of a polymer/surfactant complex that phase-separates from the bulk solution upon dilution. A standard characterization method has been developed to characterize the coacervate formation upon dilution, but the test is time and material prohibitive. We have developed a semi-automated high throughput workflow to characterize the coacervate-forming behavior of different shampoo formulations. A procedure that allows testing of real use shampoo dilutions without first formulating a complete shampoo was identified. This procedure was adapted to a Tecan liquid handler by optimizing the parameters for liquid dispensing as well as for mixing. The high throughput workflow enabled preparation and testing of hundreds of formulations with different types and levels of cationic cellulosic polymers and surfactants, and for each formulation a haze diagram was constructed. Optimal formulations and their dilutions that give substantial coacervate formation (determined by haze measurements) were identified. Results from this high throughput workflow were shown to reproduce standard haze and bench-top turbidity measurements, and this workflow has the advantages of using less material and allowing more variables to be tested with significant time savings.
Smith-Moritz, Andreia M.; Hao, Zhao; Fernández-Niño, Susana G.; Fangel, Jonatan U.; Verhertbruggen, Yves; Holman, Hoi-Ying N.; Willats, William G. T.; Ronald, Pamela C.; Scheller, Henrik V.; Heazlewood, Joshua L.; Vega-Sánchez, Miguel E.
2015-01-01
The CELLULOSE SYNTHASE-LIKE F6 (CslF6) gene was previously shown to mediate the biosynthesis of mixed-linkage glucan (MLG), a cell wall polysaccharide that is hypothesized to be tightly associated with cellulose and also have a role in cell expansion in the primary cell wall of young seedlings in grass species. We have recently shown that loss-of-function cslf6 rice mutants do not accumulate MLG in most vegetative tissues. Despite the absence of a structurally important polymer, MLG, these mutants are unexpectedly viable and only show a moderate growth compromise compared to wild type. Therefore these mutants are ideal biological systems to test the current grass cell wall model. In order to gain a better understanding of the role of MLG in the primary wall, we performed in-depth compositional and structural analyses of the cell walls of 3 day-old rice seedlings using various biochemical and novel microspectroscopic approaches. We found that cellulose content as well as matrix polysaccharide composition was not significantly altered in the MLG deficient mutant. However, we observed a significant change in cellulose microfibril bundle organization in mesophyll cell walls of the cslf6 mutant. Using synchrotron source Fourier Transform Mid-Infrared (FTM-IR) Spectromicroscopy for high-resolution imaging, we determined that the bonds associated with cellulose and arabinoxylan, another major component of the primary cell walls of grasses, were in a lower energy configuration compared to wild type, suggesting a slightly weaker primary wall in MLG deficient mesophyll cells. Taken together, these results suggest that MLG may influence cellulose deposition in mesophyll cell walls without significantly affecting anisotropic growth thus challenging MLG importance in cell wall expansion. PMID:26347754
Smith-Moritz, Andreia M.; Hao, Zhao; Fernández-Nino, Susana G.; ...
2015-08-18
The CELLULOSE SYNTHASE-LIKE F6 (CslF6) gene was previously shown to mediate the biosynthesis of mixed-linkage glucan (MLG), a cell wall polysaccharide that is hypothesized to be tightly associated with cellulose and also have a role in cell expansion in the primary cell wall of young seedlings in grass species. We have recently shown that loss-of-function cslf6 rice mutants do not accumulate MLG in most vegetative tissues. Despite the absence of a structurally important polymer, MLG, these mutants are unexpectedly viable and only show a moderate growth compromise compared to wild type. Therefore these mutants are ideal biological systems to testmore » the current grass cell wall model. In order to gain a better understanding of the role of MLG in the primary wall, we performed in-depth compositional and structural analyses of the cell walls of 3 day-old rice seedlings using various biochemical and novel microspectroscopic approaches. We found that cellulose content as well as matrix polysaccharide composition was not significantly altered in the MLG deficient mutant. However, we observed a significant change in cellulose microfibril bundle organization in mesophyll cell walls of the cslf6 mutant. Using synchrotron source Fourier Transform Mid-Infrared (FTM-IR) Spectromicroscopy for high-resolution imaging, we determined that the bonds associated with cellulose and arabinoxylan, another major component of the primary cell walls of grasses, were in a lower energy configuration compared to wild type, suggesting a slightly weaker primary wall in MLG deficient mesophyll cells. Finally, taken together, these results suggest that MLG may influence cellulose deposition in mesophyll cell walls without significantly affecting anisotropic growth thus challenging MLG importance in cell wall expansion.« less
Thermodynamics of Potassium Ferricyanide Diffusion through B-1355N Exopolysaccharide Films
USDA-ARS?s Scientific Manuscript database
Biological polymers (biopolymers) offer a degree of functionality not available in most synthetic polymers. Carbohydrate polymers (polysaccharides) are produced with great frequency in nature. Starch, cellulose and chitin are some of the most abundant natural polymers on earth. We examine here for...
A framework for multi-scale simulation of crystal growth in the presence of polymers.
Mandal, Taraknath; Huang, Wenjun; Mecca, Jodi M; Getchell, Ashley; Porter, William W; Larson, Ronald G
2017-03-01
We present a multi-scale simulation method for modeling crystal growth in the presence of polymer excipients. The method includes a coarse-grained (CG) model for small molecules of known crystal structure whose force field is obtained using structural properties from atomistic simulations. This CG model is capable of stabilizing the molecular crystal structure and capturing the crystal growth from the melt for a wide range of small organic molecules, as demonstrated by application of our method to the molecules isoniazid, urea, sulfamethoxazole, prilocaine, oxcarbazepine, and phenytoin. This CG model can also be used to study the effect of additives, such as polymers, on the inhibition of crystal growth by polymers, as exemplified by our simulation of suppression of the rate of crystal growth of phenytoin, an active pharmaceutical ingredient (API), by a cellulose excipient, functionalized with acetate (Ac), hydroxy-propyl (Hp) and succinate (Su) groups. We show that the efficacy of the cellulosic polymers in slowing crystal growth of small molecules strongly depends on the functional group substitution on the cellulose backbone, with the acetate substituent group slowing crystal growth more than does the deprotonated succinate group, which we confirm by experimental drug supersaturation studies.
Nanocellulose in Polymer Composites and Biomedical: Research and Applications
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lu, Yuan; Tekinalp, Halil L; Peter, William H
Nanocellulose materials are nano-sized cellulose fibers or crystals that are produced by bacteria or derived from plants. These materials exhibit exceptional strength characteristics, light weight, transparency, and excellent biocompatibility. Compared to some other nanomaterials, nanocellulose is renewable and less expensive to produce. As such, a wide range of applications for nanocellulose has been envisioned. Most extensively studied areas include polymer composites and biomedical applications. Cellulose nanofibrils and nanocrystals have been used to reinforce both thermoplastic and thermoset polymers. Given the hydrophilic nature of these materials, the interfacial properties with most polymers are often poor. Various surface modification procedures have thusmore » been adopted to improve the interaction between polymer matrix and cellulose nanofibrils or nanocrystals. In addition, the applications of nanocellulose as biomaterials have been explored including wound dressing, tissue repair, and medical implants. Nanocellulose materials for wound healing and periodontal tissue recovery have become commercially available, demonstrating the great potential of nanocellulose as a new generation of biomaterials. In this review, we highlight the applications of nanocellulose as reinforcing fillers for composites and the effect of surface modification on the mechanical properties as well as the application as biomaterials.« less
Zahoor; Sun, Dan; Li, Ying; Wang, Jing; Tu, Yuanyuan; Wang, Yanting; Hu, Zhen; Zhou, Shiguang; Wang, Lingqiang; Xie, Guosheng; Huang, Jianliang; Alam, Aftab; Peng, Liangcai
2017-11-01
In this study, two rice cultivars were collected from experimental fields with seven nitrogen fertilizer treatments. All biomass samples contained significantly increased cellulose contents and reduced silica levels, with variable amounts of hemicellulose and lignin from different nitrogen treatments. Under chemical (NaOH, CaO, H 2 SO 4 ) and physical (hot water) pretreatments, biomass samples exhibited much enhanced hexoses yields from enzymatic hydrolysis, with high bioethanol production from yeast fermentation. Notably, both degree of polymerization (DP) of cellulose and xylose/arabinose (Xyl/Ara) ratio of hemicellulose were reduced in biomass residues, whereas other wall polymer features (cellulose crystallinity and monolignol proportion) were variable. Integrative analysis indicated that cellulose DP, hemicellulosic Xyl/Ara and silica are the major factors that significantly affect cellulose crystallinity and biomass saccharification. Hence, this study has demonstrated that nitrogen fertilizer supply could largely enhance biomass saccharification in rice cultivars, mainly by reducing cellulose DP, hemicellulosic Xyl/Ara and silica in cell walls. Copyright © 2017 Elsevier Ltd. All rights reserved.
Water absorption behaviour of hybrid interwoven cellulosic fibre composites
NASA Astrophysics Data System (ADS)
Maslinda, A. B.; Majid, M. S. Abdul; Ridzuan, M. J. M.; Syayuthi, AR. A.
2017-10-01
The present paper investigated the water absorption behaviour of hybrid interwoven cellulosic fibre composites. Hybrid composites consisting of interwoven kenaf/jute and kenaf/hemp yarns were prepared by an infusion manufacturing technique that used epoxy as the polymer matrix. Water absorption test was conducted as elucidated in ASTM D570 standard by immersing the composite samples in tap water at room temperature until reaching their water content saturation point. For each composite type, average from five samples was recorded and the percentage of water uptake against the square root of time was plotted. As the effect of hybridization, the water uptake, diffusion and permeability coefficient of the hybrid composites were lesser than the individual woven composites.
Li, Bin; Konecke, Stephanie; Wegiel, Lindsay A; Taylor, Lynne S; Edgar, Kevin J
2013-10-15
Amorphous solid dispersions (ASD) of curcumin (Cur) in cellulose derivative matrices, hydroxypropylmethylcellulose acetate succinate (HPMCAS), carboxymethylcellulose acetate butyrate (CMCAB), and cellulose acetate adipate propionate (CAAdP) were prepared in order to investigate the structure-property relationship and identify polymer properties necessary to effectively increase Cur aqueous solution concentration. XRD results indicated that all investigated solid dispersions were amorphous, even at a 9:1 Cur:polymer ratio. Both stability against crystallization and Cur solution concentration from these ASDs were significantly higher than those from physical mixtures and crystalline Cur. Remarkably, curcumin was also stabilized against chemical degradation in solution. Chemical stabilization was polymer-dependent, with stabilization in CAAdP>CMCAB>HPMCAS>PVP, while matrices enhanced solution concentration as PVP>HPMCAS>CMCAB≈CAAdP. HPMCAS/Cur dispersions have useful combinations of pH-triggered release profile, chemical stabilization, and strong enhancement of Cur solution concentration. Copyright © 2013 Elsevier Ltd. All rights reserved.
Characterization of ethyl cellulose polymer.
Mahnaj, Tazin; Ahmed, Salah U; Plakogiannis, Fotios M
2013-01-01
Ethyl cellulose (EC) polymer was characterized for its property before considering the interactions with the plasicizer. Ethocel Std.10 FP Premium from Dow chemical company USA was tested for its solubility, morphology and thermal properties. Seven percentage of EC solution in ethanol was found to be the right viscosity used to prepare the film. The EC polymer and EC film without any plasticizers showed almost identical thermal behavior, but in X-ray diffraction showed different arrangements of crystallites and amorphous region. Dynamic mechanical analysis of film showed that without a plasticizer, EC film was not flexible and had very low elongation with high applied force. The aim of the work was to avoid using the commercially available EC dispersions Surelease® and Aquacoat®; both already have additives on it. Instead, Ethocel EC polymer (powder) was characterized in our laboratory in order to find out the properties of polymer before considering the interactions of the polymer with various plasticizers.
Sun, Xiuhua; Yang, Weichun; Geng, Yanli; Woolley, Adam T
2009-04-07
We have developed a simple and effective method for surface modification of polymer microchips by entrapping hydroxypropyl cellulose (HPC) in a spin-coated thin film on the surface. Poly(methyl methacrylate-8.5-methacrylic acid), a widely available commercial resist formulation, was utilized as a matrix for dissolving HPC and providing adherence to native polymer surfaces. Various amounts of HPC (0.1-2.0%) dissolved in the copolymer and spun on polymer surfaces were evaluated. The modified surfaces were characterized by contact angle measurement, X-ray photoelectron spectroscopy and atomic force microscopy. The developed method was applied on both poly(methyl methacrylate) and cyclic olefin copolymer microchips. A fluorescently labeled myoglobin digest, binary protein mixture, and human serum sample were all separated in these surface-modified polymer microdevices. Our work exhibits an easy and reliable way to achieve favorable biomolecular separation performance in polymer microchips.
Sun, Xiuhua; Yang, Weichun; Geng, Yanli; Woolley, Adam T.
2009-01-01
We have developed a simple and effective method for surface modification of polymer microchips by entrapping hydroxypropyl cellulose (HPC) in a spin-coated thin film on the surface. Poly(methyl methacrylate-8.5-methacrylic acid), a widely available commercial resist formulation, was utilized as a matrix for dissolving HPC and providing adherence to native polymer surfaces. Various amounts of HPC (0.1–2.0%) dissolved in the copolymer and spun on polymer surfaces were evaluated. The modified surfaces were characterized by contact angle measurement, X-ray photoelectron spectroscopy and atomic force microscopy. The developed method was applied on both poly(methyl methacrylate) and cyclic olefin copolymer microchips. A fluorescently labeled myoglobin digest, binary protein mixture, and human serum sample were all separated in these surface-modified polymer microdevices. Our work exhibits an easy and reliable way to achieve favorable biomolecular separation performance in polymer microchips. PMID:19294306
Mortazavi, Seyed Alireza; Jafariazar, Zahra; Ghadjahani, Yasaman; Mahmoodi, Hoda; Mehtarpour, Farzaneh
2014-01-01
The purpose of this study was preparation and evaluation of sustained release matrix type ocular mini-tablets of timolol maleate, as a potential formulation for the treatment of glaucoma. Following the initial studies on timolol maleate powder, it was formulated into ocular mini-tablets. The polymers investigated in this study included cellulose derivatives (HEC, CMC, EC) and Carbopol 971P. Mannitol was used as the solubilizing agent and magnesium stearate as the lubricant. Mini-tablets were prepared by through mixing of the ingredients, followed by direct compression. All the prepared formulations were evaluated in terms of physicochemical tests, including uniformity of weight, thickness, crushing strength, friability and in-vitro drug release. Four groups of formulations were prepared. The presence of different amounts of cellulose derivatives or Carbopol 971P, alone, was studied in group A formulations. In group B formulations, the effect of adding Carbopol 971P alongside different cellulose derivatives was investigated. Group C formulations were made by including mannitol as the solubilizing agent, alongside Carbopol 971P and a cellulose derivative. In group D formulations, mini-tablets were made using Carbopol 971P, alongside two different cellulose derivative. The selected formulation (C1) contained ethyl cellulose, Carbopol 971P, mannitol and magnesium stearate, which showed almost 100% drug release over 5 h. Based on kinetic studies, this formulation was found to best fit the zero-order model of drug release. However, the Higuchi and Hixson -Crowell models also showed a good fit. Hence, overall, formulation C1 was chosen as the best formulation. PMID:24734053
Preparation and characterization of directly compactible layer-by-layer nanocoated cellulose.
Strydom, Schalk J; Otto, Daniel P; Liebenberg, Wilna; Lvov, Yuri M; de Villiers, Melgardt M
2011-02-14
Microcrystalline cellulose is a commonly used direct compression tablet diluent and binder. It is derived from purified α-cellulose in an environmentally unfriendly process that involves mineral acid catalysed hydrolysis. In this study Kraft softwood fibers was nanocoated using a layer-by-layer self-assembling process. Powder flow and compactibility results showed that the application of nano-thin polymer layers on the fibers turned non-flowing, non-compacting cellulose into powders that can be used in the direct compression of tablets. The powder flow properties and tableting indices of compacts compressed from these nanocoated microfibers were similar or better than that of directly compactible microcrystalline cellulose powders. Cellulose microfibers coated with four PSS/PVP bilayers had the best compaction properties while still producing tablets that were able to absorb water and disintegrate and did not retard the dissolution of a model drug acetaminophen. The advantages of nanocoating rather than traditional pharmaceutical coating are that it add less than 1% to the weight of the fibers and allows control of the molecular properties of the surface and the thickness of the coat to within a few nanometers. This process is potentially friendlier to the environment because of the type and quantity of materials used. Also, it does not involve acid-catalyzed hydrolysis and neutralization of depolymerized cellulose. Copyright © 2010 Elsevier B.V. All rights reserved.
Recent advances in cellulose and chitosan based membranes for water purification: A concise review.
Thakur, Vijay Kumar; Voicu, Stefan Ioan
2016-08-01
Recently membrane technology has emerged as a new promising and pervasive technology due to its innate advantages over traditional technologies such as adsorption, distillation and extraction. In this article, some of the recent advances in developing polymeric composite membrane materials for water purification from natural polysaccharide based polymers namely cellulose derivatives and chitosan are concisely reviewed. The impact of human social, demographic and industrial evolution along with expansion through environment has significantly affected the quality of water by pollution with large quantities of pesticides, minerals, drugs or other residues. At the forefront of decontamination and purification techniques, we found the membrane materials from polymers as a potential alternative. In an attempt to reduce the number of technical polymers widely used in the preparation of membranes, many researchers have reported new solutions for desalination or retention of organic yeasts, based on bio renewable polymers like cellulose derivatives and chitosan. These realizations are presented and discussed in terms of the most important parameters of membrane separation especially water flux and retention in this article. Published by Elsevier Ltd.
Omadjela, Okako; Narahari, Adishesh; Strumillo, Joanna; Mélida, Hugo; Mazur, Olga; Bulone, Vincent; Zimmer, Jochen
2013-10-29
Cellulose is a linear extracellular polysaccharide. It is synthesized by membrane-embedded glycosyltransferases that processively polymerize UDP-activated glucose. Polymer synthesis is coupled to membrane translocation through a channel formed by the cellulose synthase. Although eukaryotic cellulose synthases function in macromolecular complexes containing several different enzyme isoforms, prokaryotic synthases associate with additional subunits to bridge the periplasm and the outer membrane. In bacteria, cellulose synthesis and translocation is catalyzed by the inner membrane-associated bacterial cellulose synthase (Bcs)A and BcsB subunits. Similar to alginate and poly-β-1,6 N-acetylglucosamine, bacterial cellulose is implicated in the formation of sessile bacterial communities, termed biofilms, and its synthesis is likewise stimulated by cyclic-di-GMP. Biochemical studies of exopolysaccharide synthesis are hampered by difficulties in purifying and reconstituting functional enzymes. We demonstrate robust in vitro cellulose synthesis reconstituted from purified BcsA and BcsB proteins from Rhodobacter sphaeroides. Although BcsA is the catalytically active subunit, the membrane-anchored BcsB subunit is essential for catalysis. The purified BcsA-B complex produces cellulose chains of a degree of polymerization in the range 200-300. Catalytic activity critically depends on the presence of the allosteric activator cyclic-di-GMP, but is independent of lipid-linked reactants. Our data reveal feedback inhibition of cellulose synthase by UDP but not by the accumulating cellulose polymer and highlight the strict substrate specificity of cellulose synthase for UDP-glucose. A truncation analysis of BcsB localizes the region required for activity of BcsA within its C-terminal membrane-associated domain. The reconstituted reaction provides a foundation for the synthesis of biofilm exopolysaccharides, as well as its activation by cyclic-di-GMP.
Omadjela, Okako; Narahari, Adishesh; Strumillo, Joanna; Mélida, Hugo; Mazur, Olga; Bulone, Vincent; Zimmer, Jochen
2013-01-01
Cellulose is a linear extracellular polysaccharide. It is synthesized by membrane-embedded glycosyltransferases that processively polymerize UDP-activated glucose. Polymer synthesis is coupled to membrane translocation through a channel formed by the cellulose synthase. Although eukaryotic cellulose synthases function in macromolecular complexes containing several different enzyme isoforms, prokaryotic synthases associate with additional subunits to bridge the periplasm and the outer membrane. In bacteria, cellulose synthesis and translocation is catalyzed by the inner membrane-associated bacterial cellulose synthase (Bcs)A and BcsB subunits. Similar to alginate and poly-β-1,6 N-acetylglucosamine, bacterial cellulose is implicated in the formation of sessile bacterial communities, termed biofilms, and its synthesis is likewise stimulated by cyclic-di-GMP. Biochemical studies of exopolysaccharide synthesis are hampered by difficulties in purifying and reconstituting functional enzymes. We demonstrate robust in vitro cellulose synthesis reconstituted from purified BcsA and BcsB proteins from Rhodobacter sphaeroides. Although BcsA is the catalytically active subunit, the membrane-anchored BcsB subunit is essential for catalysis. The purified BcsA-B complex produces cellulose chains of a degree of polymerization in the range 200–300. Catalytic activity critically depends on the presence of the allosteric activator cyclic-di-GMP, but is independent of lipid-linked reactants. Our data reveal feedback inhibition of cellulose synthase by UDP but not by the accumulating cellulose polymer and highlight the strict substrate specificity of cellulose synthase for UDP-glucose. A truncation analysis of BcsB localizes the region required for activity of BcsA within its C-terminal membrane-associated domain. The reconstituted reaction provides a foundation for the synthesis of biofilm exopolysaccharides, as well as its activation by cyclic-di-GMP. PMID:24127606
New urea-absorbing polymers for artificial kidney machines
NASA Technical Reports Server (NTRS)
Mueller, W. A.; Hsu, G. C.; Marsh, H. E., Jr.
1975-01-01
Etherified polymer is made from modified cellulose derivative which is reacted with periodate. It will absorb 2 grams of urea per 100 grams of polymer. Indications are that polymers could be used to help remove uremic wastes in artificial kidneys, or they could be administered orally as therapy for uremia.
Cellulose nanocrystals the next big nano-thing?
Michael T. Postek; Andras Vladar; John Dagata; Natalia Farkas; Bin Ming; Ronald Sabo; Theodore H. Wegner; James Beecher
2008-01-01
Biomass surrounds us from the smallest alga to the largest redwood tree. Even the largest trees owe their strength to a newly-appreciated class of nanomaterials known as cellulose nanocrystals (CNC). Cellulose, the worldâs most abundant natural, renewable, biodegradable polymer, occurs as whisker like microfibrils that are biosynthesized and deposited in plant material...
Mineral-Ground Micro-Fibrillated Cellulose Reinforcement for Polymer Compounds
DOE Office of Scientific and Technical Information (OSTI.GOV)
Phipps, Jon; Ireland, Sean; Skuse, David
2017-01-01
ORNL worked with Imerys to demonstrate reinforcement of additive manufacturing feedstock materials using mineral-ground microfibrillated cellulose (MFC). Properly prepared/dried mineral-ground cellulose microfibrils significantly improved mechanical properties of both ABS and PLA resins. While tensile strength increases up to ~40% were observed, elastic modulus of the both resins doubled with the addition of 30% MFC.
Fiber and nonstarch polysaccharide content and variation in common crops used in broiler diets.
Knudsen, Knud Erik Bach
2014-09-01
The current paper reviews content and variation in fiber and nonstarch polysaccharides (NSP) of common crops used in broiler diets. The cereal grain is a complex structure, and its cell walls (CW) differ in their composition and hence properties. Arabinoxylan (AX), mixed linkage (1→3; 1→4)-β-glucan (β-glucan), cellulose, and the noncarbohydrate component lignin are the predominant polymers in cereals. They occur in different proportions depending on the species and tissue type. Rye, triticale, wheat, corn, and sorghum are all rich in AX, whereas barley and oats contain a high level of β-glucan. The AX from rye, wheat, and triticale and β-glucan from barley and oats are to a large extent soluble, whereas the solubility of AX found in corn and sorghum is lower than the other cereals. The ratio of arabinose to xylose gives a crude indication of the AX structure, which varies between the endosperm, the aleurone and the outer grain layers as well as between the same tissues from different grains. Varietal differences in AX structure of the endosperm are also identified. From the analysis of the released oligomers after hydrolysis with a specific (1→3,1→4)-β-d-glucan hydrolase, it is found that the ratio of trisaccharides (degree of polymerization 3) and tetrasaccharides (degree of polymerization 4) varies depending on the source, being higher in barley than in oats but lower than in wheat. The molecular weight of β-glucan is higher than that of AX, and both polymers contribute to the viscosity of the extract. However, because AX molecules are more resistant to degradation than β-glucan, the use of AX rich grains in broiler diets is usually more problematic than those containing high concentrations of β-glucan. The cereal coproducts (brans and hulls) are concentrated sources of cellulose, lignin, and insoluble AX, but β-glucan can also be present mainly in rye and wheat brans. The CW composition of seeds and grains of protein crops and feedstuffs are different from that of cereals. The main CW polymers are pectic substances (homogalacturonan, rhamnogalacturonan type I and II, xylogalacturonan, and arabinogalactans type I and II), xyloglucans, and cellulose, but there are significant differences in the composition of the parenchymatous (cotyledon) tissues and that of the hulls. In the hulls, cellulose is the predominant polysaccharide, followed by acidic xylans and pectic substances. The implications of the heterogeneous CW for the action of exogenous enzymes are discussed. © 2014 Poultry Science Association Inc.
Barmpalexis, Panagiotis; Grypioti, Agni
2018-06-01
This study describes the development of a new esomeprazole (ESO) delayed release gastro-resistant formulation with improved storage stability. A three-step (drug-, sub(seal)- and enteric-) coating process was employed with the aid of a fluid bed coater. Several formulation factors (namely, size and quantity of starting non-pareil sugar spheres, binder quantity during drug-layering, sub(seal)-coating polymer type, and quantity and enteric coating quantity) were evaluated and the whole process was modeled with the aid of feed-forward back-propagation artificial neural networks (ANNs). Results showed that the selection of small-sized starting spheres (45/60 mesh size) leads to pellet agglomeration, while as sub(seal)-coating weight gain increases a reduction in ESO dissolution rate is observed. The enteric-coating applied (Eudragit L30D-55) showed good gastro-resistant performance in both 0.1 N HCl and pH 4.5 media, while immediate release profiles with more than 85% of ESO being released in less than 30 min were obtained. The effect of cellulose-based sub(seal)-coating polymers, (namely, hydroxypropyl cellulose and hydroxypropylmethyl cellulose) on formulation's storage stability at 40 ± 2 °C/75 ± 5%RH indicated that only hydroxypropylmethyl cellulose was able to stabilize ESO delayed-release formulations in terms of assay, dissolution, impurities, and gastro-resistance performance. Finally, scanning electron microscopy (SEM) analysis revealed smooth and homogeneous external surface/coating layers in all three levels (drug-, sub(seal)-, and enteric- coating), while x-ray diffraction showed no polymorphic transformations.
Quintanar-Guerrero, D; Allémann, E; Fessi, H; Doelker, E
1999-10-25
Pseudolatexes were obtained by a new process based on an emulsification-diffusion technique involving partially water-miscible solvents. The preparation method consisted of emulsifying an organic solution of polymer (saturated with water) in an aqueous solution of a stabilizing agent (saturated with solvent) using conventional stirrers, followed by direct solvent distillation. The technique relies on the rapid displacement of the solvent from the internal into the external phase which thereby provokes polymer aggregation. Nanoparticle formation is believed to occur because rapid solvent diffusion produces regions of local supersaturation near the interface, and nanoparticles are formed due to the ensuing interfacial phase transformations and polymer aggregation that occur in these interfacial domains. Using this method, it was possible to prepare pseudolatexes of biodegradable and non-biodegradable polymers such as poly(D,L-lactic acid) and poly(epsilon-caprolactone), Eudragit E, cellulose acetate phthalate, cellulose acetate trimellitate using ethyl acetate or 2-butanone as partially water-miscible solvents and poly(vinyl alcohol) or poloxamer 407 as stabilizing agent. A transition from nano- to microparticles was observed at high polymer concentrations. At concentrations above 30% w/v of Eudragit E in ethyl acetate or cellulose acetate phthalate in 2-butanone only microparticles were obtained. This behaviour was attributed to decreased transport of polymer molecules into the aqueous phase.
Chemical and physicochemical pretreatment of lignocellulosic biomass: a review.
Brodeur, Gary; Yau, Elizabeth; Badal, Kimberly; Collier, John; Ramachandran, K B; Ramakrishnan, Subramanian
2011-01-01
Overcoming the recalcitrance (resistance of plant cell walls to deconstruction) of lignocellulosic biomass is a key step in the production of fuels and chemicals. The recalcitrance is due to the highly crystalline structure of cellulose which is embedded in a matrix of polymers-lignin and hemicellulose. The main goal of pretreatment is to overcome this recalcitrance, to separate the cellulose from the matrix polymers, and to make it more accessible for enzymatic hydrolysis. Reports have shown that pretreatment can improve sugar yields to higher than 90% theoretical yield for biomass such as wood, grasses, and corn. This paper reviews different leading pretreatment technologies along with their latest developments and highlights their advantages and disadvantages with respect to subsequent hydrolysis and fermentation. The effects of different technologies on the components of biomass (cellulose, hemicellulose, and lignin) are also reviewed with a focus on how the treatment greatly enhances enzymatic cellulose digestibility.
Chemical and Physicochemical Pretreatment of Lignocellulosic Biomass: A Review
Brodeur, Gary; Yau, Elizabeth; Badal, Kimberly; Collier, John; Ramachandran, K. B.; Ramakrishnan, Subramanian
2011-01-01
Overcoming the recalcitrance (resistance of plant cell walls to deconstruction) of lignocellulosic biomass is a key step in the production of fuels and chemicals. The recalcitrance is due to the highly crystalline structure of cellulose which is embedded in a matrix of polymers-lignin and hemicellulose. The main goal of pretreatment is to overcome this recalcitrance, to separate the cellulose from the matrix polymers, and to make it more accessible for enzymatic hydrolysis. Reports have shown that pretreatment can improve sugar yields to higher than 90% theoretical yield for biomass such as wood, grasses, and corn. This paper reviews different leading pretreatment technologies along with their latest developments and highlights their advantages and disadvantages with respect to subsequent hydrolysis and fermentation. The effects of different technologies on the components of biomass (cellulose, hemicellulose, and lignin) are also reviewed with a focus on how the treatment greatly enhances enzymatic cellulose digestibility. PMID:21687609
Masmoudi, Fatma; Bessadok, Atef; Dammak, Mohamed; Jaziri, Mohamed; Ammar, Emna
2016-10-01
The plastic materials used for packaging are increasing leading to a considerable amount of undegradable solid wastes. This work deals with the reduction of conventional plastics waste and the natural resources preservation by using cellulosic polymers from renewable resources (alfa and luffa). Plasticized starch films syntheses were achieved at a laboratory scale. These natural films showed some very attractive mechanical properties at relatively low plasticizers levels (12 to 17 % by weight). Furthermore, mixtures including polylactic acid polymer (PLA) and cellulose fibers extracted from alfa and luffa were investigated by melt extrusion technique. When used at a rate of 10 %, these fibers improved the mixture mechanical properties. Both developed materials were biodegradable, but the plasticized starch exhibited a faster biodegradation kinetic compared to the PLA/cellulose fibers. These new materials would contribute to a sustainable development and a waste reduction.
NASA Astrophysics Data System (ADS)
Aprilia, N. A. S.; Mulyati, S.; Alam, P. N.; Karmila; Ambarita, A. C.
2018-04-01
Nanocellulose from sugarcane bagasse for reinforcement in polymer composites has isolated from formic acid (FA) with different concentration. This research was conducted with three level concentration of FA ei. 15, 30 and 50%. The nanocellulose were successfully prepared with variations of total yields of 66.66, 67.33 and 69.33% respectively with increase of FA concentrations at 6 hours of hidrolysis time. The obtained nanocellulose were characterized by fourier transform infrared (FT-IR) spectroscopy confirmed the introduction of carboxyl goups on the surface of cellulose. The X-ray diffraction (XRD) spectra proved the existence of cellulose, with a highly crystalline of 62.466, 71.033, and 76.296% with increase of FA concentrations. The size of crystallinity of nanocellulose were decreased with increased of FA concentration. The result investigated that size of crystallinity of nano cellulose reduced from 4.37, 4.15 and 3.94 nm.
Cellulose-based magnetoelectric composites.
Zong, Yan; Zheng, Tian; Martins, Pedro; Lanceros-Mendez, S; Yue, Zhilian; Higgins, Michael J
2017-06-28
Since the first magnetoelectric polymer composites were fabricated more than a decade ago, there has been a reluctance to use piezoelectric polymers other than poly(vinylidene fluoride) and its copolymers due to their well-defined piezoelectric mechanism and high piezoelectric coefficients that lead to superior magnetoelectric coefficients of >1 V cm -1 Oe -1 . This is the current situation despite the potential for other piezoelectric polymers, such as natural biopolymers, to bring unique, added-value properties and functions to magnetoelectric composite devices. Here we demonstrate a cellulose-based magnetoelectric laminate composite that produces considerable magnetoelectric coefficients of ≈1.5 V cm -1 Oe -1 , comprising a Fano resonance that is ubiquitous in the field of physics, such as photonics, though never experimentally observed in magnetoelectric composites. The work successfully demonstrates the concept of exploring new advances in using biopolymers in magnetoelectric composites, particularly cellulose, which is increasingly employed as a renewable, low-cost, easily processable and degradable material.Magnetoelectric materials by converting a magnetic input to a voltage output holds promise in contactless electrodes that find applications from energy harvesting to sensing. Zong et al. report a promising laminate composite that combines a piezoelectric biopolymer, cellulose, and a magnetic material.
Porous cellulosic adsorbent for the removal of Cd (II), Pb(II) and Cu(II) ions from aqueous media
NASA Astrophysics Data System (ADS)
Barsbay, Murat; Kavaklı, Pınar Akkaş; Tilki, Serhad; Kavaklı, Cengiz; Güven, Olgun
2018-01-01
The main objective of this work is to prepare a renewable cellulosic adsorbent by γ-initiated grafting of poly(glycidyl methacrylate) (PGMA) from cellulose substrate and subsequent modification of PGMA with chelating species, iminodiacetic acid (IDA), for Cd (II), Pb(II) and Cu(II) removal from aqueous media. Modification of PGMA grafted cellulose with IDA in aqueous solution under mild conditions has proceeded efficiently to yield a natural-based and effective porous adsorbent with well-defined properties as provided by the controlled polymerization technique, namely RAFT, applied during the radiation-induced graft copolymerization step and with sufficient degree of IDA immobilization as confirmed by XPS, FTIR, contact angle measurements and elemental analysis. In order to examine the Cd (II), Pb(II) and Cu(II) removing performance of the resulting adsorbent, batch experiments were carried out by ICP-MS. The adsorption capacities were determined as 53.4 mg Cd(II)/g polymer, 52.0 mg Pb(II)/g polymer and 69.6 mg Cu(II)/g polymer at initial feed concentration of 250 ppm, showing the promising potential of the natural-based adsorbent to steadily and efficiently chemisorb toxic metal ions.
Surface structure, crystallographic and ice-nucleating properties of cellulose
NASA Astrophysics Data System (ADS)
Hiranuma, Naruki; Möhler, Ottmar; Kiselev, Alexei; Saathoff, Harald; Weidler, Peter; Shutthanandan, Shuttha; Kulkarni, Gourihar; Jantsch, Evelyn; Koop, Thomas
2015-04-01
Increasing evidence of the high diversity and efficient freezing ability of biological ice-nucleating particles is driving a reevaluation of their impact upon climate. Despite their potential importance, little is known about their atmospheric abundance and ice nucleation efficiency, especially non-proteinaceous ones, in comparison to non-biological materials (e.g., mineral dust). Recently, microcrystalline cellulose (MCC; non-proteinaceous plant structural polymer) has been identified as a potential biological ice-nucleating particle. However, it is still uncertain if the ice-nucleating activity is specific to the MCC structure or generally relevant to all cellulose materials, such that the results of MCC can be representatively scaled up to the total cellulose content in the atmosphere to address its role in clouds and the climate system. Here we use the helium ion microscopy (HIM) imaging and the X-ray diffraction (XRD) technique to characterize the nanoscale surface structure and crystalline properties of the two different types of cellulose (MCC and fibrous cellulose extracted from natural wood pulp) as model proxies for atmospheric cellulose particles and to assess their potential accessibility for water molecules. To complement these structural characterizations, we also present the results of immersion freezing experiments using the cold stage-based droplet freezing BINARY (Bielefeld Ice Nucleation ARaY) technique. The HIM results suggest that both cellulose types have a complex porous morphology with capillary spaces between the nanoscale fibrils over the microfiber surface. These surface structures may make cellulose accessible to water. The XRD results suggest that the structural properties of both cellulose materials are in agreement (i.e., P21 space group; a=7.96 Å, b=8.35 Å, c=10.28 Å) and comparable to the crystallographic properties of general monoclinic cellulose (i.e., Cellulose Iβ). The results obtained from the BINARY measurements suggest that there is no significant difference of the immersion ice nucleation activity of MCC and fibrous cellulose in supercooled water. Overall, our findings support the view that MCC may be a good proxy for inferring water uptake, wettability and ice nucleating properties of various cellulose materials. In addition, we discuss the ice-nucleating efficiencies of both cellulose samples and plant debris from the AIDA (Aerosol Interaction and Dynamics in the Atmosphere) chamber experiments in comparison to the BINARY results. The influence of the acid processing of cellulose on its ice nucleation propensity may also be discussed to further demonstrate their atmospheric relevancy. Acknowledgement: We acknowledge support by German Research Society (DFG) and Ice Nuclei research UnIT (FOR 1525 INUIT).
Rapid synthesis of graft copolymers from natural cellulose fibers.
Thakur, Vijay Kumar; Thakur, Manju Kumari; Gupta, Raju Kumar
2013-10-15
Cellulose is the most abundant natural polysaccharide polymer, which is used as such or its derivatives in a number of advanced applications, such as in paper, packaging, biosorption, and biomedical. In present communication, in an effort to develop a proficient way to rapidly synthesize poly(methyl acrylate)-graft-cellulose (PMA-g-cellulose) copolymers, rapid graft copolymerization synthesis was carried out under microwave conditions using ferrous ammonium sulfate-potassium per sulfate (FAS-KPS) as redox initiator. Different reaction parameters such as microwave radiation power, ratio of monomer, solvent and initiator concentrations were optimized to get the highest percentage of grafting. Grafting percentage was found to increase with increase in microwave power up to 70%, and maximum 36.73% grafting was obtained after optimization of all parameters. Fourier transforms infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA/DTA/DTG) analysis were used to confirm the graft copolymerization of poly(methyl acrylate) (PMA) onto the mercerized cellulose. The grafted cellulosic polymers were subsequently subjected to the evaluation of different physico-chemical properties in order to access their application in everyday life, in a direction toward green environment. The grafted copolymers demonstrated increased chemical resistance, and higher thermal stability. Published by Elsevier Ltd.
Lee, Koon-Yang; Tammelin, Tekla; Schulfter, Kerstin; Kiiskinen, Harri; Samela, Juha; Bismarck, Alexander
2012-08-01
This work investigates the surface and bulk properties of nanofibrillated cellulose (NFC) and bacterial cellulose (BC), as well as their reinforcing ability in polymer nanocomposites. BC possesses higher critical surface tension of 57 mN m(-1) compared to NFC (41 mN m(-1)). The thermal degradation temperature in both nitrogen and air atmosphere of BC was also found to be higher than that of NFC. These results are in good agreement with the higher crystallinity of BC as determined by XRD, measured to be 71% for BC as compared to NFC of 41%. Nanocellulose papers were prepared from BC and NFC. Both papers possessed similar tensile moduli and strengths of 12 GPa and 110 MPa, respectively. Nanocomposites were manufactured by impregnating the nanocellulose paper with an epoxy resin using vacuum assisted resin infusion. The cellulose reinforced epoxy nanocomposites had a stiffness and strength of approximately ∼8 GPa and ∼100 MPa at an equivalent fiber volume fraction of 60 vol.-%. In terms of the reinforcing ability of NFC and BC in a polymer matrix, no significant difference between NFC and BC was observed.
Lertngim, Anantaya; Phiriyawirut, Manisara; Yuwawech, Kitti; Sangkhun, Weradesh; Kumnorkaew, Pisist; Muangnapoh, Tanyakorn
2017-01-01
This research concerns the development of Surlyn film reinforced with micro-/nanofibrillated celluloses (MFC) for use as an encapsulant in organic photovoltaic (OPV) cells. The aim of this work was to investigate the effects of fibre types and the mixing methods on the structure–properties of the composite films. Three types of cellulose micro/nanofibrils were prepared: the as-received MFC, the dispersed MFC and the esterified MFC. The fibres were mixed with Surlyn via an extrusion process, using two different mixing methods. It was found that the extent of fibre disintegration and tensile modulus of the composite films prepared by the master-batching process was superior to that of the composite system prepared by the direct mixing method. Using the esterified MFC as a reinforcement, compatibility between polymer and the fibre increased, accompanied with the improvement of the percentage elongation of the Surlyn composite film. The percentage of light transmittance of the Surlyn/MFC films was above 88, regardless of the fibre types and fibre concentrations. The water vapour transmission rate of the Surlyn/esterified MFC film was 65% lower than that of the neat Surlyn film. This contributed to the longer lifetime of the OPV encapsulated with the Surlyn/esterified MFC film. PMID:29134083
NASA Astrophysics Data System (ADS)
Lertngim, Anantaya; Phiriyawirut, Manisara; Wootthikanokkhan, Jatuphorn; Yuwawech, Kitti; Sangkhun, Weradesh; Kumnorkaew, Pisist; Muangnapoh, Tanyakorn
2017-10-01
This research concerns the development of Surlyn film reinforced with micro-/nanofibrillated celluloses (MFC) for use as an encapsulant in organic photovoltaic (OPV) cells. The aim of this work was to investigate the effects of fibre types and the mixing methods on the structure-properties of the composite films. Three types of cellulose micro/nanofibrils were prepared: the as-received MFC, the dispersed MFC and the esterified MFC. The fibres were mixed with Surlyn via an extrusion process, using two different mixing methods. It was found that the extent of fibre disintegration and tensile modulus of the composite films prepared by the master-batching process was superior to that of the composite system prepared by the direct mixing method. Using the esterified MFC as a reinforcement, compatibility between polymer and the fibre increased, accompanied with the improvement of the percentage elongation of the Surlyn composite film. The percentage of light transmittance of the Surlyn/MFC films was above 88, regardless of the fibre types and fibre concentrations. The water vapour transmission rate of the Surlyn/esterified MFC film was 65% lower than that of the neat Surlyn film. This contributed to the longer lifetime of the OPV encapsulated with the Surlyn/esterified MFC film.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Smith-Moritz, Andreia M.; Hao, Zhao; Fernández-Nino, Susana G.
The CELLULOSE SYNTHASE-LIKE F6 (CslF6) gene was previously shown to mediate the biosynthesis of mixed-linkage glucan (MLG), a cell wall polysaccharide that is hypothesized to be tightly associated with cellulose and also have a role in cell expansion in the primary cell wall of young seedlings in grass species. We have recently shown that loss-of-function cslf6 rice mutants do not accumulate MLG in most vegetative tissues. Despite the absence of a structurally important polymer, MLG, these mutants are unexpectedly viable and only show a moderate growth compromise compared to wild type. Therefore these mutants are ideal biological systems to testmore » the current grass cell wall model. In order to gain a better understanding of the role of MLG in the primary wall, we performed in-depth compositional and structural analyses of the cell walls of 3 day-old rice seedlings using various biochemical and novel microspectroscopic approaches. We found that cellulose content as well as matrix polysaccharide composition was not significantly altered in the MLG deficient mutant. However, we observed a significant change in cellulose microfibril bundle organization in mesophyll cell walls of the cslf6 mutant. Using synchrotron source Fourier Transform Mid-Infrared (FTM-IR) Spectromicroscopy for high-resolution imaging, we determined that the bonds associated with cellulose and arabinoxylan, another major component of the primary cell walls of grasses, were in a lower energy configuration compared to wild type, suggesting a slightly weaker primary wall in MLG deficient mesophyll cells. Finally, taken together, these results suggest that MLG may influence cellulose deposition in mesophyll cell walls without significantly affecting anisotropic growth thus challenging MLG importance in cell wall expansion.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Xi, Xiaoning; Tittmann, Bernhard; Kim, Seong H.
An atomic force microscopy based nanoindentation method was employed to study how the structure of cellulose microfibril packing and matrix polymers affect elastic modulus of fully hydrated primary plant cell walls. The isolated, single-layered abaxial epidermis cell wall of an onion bulb was used as a test system since the cellulose microfibril packing in this cell wall is known to vary systematically from inside to outside scales and the most abundant matrix polymer, pectin, can easily be altered through simple chemical treatments such as ethylenediaminetetraacetic acid and calcium ions. Experimental results showed that the pectin network variation has significant impactsmore » on the cell wall modulus, and not the cellulose microfibril packing.« less
Immobilization of Lactase onto Various Polymer Nanofibers for Enzyme Stabilization and Recycling.
Jin, Lihua; Li, Ye; Ren, Xiang-Hao; Lee, Jung-Heon
2015-08-01
Five different polymer nanofibers, namely, polyaniline nanofiber (PANI), magnetically separable polyaniline nanofiber (PAMP), magnetically separable DEAE cellulose fiber (DEAE), magnetically separable CM cellulose fiber (CM), and polystyrene nanofiber (PSNF), have been used for the immobilization of lactase (E.C. 3.2.1.23). Except for CM and PSNF, three polymers showed great properties. The catalytic activities (kcat) of the free, PANI, PAMP, and magnetic DEAE-cellulose were determined to be 4.0, 2.05, 0.59, and 0.042 mM/min·mg protein, respectively. The lactase immobilized on DEAE, PANI, and PAMP showed improved stability and recyclability. PANI- and PAMP-lactase showed only a 0-3% decrease in activity after 3 months of vigorous shaking conditions (200 rpm) and at room temperature (25°C). PANI-, PAMP-, and DEAE-lactase showed a high percentage of conversion (100%, 47%, and 12%) after a 1 h lactose hydrolysis reaction. The residual activities of PANI-, PAMP-, and DEAE-lactase after 10 times of recycling were 98%, 96%, and 97%, respectively.
NASA Astrophysics Data System (ADS)
Rapp, F.; Schneider, A.; Elsner, P.
2014-05-01
Biopolymers are becoming increasingly important to both industry and consumers. With regard to waste management, CO2 balance and the conservation of petrochemical resources, increasing efforts are being made to replace standard plastics with bio-based polymers. Nowadays biopolymers can be built for example of cellulose, lactic acid, starch, lignin or bio mass. The paper will present material properties of selected cellulose based polymers (cellulose propionate [CP], cellulose acetate butyrate [CAB]) and corresponding processing conditions for particle foams as well as characterization of produced parts. Special focus is given to the raw material properties by analyzing thermal behavior (differential scanning calorimetry), melt strength (Rheotens test) and molecular weight distribution (gel-permeation chromatography). These results will be correlated with the foaming behavior in a continuous extrusion process with physical blowing agents and underwater pelletizer. Process set-up regarding particle foam technology, including extrusion foaming and pre-foaming, will be shown. The characteristics of the resulting foam beads will be analyzed regarding part density, cell morphology and geometry. The molded parts will be tested on thermal conductivity as well as compression behavior (E-modulus, compression strength).
HPMC reinforced with different cellulose nanoparticles
USDA-ARS?s Scientific Manuscript database
Synthetic polymers, made almost entirely from chemicals derived from crude oil, are widely used as primary packaging in the food industry causing environmental issues. Hydroxypropyl Methyl Cellulose (HPMC) can be used as bio-based packaging material. In this study, the application of nanotechnology ...
Cellulose based polymeric systems in drug delivery
USDA-ARS?s Scientific Manuscript database
The pharmaceutical industry requires the development of biodegradable, biocompatible, non toxic, site specific drug delivery polymers, which can be easily coupled with drugs to be delivered orally, topically, locally, or parenterally. The use of the most abundant biopolymer, cellulose along with its...
Novel route of synthesis for cellulose fiber-based hybrid polyurethane
NASA Astrophysics Data System (ADS)
Ikhwan, F. H.; Ilmiati, S.; Kurnia Adi, H.; Arumsari, R.; Chalid, M.
2017-07-01
Polyurethanes, obtained by the reaction of a diisocyanate compound with bifunctional or multifunctional reagent such as diols or polyols, have been studied intensively and well developed. The wide range modifier such as chemical structures and molecular weight to build polyurethanes led to designs of materials that may easily meet the functional product demand and to the extraordinary spreading of these materials in market. Properties of the obtained polymer are related to the chemical structure of polyurethane backbone. A number polyurethanes prepared from biomass-based monomers have been reported. Cellulose fiber, as a biomass material is containing abundant hydroxyl, promising material as chain extender for building hybrid polyurethanes. In previous researches, cellulose fiber was used as filler in synthesis of polyurethane composites. This paper reported a novel route of hybrid polyurethane synthesis, which a cellulose fiber was used as chain extender. The experiment performed by reacting 4,4’-Methylenebis (cyclohexyl isocyanate) (HMDI) and polyethylene glycol with variation of molecular weight to obtained pre-polyurethane, continued by adding micro fiber cellulose (MFC) with variation of type and composition in the mixture. The experiment was evaluated by NMR, FTIR, SEM and STA measurement. NMR and FTIR confirmed the reaction of the hybrid polyurethane. STA showed hybrid polyurethane has good thermal stability. SEM showed good distribution and dispersion of sorghum-based MFC.
In Situ Stabilization of Persistent Organic Contaminants in Marine Sediments
2004-04-01
dyes (25, 26), amino acids (27), and polymer additives (28, 29). In this study we extend the capabilities of µL2MS to detect PCBs. Using 212 nm...organic carbon followed by treatment with acid to remove inorganic carbon and analysis of the remaining carbon. The soot carbon material isolated by...aliphatic natural organic matter types (algae, cellulose, collagen, cuticle, lignin, kerogen, and humic acid ) and concluded that aliphatic organic matter
Pircher, Nicole; Fischhuber, David; Carbajal, Leticia; Strauß, Christine; Nedelec, Jean-Marie; Kasper, Cornelia; Rosenau, Thomas; Liebner, Falk
2015-09-01
1Biocompatible cellulose-based aerogels composed of nanoporous struts, which embed interconnected voids of controlled micron-size, have been prepared employing temporary templates of fused porogens, reinforcement by interpenetrating PMMA networks and supercritical carbon dioxide drying. Different combinations of cellulose solvent (Ca(SCN) 2 /H 2 O/LiCl or [EMIm][OAc]/DMSO) and anti-solvent (EtOH), porogen type (paraffin wax or PMMA spheres) and porogen size (various fractions in the range of 100-500 μm) as well as intensity of PMMA reinforcement have been investigated to tailor the materials for cell scaffolding applications. All aerogels exhibited an open and dual porosity (micronporosity >100 μm and nanoporosity extending to the low micrometer range). Mechanical properties of the dual-porous aerogels under compressive stress were considerably improved by introduction of interpenetrating PMMA networks. The effect of the reinforcing polymer on attachment, spreading, and proliferation of NIH 3T3 fibroblast cells, cultivated on selected dual-porous aerogels to pre-evaluate their biocompatibility was similarly positive.
NASA Astrophysics Data System (ADS)
Pirahmadi, Pegah; Kokabi, Mehrdad
2018-01-01
Most research on shape memory polymers has been confined to neat polymers in their dry state, while, some hydrogel networks are known for their shape memory properties. Hydrogels have low glass transition temperatures which are below 100°C depend on the content of water. But they are usually weak and brittle, and not suitable for structural applications due to their low mechanical strengths because of these materials have large amount of water (>50%), so they could not remember original shape perfectly. Bacterial cellulose nanofibers with perfect properties such as high water holding capacity, high crystallinity, high tensile strength and good biocompatibility can dismiss all the drawbacks. In the present study, polyvinyl alcohol/bacterial cellulose nanocomposite hydrogel prepared by repetitive freezing-thawing method. The bacterial cellulose was used as reinforcement to improve the mechanical properties and stimuli response. Differential scanning calorimetry was employed to obtain the glass transition temperature. Nanocomposite morphology was characterized by field-emission scanning electron microscopy and mechanical properties were investigated by standard tensile test. Finally, the effect of bacterial cellulose nanofiber on shape memory behavior of polyvinyl alcohol/bacterial cellulose nanocomposite hydrogel was investigated. It is found that switching temperature of this system is the glass transition temperature of the nano domains formed within the system. The results also show increase of shape recovery, and shape recovery speed due to presence of bacterial cellulose.
Pillai, Karthik; Navarro Arzate, Fernando; Zhang, Wei; Renneckar, Scott
2014-01-01
Woody materials are comprised of plant cell walls that contain a layered secondary cell wall composed of structural polymers of polysaccharides and lignin. Layer-by-layer (LbL) assembly process which relies on the assembly of oppositely charged molecules from aqueous solutions was used to build a freestanding composite film of isolated wood polymers of lignin and oxidized nanofibril cellulose (NFC). To facilitate the assembly of these negatively charged polymers, a positively charged polyelectrolyte, poly(diallyldimethylammomium chloride) (PDDA), was used as a linking layer to create this simplified model cell wall. The layered adsorption process was studied quantitatively using quartz crystal microbalance with dissipation monitoring (QCM-D) and ellipsometry. The results showed that layer mass/thickness per adsorbed layer increased as a function of total number of layers. The surface coverage of the adsorbed layers was studied with atomic force microscopy (AFM). Complete coverage of the surface with lignin in all the deposition cycles was found for the system, however, surface coverage by NFC increased with the number of layers. The adsorption process was carried out for 250 cycles (500 bilayers) on a cellulose acetate (CA) substrate. Transparent free-standing LBL assembled nanocomposite films were obtained when the CA substrate was later dissolved in acetone. Scanning electron microscopy (SEM) of the fractured cross-sections showed a lamellar structure, and the thickness per adsorption cycle (PDDA-Lignin-PDDA-NC) was estimated to be 17 nm for two different lignin types used in the study. The data indicates a film with highly controlled architecture where nanocellulose and lignin are spatially deposited on the nanoscale (a polymer-polymer nanocomposites), similar to what is observed in the native cell wall. PMID:24961302
NASA Astrophysics Data System (ADS)
Benosmane, Nadjib; Boutemeur, Baya; Hamdi, Safouane M.; Hamdi, Maamar
2018-03-01
Nowadays, there are increasingly stringent regulations requiring more and more treatment of industrial effluents to generate product waters which could be easily reused or disposed of to the environment without any harmful effects. In the present work, the removal of phenol from aqueous solution across polymer inclusion membrane (PIM), based on mixture of cellulose triacetate and cellulose acetate as support (75/25%), calix[4]resorcinarene derivative as a carrier and 2-nitrophenyl octyl ether (2-NPOE) as plasticizer was investigated. The experimental part of this investigation involved the influence of carrier nature, plasticizer concentration, pH phases, and phenol initial concentration on the removal efficiency of phenol from synthetic wastewater. A PIM containing 0.1 g (of mixture polymer), (0.15 g/g mixture of polymer) of carrier and (0.03 ml/g mixture of polymer) of 2-NPOE provided the highest percentage of phenol removal efficiency over a 6-day transport; the removal was found to be about 95%, indeed the removal was found to be highly dependent of pH phases. The feed solution in these transport experiments was at pH 2, while the stripping solution contained 0.20 M NaOH. This study claims that the PIM with a mixture of cellulose derivatives can be used effectively to remove phenols from wastewaters.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
1986-01-01
The goal of this program is to develop polymer membranes useful in the preparation of hydrogen from coal-derived synthesis gas. During this quarter the first experiment were aimed at developing high performance composite membranes for the separation of hydrogen from nitrogen and carbon monoxide. Three polymers have been selected as materials for these membranes: polyetherimide cellulose acetate and ethylcellulose. This quarter the investigators worked on polyetherimide and cellulose acetate membranes. The overall structure of these membranes is shown schematically in Figure 1. As shown, a microporous support membrane is first coated with a high flux intermediate layer then with anmore » ultrathin permselective layer and finally, if necessary, a thin protective high flux layer. 1 fig., 4 tabs.« less
Chebli, Youssef; Kaneda, Minako; Zerzour, Rabah; Geitmann, Anja
2012-12-01
The pollen tube is a cellular protuberance formed by the pollen grain, or male gametophyte, in flowering plants. Its principal metabolic activity is the synthesis and assembly of cell wall material, which must be precisely coordinated to sustain the characteristic rapid growth rate and to ensure geometrically correct and efficient cellular morphogenesis. Unlike other model species, the cell wall of the Arabidopsis (Arabidopsis thaliana) pollen tube has not been described in detail. We used immunohistochemistry and quantitative image analysis to provide a detailed profile of the spatial distribution of the major cell wall polymers composing the Arabidopsis pollen tube cell wall. Comparison with predictions made by a mechanical model for pollen tube growth revealed the importance of pectin deesterification in determining the cell diameter. Scanning electron microscopy demonstrated that cellulose microfibrils are oriented in near longitudinal orientation in the Arabidopsis pollen tube cell wall, consistent with a linear arrangement of cellulose synthase CESA6 in the plasma membrane. The cellulose label was also found inside cytoplasmic vesicles and might originate from an early activation of cellulose synthases prior to their insertion into the plasma membrane or from recycling of short cellulose polymers by endocytosis. A series of strategic enzymatic treatments also suggests that pectins, cellulose, and callose are highly cross linked to each other.
Active packaging using regenerated cellulose and hydroxypropyl amylopectin for fresh food products
USDA-ARS?s Scientific Manuscript database
As an alternate to non-sustainable plastic packaging, polymer blends were engineered using regenerated cellulose and a hydroxypropyl functionalized starch derivative. Initially, films were cast out of solution to determine optimum blend composition, and then components were reactively extruded to in...
-6223 Research Interests Molecular mechanisms of cellulose-degrading enzymes Structure-function relationships of biomass-derived polymers Structure-function relationships in glycoside hydrolases Methane potential protein engineering targets. Structure-Function Relationships of Biomass-Derived Polymers
Laffleur, Flavia; Bacher, Lukas; Netsomboon, Kesinee
2016-01-01
To design a novel preactived carboxymethyl cellulose derivative. First, carboxymethyl cellulose (CMC) was chemically modified by amide bond formation between primary amino group of cysteine (CYS) and carboxylic moiety of CMC mediated by carbodiimide. Second, obtained CMCCYS was preactivated with 2,2'-dithiodinicotinic acid. Designed CMC-S-S-MNA was characterized by FT-IR. Furthermore, cytotoxicity was conducted on Caco-2 cell line. Swelling behavior, erosion and release of novel CMC-S-S-MNA were performed compared with thiolated and unmodified cellulose, respectively. CMC-S-S-MNA showed no harmful effect on cells. CMC-S-S-MNA exhibited 2.13-fold higher stability in comparison to unmodified cellulose. Furthermore, preactivated carboxymethyl cellulose-cysteine revealed 1.9-fold controlled released compared with respective unmodified carboxymethyl cellulose. Novel preactivated carboxymethyl cellulose represents a versatile excipient for drug delivery.
NASA Astrophysics Data System (ADS)
Tze, William Tai-Yin
The overall objective of this dissertation was to gain an understanding of the relationship between interfacial chemistry and the micromechanics of the cellulose-fiber/polymer composites. Regenerated cellulose (lyocell) fibers were treated with amine-, phenylamine-, phenyl-, and octadecyl-silanes, and also styrene-maleic anhydride copolymer. Inverse gas chromatography was conducted to evaluate the modified surfaces and to examine the adsorption behavior of ethylbenzene, a model compound for polystyrene, onto the fibers. Micro-composites were formed by depositing micro-droplets of polystyrene onto single fibers. The fiber was subjected to a tensile strain, and Raman spectroscopy was employed to determine the point-to-point variation of the strain- and stress-sensitive 895 cm-1 band of cellulose along the embedded region. Inverse gas chromatography studies reveal that the Ia-b values, calculated by matching the Lewis acid parameter ( KA) and basic parameter (KB) between polystyrene and different fibers, were closely correlated to the acid-base adsorption enthalpies of ethylbenzene onto the corresponding fibers. Hence, Ia-b was subsequently used as a convenient indicator for fiber/matrix acid-base interaction. The Raman micro-spectroscopic studies demonstrate that the interfacial tensile strain and stress are highest at the edge of the droplet, and these values decline from the edge region to the middle region of the embedment. The maximum of these local strains corresponds to a strain-control fracture of the matrix polymer. The minimum of the local tensile stress corresponds to the extent of fiber-to-matrix load transfer. The slope of the tensile stress profile allows for an estimation of the maximum interfacial shear stress, which is indicative of fiber/polymer (practical) adhesion. As such, a novel micro-Raman tensile technique was established for evaluating the ductile-fiber/brittle-polymer system in this study. The micro-Raman tensile technique provided maximum interfacial shear stress values of 8.0 to 13.8 MPa, ranking functional groups according to their practical adhesion to polystyrene: alkyl < untreated < phenyl = phenylamine = styrene copolymer < amine. Overall, interfacial bonding can be increased by increasing the acid-base interactions (Ia-b) or reducing the chemical incompatibility (Deltadelta) between the fibers and matrix. Therefore, interfacial chemistry can be employed to enhance and predict cellulose-fiber/polymer adhesion to better engineer composite properties and ultimately better utilize bio-resources.
Kouko, Jarmo; Setälä, Harri; Tanaka, Atsushi; Khakalo, Alexey; Ropponen, Jarmo; Retulainen, Elias
2018-04-15
Wood fiber-based packaging materials, as renewable materials, have growing market potential due to their sustainability. A new breakthrough in cellulose-based packaging requires some improvement in the mechanical properties of paper. Bleached softwood kraft pulp was mechanically treated, in two stages, using high- and low-consistency refining, sequentially. Chemical treatment of pulp using the oxyalkylation method was applied to modify a portion of fiber material, especially the fiber surface, and its compatibility with polymer dispersions including one carbohydrate polymer. The results showed that the compatibility of the cellulosic fibers with some polymers could be improved with oxyalkylation. By adjusting mechanical and chemical treatments, and the thermoforming conditions, the formability of paper was improved, but simultaneously the strength and stiffness decreased. The results suggest that the formability of the paper is not a direct function of the extensibility of the applied polymer, but also depends on the fiber network structure and surface energy. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.
Electrospun nanofibers of poly(vinyl alcohol)reinforced with cellulose nanofibrils
USDA-ARS?s Scientific Manuscript database
In this work, nanofibers of poly(vinyl alcohol) (PVA) reinforced with cellulose nanofibrils (CnF) were produced by electrospinning. The effects of applied voltage, polymer concentration and injection rate, tip-to-collector distance (TCD), rotation speed of the collector, and relative humidity on mor...
Effects of cationic hydroxyethyl cellulose on glucose tolerance and obesity
USDA-ARS?s Scientific Manuscript database
Cholestyramine is a cationic polymer prescribed to lower cholesterol in humans. We investigated the effects of cationic hydroxyethyl cellulose (cHEC) on weight loss and metabolic disorders associated with obesity using both hamster and diet-induced obese mouse models. Golden Syrian hamsters and ob...
In vitro and in vivo characteristics of a thermogelling rectal delivery system of etodolac.
Barakat, Nahla S
2009-01-01
Rectal etodolac-Poloxamer gel systems composed of Poloxamer and bioadhesive polymers were developed and evaluated. Hydroxypropylmethyl cellulose, poly)vinyl) pyrrolidone, methyl cellulose, hydroxyethylcellulose, and carbopol were examined as mucoadhesive polymers. The characteristics of the rectal gels differed according to the properties of mucoadhesive polymers. The physicochemical properties such as gelation temperature, gel strength, and bioadhesive force of various formulations were investigated. The analysis of release mechanism showed that the release of etodolac was proportional to the square root of time, indicating that etodolac might be released from the suppositories by Fickian diffusion. The anti-inflammatory effect of etodolac-Poloxamer gel system was also studied in rats. Moreover, liquid suppository of etodolac did not cause any morphological damage to the rectal tissues. These results suggested that in situ gelling liquid suppository with etodolac and mucoadhesive polymer was a physically safe, convenient, and effective rectal dosage form for etodolac.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rapp, F., E-mail: florian.rapp@ict.fraunhofer.de, E-mail: anja.schneider@ict.fraunhofer.de; Schneider, A., E-mail: florian.rapp@ict.fraunhofer.de, E-mail: anja.schneider@ict.fraunhofer.de; Elsner, P., E-mail: peter.elsner@ict.fraunhofer.de
2014-05-15
Biopolymers are becoming increasingly important to both industry and consumers. With regard to waste management, CO{sub 2} balance and the conservation of petrochemical resources, increasing efforts are being made to replace standard plastics with bio-based polymers. Nowadays biopolymers can be built for example of cellulose, lactic acid, starch, lignin or bio mass. The paper will present material properties of selected cellulose based polymers (cellulose propionate [CP], cellulose acetate butyrate [CAB]) and corresponding processing conditions for particle foams as well as characterization of produced parts. Special focus is given to the raw material properties by analyzing thermal behavior (differential scanning calorimetry),more » melt strength (Rheotens test) and molecular weight distribution (gel-permeation chromatography). These results will be correlated with the foaming behavior in a continuous extrusion process with physical blowing agents and underwater pelletizer. Process set-up regarding particle foam technology, including extrusion foaming and pre-foaming, will be shown. The characteristics of the resulting foam beads will be analyzed regarding part density, cell morphology and geometry. The molded parts will be tested on thermal conductivity as well as compression behavior (E-modulus, compression strength)« less
NASA Astrophysics Data System (ADS)
Andrews, Mark P.; Kanigan, Tanya
2007-06-01
Orientation anisotropies in structural properties relevant to the use of cellulosic polymers as membranes for lab-on-chips were investigated for cellulose acetate (CA) and regenerated cellulose (RC) films deposited as slab waveguides. Anisotropy was probed with mode and polarization state selected guided wave Raman spectroscopy. CA exhibits partial chain orientation in the plane of the film, and this orientation is independent of sample substrate and film preparation conditions. RC films also show in-plane anisotropy, where the hexose sugar rings lie roughly in the plane of the film. Explanations are given of the role of artifacts in interpreting waveguide Raman spectra, including anomalous contributions to Raman spectra that arise from deviations from right angle scattering geometry, mode-dependent contributions to longitudinal electric field components and TE<-->TM mode conversion. We explore diffusion profiles of small molecules in cellulosic films by adaptations of an inverse-Wentzel-Kramers-Brillouin (iWKB) recursive, noninteger virtual mode index algorithm. Perturbations in the refractive index distribution, n(z), are recovered from the measured relative propagation constants, neffective,m, of the planar waveguide. The refractive index distribution then yields the diffusion profile.
Muselík, Jan; Wojnarová, Lenka; Masteiková, Ruta; Sopuch, Tomáš
2013-04-01
Carboxymethyl cellulose, especially its sodium salt, is a versatile pharmaceutical excipient. From a therapeutic point of view, sodium salt of carboxymethyl cellulose is used in the production of modern wound dressings to allow moist wound healing. Wound dressings must be sterile and stable throughout their shelf life and have to be able to withstand different temperature conditions. At the present time, a number of sterilization methods are available. In the case of polymeric materials, the selected sterilization process must not induce any changes in the polymer structure, such as polymer chains cleavage, changes in cross-linking, etc. This paper evaluates the influence of different sterilization methods (γ-radiation, β-radiation, ethylene oxide) on the stability of carboxymethyl cellulose and the results of long-term and accelerated stability testing. Evaluation of samples was performed using size-exclusion chromatography. The obtained results showed that ethylene oxide sterilization was the least aggressive variant of the sterilization methods tested. When the γ-radiation sterilization was used, the changes in the size of the carboxymethyl cellulose molecule occurred. In the course of accelerated and long term stability studies, no further degradation changes were observed, and thus sterilized samples are suitable for long term storage.
Dispersion of cellulose nanofibers in biopolymer based nanocomposites
NASA Astrophysics Data System (ADS)
Wang, Bei
The focus of this work was to understand the fundamental dispersion mechanism of cellulose based nanofibers in bionanocomposites. The cellulose nanofibers were extracted from soybean pod and hemp fibers by chemo-mechanical treatments. These are bundles of cellulose nanofibers with a diameter ranging between 50 to 100 nm and lengths of thousands of nanometers which results in very high aspect ratio. In combination with a suitable matrix polymer, cellulose nanofiber networks show considerable potential as an effective reinforcement for high quality specialty applications of bio-based nanocomposites. Cellulose fibrils have a high density of --OH groups on the surface, which have a tendency to form hydrogen bonds with adjacent fibrils, reducing interaction with the surrounding matrix. The use of nanofibers has been mostly restricted to water soluble polymers. This thesis is focused on synthesizing the nanocomposite using a solid phase matrix polypropylene (PP) or polyethylene (PE) by hot compression and poly (vinyl alcohol) (PVA) in an aqueous phase by film casting. The mechanical properties of nanofiber reinforced PVA film demonstrated a 4-5 fold increase in tensile strength, as compared to the untreated fiber-blend-PVA film. It is necessary to reduce the entanglement of the fibrils and improve their dispersion in the matrix by surface modification of fibers without deteriorating their reinforcing capability. Inverse gas chromatography (IGC) was used to explore how various surface treatments would change the dispersion component of surface energy and acid-base character of cellulose nanofibers and the effect of the incorporation of these modified nanofibers into a biopolymer matrix on the properties of their nano-composites. Poly (lactic acid) (PLA) and polyhydroxybutyrate (PHB) based nanocomposites using cellulose nanofibers were prepared by extrusion, injection molding and hot compression. The IGC results indicated that styrene maleic anhydride coated and ethylene-acrylic acid coated fibers improved their potential to interact with both acidic and basic resins. From transmission electron micrograph, it was shown that the nanofibers were partially dispersed in the polymer matrix. The mechanical properties of the nanocomposites were lower than those predicted by theoretical calculations for both nanofiber reinforced biopolymers.
Ko, Hsu-Feng; Sfeir, Charles; Kumta, Prashant N.
2010-01-01
Recent developments in tissue engineering approaches frequently revolve around the use of three-dimensional scaffolds to function as the template for cellular activities to repair, rebuild and regenerate damaged or lost tissues. While there are several biomaterials to select as three-dimensional scaffolds, it is generally agreed that a biomaterial to be used in tissue engineering needs to possess certain material characteristics such as biocompatibility, suitable surface chemistry, interconnected porosity, desired mechanical properties and biodegradability. The use of naturally derived polymers as three-dimensional scaffolds has been gaining widespread attention owing to their favourable attributes of biocompatibility, low cost and ease of processing. This paper discusses the synthesis of various polysaccharide-based, naturally derived polymers, and the potential of using these biomaterials to serve as tissue engineering three-dimensional scaffolds is also evaluated. In this study, naturally derived polymers, specifically cellulose, chitosan, alginate and agarose, and their composites, are examined. Single-component scaffolds of plain cellulose, plain chitosan and plain alginate as well as composite scaffolds of cellulose–alginate, cellulose–agarose, cellulose–chitosan, chitosan–alginate and chitosan–agarose are synthesized, and their suitability as tissue engineering scaffolds is assessed. It is shown that naturally derived polymers in the form of hydrogels can be synthesized, and the lyophilization technique is used to synthesize various composites comprising these natural polymers. The composite scaffolds appear to be sponge-like after lyophilization. Scanning electron microscopy is used to demonstrate the formation of an interconnected porous network within the polymeric scaffold following lyophilization. It is also established that HeLa cells attach and proliferate well on scaffolds of cellulose, chitosan or alginate. The synthesis protocols reported in this study can therefore be used to manufacture naturally derived polymer-based scaffolds as potential biomaterials for various tissue engineering applications. PMID:20308112
Mechanical Properties versus Morphology of Ordered Polymers. Volume III. Part I
1982-08-01
measured by wide angle x-ray scattering and differential scanning calorimetry, is unrelated to the diffuse scattered intensity [62]. Cellulose acetate which...increasing void fraction, in air swollen cellulose . Comparison of the volume fraction of voids calculated from the SAXS integrated intensity with...1964). 63. P.H. Hermans, D. Heikens, and A. Weidinger, "A Quantitative Investigation on the X-Ray Small Angle Scattering of Cellulose Fibers. Part II
Drovetskaya, T V; Kreeger, R L; Amos, J L; Davis, C B; Zhou, S
2004-01-01
A new class of cationic conditioning polymers (Polymer SL) has been prepared and evaluated in shampoo formulations. Polymer SL is a family of high viscosity quaternized hydroxyethyl cellulose (HEC) polymers with cationic substitution of trimethyl ammonium and dimethyldodecyl ammonium (Figure 1). SL compositions benefit from hydrophobic character to deliver superior conditioning performance in hair care applications. At the same time, low levels of hydrophobes have been chosen to assure good compatibility with surfactant systems without the complications of associative thickening. The polymers have been evaluated in clear shampoo formulations and two-in-one silicone containing shampoos using objective lab methods and subjective panel evaluation on hair tresses. Commercial conditioning polymers: Polyquaternium-10 (PQ-10) (UCARE Polymer LR-30M) and Guar Hydroxypro-pyltrimethylammonium Chloride (Jaguar C-13S) were used as performance benchmarks. The new hydrophobically-modified cationic polymers demonstrated superior performance in all major categories of conditioning and showed improved silicone deposition from two-in-one systems. Moreover, they retained other good qualities of their PQ-10 structural analogs such as enabling crystal clear formulations and showing no build-up or volume-down effects on hair. These new olymers were also found to be efficient conditioning agents in different surfactant systems with or without silicones.
Regenerated cellulose/wool blend enhanced biomimetic hydroxyapatite mineralization.
Salama, Ahmed; El-Sakhawy, Mohamed
2016-11-01
The current article investigates the effect of bioactive cellulose/wool blend on calcium phosphate biomimetic mineralization. Regenerated cellulose/wool blend was prepared by dissolution-regeneration of neat cellulose and natural wool in 1-butyl-3-methyl imidazolium chloride [Bmim][Cl], as a solvent for the two polymers. Crystalline hydroxyapatite nanofibers with a uniform size, shape and dimension were formed after immersing the bioactive blend in simulated body fluid. The cytotoxicity of cellulose/wool/hydroxyapatite was studied using animal fibroblast baby hamster kidney cells (BHK-21) and the result displayed good cytocompatability. This research work presents a green processing method for the development of novel cellulose/wool/hydroxyapatite hybrid materials for tissue engineering applications. Copyright © 2016 Elsevier B.V. All rights reserved.
Polymer-grafted cellulose nanocrystals as pH-responsive reversible flocculants.
Kan, Kevin H M; Li, Jian; Wijesekera, Kushlani; Cranston, Emily D
2013-09-09
Cellulose nanocrystals (CNCs) are a sustainable nanomaterial with applications spanning composites, coatings, gels, and foams. Surface modification routes to optimize CNC interfacial compatibility and functionality are required to exploit the full potential of this material in the design of new products. In this work, CNCs have been rendered pH-responsive by surface-initiated graft polymerization of 4-vinylpyridine with the initiator ceric(IV) ammonium nitrate. The polymerization is a one-pot, water-based synthesis carried out under sonication, which ensures even dispersion of the cellulose nanocrystals during the reaction. The resultant suspensions of poly(4-vinylpyridine)-grafted cellulose nanocrystals (P4VP-g-CNCs) show reversible flocculation and sedimentation with changes in pH; the loss of colloidal stability is visible by eye even at concentrations as low as 0.004 wt %. The presence of grafted polymer and the ability to tune the hydrophilic/hydrophobic properties of P4VP-g-CNCs were characterized by Fourier transform infrared spectroscopy, elemental analysis, electrophoretic mobility, mass spectrometry, transmittance spectroscopy, contact-angle measurements, thermal analysis, and various microscopies. Atomic force microscopy showed no observable changes in the CNC dimensions or degree of aggregation after polymer grafting, and a liquid crystalline nematic phase of the modified CNCs was detected by polarized light microscopy. Controlled stability and wettability of P4VP-g-CNCs is advantageous both in composite design, where cellulose nanocrystals generally have limited dispersibility in nonpolar matrices, and as biodegradable flocculants. The responsive nature of these novel nanoparticles may offer new applications for CNCs in biomedical devices, as clarifying agents, and in industrial separation processes.
A green approach is described that generates bulk quantities of nanocomposites containing transition metals such as Cu, Ag, In and Fe at room temperature using a biodegradable polymer carboxymethyl cellulose (CMC) by reacting respective metal salts with sodium salt of CMC in aqu...
Study on stimulus-responsive cellulose-based polymeric materials
NASA Astrophysics Data System (ADS)
Luo, Hongsheng
Stimulus-responsive cellulose-based polymeric materials were developed by physical and chemical approaches. The thermal, structural, mechanical and morphological properties of the samples were comprehensively investigated by multiple tools. Shape memory effect (SME), programming-structure-property relationship and underling mechanisms were emphasized in this study. Some new concepts, such as heterogeneous-twin-switch, path-dependent multi-shape, rapidly switchable water-sensitive SME were established. The samples were divided into two categories. For the first category, cellulose nano-whiskers (CNWs) were incorporated into crystalline shape memory polyurethane (SMPU) and thermal plastic polyurethane (TPU). The CNW-SMPU nano-composites had heterogeneous switches. Triple- and multi-shape effects were achieved for the CNW-SMPU nano-composites by applying into appropriate thermal-aqueous-mechanical programming. Furthermore, the thermally triggered shape recovery of the composites was found to be tuneable, depending on the PCN content. Theoretical prediction along with numerical analysis was conducted, providing evidence on the possible microstructure of the CNW-SMPU nano-composites. Rapidly switchable water-sensitive SME of the CNW-TPU nano-composites was unprecedentedly studied, which originated from the reversible regulation of hydrogen bonding by water. The samples in the second category consisted of cellulose-polyurethane (PU) blends, cellulose-poly(acrylic acid) (PAA) composites and modified cellulose with supramolecular switches, featuring the requirement of homogeneous cellulose solution in the synthesis process. The reversible behaviours of the cellulose-PU blends in wet-dry cycles as well as the underlying shape memory mechanism were characterized and disclosed. The micro-patterns of the blends were found to be self-similar in fractal dimensions. Cellulose-PAA semi-interpenetrating networks exhibited mechanical adaptability in wet-dry cycles. A type of thermally reversible quadruple hydrogen bonding units, ureidopyrimidinone (UPy), reacted with the cellulose as pendent side-groups, which may impart the modified cellulose with thermal sensitivity. It is the first attempt to explore the natural cellulose as smart polymeric materials systematically and comprehensively. The concepts originally created in the study provided new viewpoints and routes for the development of novel shape memory polymers. The findings significantly benefits extension of the potential application of the cellulose in smart polymeric materials field.
Recent Progress on Cellulose-Based Electro-Active Paper, Its Hybrid Nanocomposites and Applications
Khan, Asif; Abas, Zafar; Kim, Heung Soo; Kim, Jaehwan
2016-01-01
We report on the recent progress and development of research into cellulose-based electro-active paper for bending actuators, bioelectronics devices, and electromechanical transducers. The cellulose electro-active paper is characterized in terms of its biodegradability, chirality, ample chemically modifying capacity, light weight, actuation capability, and ability to form hybrid nanocomposites. The mechanical, electrical, and chemical characterizations of the cellulose-based electro-active paper and its hybrid composites such as blends or coatings with synthetic polymers, biopolymers, carbon nanotubes, chitosan, and metal oxides, are explained. In addition, the integration of cellulose electro-active paper is highlighted to form various functional devices including but not limited to bending actuators, flexible speaker, strain sensors, energy harvesting transducers, biosensors, chemical sensors and transistors for electronic applications. The frontiers in cellulose paper devices are reviewed together with the strategies and perspectives of cellulose electro-active paper and cellulose nanocomposite research and applications. PMID:27472335
Recent Progress on Cellulose-Based Electro-Active Paper, Its Hybrid Nanocomposites and Applications.
Khan, Asif; Abas, Zafar; Kim, Heung Soo; Kim, Jaehwan
2016-07-26
We report on the recent progress and development of research into cellulose-based electro-active paper for bending actuators, bioelectronics devices, and electromechanical transducers. The cellulose electro-active paper is characterized in terms of its biodegradability, chirality, ample chemically modifying capacity, light weight, actuation capability, and ability to form hybrid nanocomposites. The mechanical, electrical, and chemical characterizations of the cellulose-based electro-active paper and its hybrid composites such as blends or coatings with synthetic polymers, biopolymers, carbon nanotubes, chitosan, and metal oxides, are explained. In addition, the integration of cellulose electro-active paper is highlighted to form various functional devices including but not limited to bending actuators, flexible speaker, strain sensors, energy harvesting transducers, biosensors, chemical sensors and transistors for electronic applications. The frontiers in cellulose paper devices are reviewed together with the strategies and perspectives of cellulose electro-active paper and cellulose nanocomposite research and applications.
Enhanced transport of biodegradable polymer-coated nanoiron particles in sand columns
NASA Astrophysics Data System (ADS)
Jung, B.; O'Carroll, D.; Sleep, B.
2009-05-01
The use of nanoscale zerovalent iron has shown promise as a technology for remediation of subsurface contamination by chlorinated solvents. However, the delivery of nanoiron particles to target contaminated subsurface zones is hindered by the aggregation of particles due to magnetic attraction. To overcome the limitations of aggregation and increase nanoiron mobility in porous media, nanoiron particles have been coated with various polymers. Polymer adsorption onto nanoiron particles provides electrosteric stabilization, increases the mobility, and decreases the attachment onto the soil surface. Various polymers were investigated in this study, including carboxylmethyl cellulose (CMC) and guar gum, both of which are biodegradable. In sand column experiments the transport of nanoiron particles was investigated as a function of type of electrolyte, ionic strength, flow velocity, and nanoiron particle concentration. Settling curves showed the enhanced stability of polymer-coated nanoiron particles compared to bare commercial nanoiron particles (bare RNIP-10DS). A newly developed nanoparticle transport numerical model was used to quantify the attachment efficiency, as well as investigate dominant nanoparticle transport and removal mechanisms. Finally the particle-collector interaction energy was predicted using DLVO (Derjaguin-Landau-Verwey-Overbeek) theory.
Kaabi Falahieh Asl, Sara; Nemeth, Sandor; Tan, Ming Jen
2016-11-01
Ceramic type coatings on metallic implants, such as calcium phosphate (Ca-P), are generally stiff and brittle, potentially leading to the early failure of the bone-implant interface. To reduce material brittleness, polyacrylic acid and carboxymethyl cellulose were used in this study to deposit two types of novel Ca-P/polymer composite coatings on AZ31 magnesium alloy using a one-step hydrothermal process. X-ray diffraction and scanning electron microscopy showed that the deposited Ca-P crystal phase and morphology could be controlled by the type and concentration of polymer used. Incorporation of polymer in the Ca-P coatings reduced the coating elastic modulus bringing it close to that of magnesium and that of human bone. Nanoindentation test results revealed significantly decreased cracking tendency with the incorporation of polymer in the Ca-P coating. Apart from mechanical improvements, the protective composite layers had also enhanced the corrosion resistance of the substrate by a factor of 1000 which is sufficient for implant application. Cell proliferation studies indicated that the composite coatings induced better cell attachment compared with the purely inorganic Ca-P coating, confirming that the obtained composite materials could be promising candidates for surface protection of magnesium for implant application with the multiple functions of corrosion protection, interfacial stress reduction, and cell attachment/cell growth promotion. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1643-1657, 2016. © 2015 Wiley Periodicals, Inc.
NASA Astrophysics Data System (ADS)
Won, Lee Ji; Kim, Jae Hong; Thogiti, Suresh
2018-05-01
A novel polymer blend electrolyte for dye-sensitized solar cells (DSSCs) was synthesized by quasi-solidifying a liquid-based electrolyte containing an iodide/triiodide redox couple and supporting salts with a mixture of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and indigenous hydroxypropyl methyl cellulose (HPMC). A high ionic conductivity of 8.8 × 10-4 S cm-1 was achieved after introducing 5 wt% of HPMC with respect to the weight of PVDH-HFP. DSSCs were fabricated using gel polymer blend electrolytes, and the J-V characteristics of the fabricated devices were analyzed. Under optimal conditions, the photovoltaic conversion efficiency of cells with the novel HPMC-blended gel electrolyte (5.34%) was significantly greater than that of cells without HPMC (3.97%).
NASA Astrophysics Data System (ADS)
Chai, M. N.; Isa, M. I. N.
2016-06-01
The plasticized solid bio-polymer electrolytes (SBEs) system has been formed by introducing glycerol (Gly) as the plasticizer into the carboxymethyl cellulose (CMC) doped with oleic acid (OA) via solution casting techniques. The ionic conductivity of the plasticized SBEs has been studied using Electrical Impedance Spectroscopy. The highest conductivity achieved is 1.64 × 10-4 S cm-1 for system containing 40 wt. % of glycerol. FTIR deconvolution technique had shown that the conductivity of CMC-OA-Gly SBEs is primarily influenced by the number density of mobile ions. Transference number measurement has shown that the cation diffusion coefficient and ionic mobility is higher than anion which proved the plasticized polymer system is a proton conductor.
1986-09-01
since the first fibers based on modified cellulose were developed at the end of the 19th century. Recent advances in fiber science have focused on high...investigations to date have focused on the wet spinning of such flexible extended chain polymers as cellulosic materials (30), proteins (31,32), and...instabilities. Materials such as coagulated cellulose , PAN, poly (amino acids), and wet wood possess an interconnected fibrillar structure (30,32,35
Chebli, Youssef; Kaneda, Minako; Zerzour, Rabah; Geitmann, Anja
2012-01-01
The pollen tube is a cellular protuberance formed by the pollen grain, or male gametophyte, in flowering plants. Its principal metabolic activity is the synthesis and assembly of cell wall material, which must be precisely coordinated to sustain the characteristic rapid growth rate and to ensure geometrically correct and efficient cellular morphogenesis. Unlike other model species, the cell wall of the Arabidopsis (Arabidopsis thaliana) pollen tube has not been described in detail. We used immunohistochemistry and quantitative image analysis to provide a detailed profile of the spatial distribution of the major cell wall polymers composing the Arabidopsis pollen tube cell wall. Comparison with predictions made by a mechanical model for pollen tube growth revealed the importance of pectin deesterification in determining the cell diameter. Scanning electron microscopy demonstrated that cellulose microfibrils are oriented in near longitudinal orientation in the Arabidopsis pollen tube cell wall, consistent with a linear arrangement of cellulose synthase CESA6 in the plasma membrane. The cellulose label was also found inside cytoplasmic vesicles and might originate from an early activation of cellulose synthases prior to their insertion into the plasma membrane or from recycling of short cellulose polymers by endocytosis. A series of strategic enzymatic treatments also suggests that pectins, cellulose, and callose are highly cross linked to each other. PMID:23037507
McLaughlin, Kimberley; Folorunso, Ayorinde O; Deeni, Yusuf Y; Foster, Dona; Gorbatiuk, Oksana; Hapca, Simona M; Immoor, Corinna; Koza, Anna; Mohammed, Ibrahim U; Moshynets, Olena; Rogalsky, Sergii; Zawadzki, Kamil; Spiers, Andrew J
2017-06-01
Although bacterial cellulose synthase (bcs) operons are widespread within the Proteobacteria phylum, subunits required for the partial-acetylation of the polymer appear to be restricted to a few γ-group soil, plant-associated and phytopathogenic pseudomonads, including Pseudomonas fluorescens SBW25 and several Pseudomonas syringae pathovars. However, a bcs operon with acetylation subunits has also been annotated in the unrelated β-group respiratory pathogen, Bordetella avium 197N. Our comparison of subunit protein sequences and GC content analyses confirms the close similarity between the B. avium 197N and pseudomonad operons and suggests that, in both cases, the cellulose synthase and acetylation subunits were acquired as a single unit. Using static liquid microcosms, we can confirm that B. avium 197N expresses low levels of cellulose in air-liquid interface biofilms and that biofilm strength and attachment levels could be increased by elevating c-di-GMP levels like the pseudomonads, but cellulose was not required for biofilm formation itself. The finding that B. avium 197N is capable of producing cellulose from a highly-conserved, but relatively uncommon bcs operon raises the question of what functional role this modified polymer plays during the infection of the upper respiratory tract or survival between hosts, and what environmental signals control its production. Copyright © 2017 Institut Pasteur. All rights reserved.
Acetone-based cellulose solvent.
Kostag, Marc; Liebert, Tim; Heinze, Thomas
2014-08-01
Acetone containing tetraalkylammonium chloride is found to be an efficient solvent for cellulose. The addition of an amount of 10 mol% (based on acetone) of well-soluble salt triethyloctylammonium chloride (Et3 OctN Cl) adjusts the solvent's properties (increases the polarity) to promote cellulose dissolution. Cellulose solutions in acetone/Et3 OctN Cl have the lowest viscosity reported for comparable aprotic solutions making it a promising system for shaping processes and homogeneous chemical modification of the biopolymer. Recovery of the polymer and recycling of the solvent components can be easily achieved. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Sustainable Elastomers from Renewable Biomass.
Wang, Zhongkai; Yuan, Liang; Tang, Chuanbing
2017-07-18
Sustainable elastomers have undergone explosive growth in recent years, partly due to the resurgence of biobased materials prepared from renewable natural resources. However, mounting challenges still prevail: How can the chemical compositions and macromolecular architectures of sustainable polymers be controlled and broadened? How can their processability and recyclability be enabled? How can they compete with petroleum-based counterparts in both cost and performance? Molecular-biomass-derived polymers, such as polymyrcene, polymenthide, and poly(ε-decalactone), have been employed for constructing thermoplastic elastomers (TPEs). Plant oils are widely used for fabricating thermoset elastomers. We use abundant biomass, such as plant oils, cellulose, rosin acids, and lignin, to develop elastomers covering a wide range of structure-property relationships in the hope of delivering better performance. In this Account, recent progress in preparing monomers and TPEs from biomass is first reviewed. ABA triblock copolymer TPEs were obtained with a soft middle block containing a soybean-oil-based monomer and hard outer blocks containing styrene. In addition, a combination of biobased monomers from rosin acids and soybean oil was formulated to prepare triblock copolymer TPEs. Together with the above-mentioned approaches based on block copolymers, multigraft copolymers with a soft backbone and rigid side chains are recognized as the first-generation and second-generation TPEs, respectively. It has been recently demonstrated that multigraft copolymers with a rigid backbone and elastic side chains can also be used as a novel architecture of TPEs. Natural polymers, such as cellulose and lignin, are utilized as a stiff, macromolecular backbone. Cellulose/lignin graft copolymers with side chains containing a copolymer of methyl methacrylate and butyl acrylate exhibited excellent elastic properties. Cellulose graft copolymers with biomass-derived polymers as side chains were further explored to enhance the overall sustainability. Isoprene polymers were grafted from a cellulosic backbone to afford Cell-g-polyisoprene copolymers. Via cross-linking of these graft copolymers, human-skin-mimic elastomers and high resilient elastomers with a well-defined network structure were achieved. The mechanical properties of these resilient elastomers could be finely controlled by tuning the cellulose content. As isoprene can be produced by engineering of microorganisms, these elastomers could be a renewable alternative to petroleum products. In summary, triblock copolymer and graft copolymer TPEs with biomass components, skin-mimic elastomers, high resilient biobased elastomers, and engineering of macromolecular architectures for elastomers are discussed. These approaches and design provide us knowledge on the potential to make sustainable elastomers for various applications to compete with petroleum-based counterparts.
X-ray coherent diffraction imaging of cellulose fibrils in situ.
Lal, Jyotsana; Harder, Ross; Makowski, Lee
2011-01-01
Cellulose is the most abundant renewable source of organic molecules on earth[1]. As fossil fuel reserves become depleted, the use of cellulose as a feed stock for fuels and chemicals is being aggressively explored. Cellulose is a linear polymer of glucose that packs tightly into crystalline fibrils that make up a substantial proportion of plant cell walls. Extraction of the cellulose chains from these fibrils in a chemically benign process has proven to be a substantial challenge [2]. Monitoring the deconstruction of the fibrils in response to physical and chemical treatments would expedite the development of efficient processing methods. As a step towards achieving that goal, we here describe Bragg-coherent diffraction imaging (CDI) as an approach to producing images of cellulose fibrils in situ within vascular bundles from maize.
Mechanical and thermal properties of waterborne epoxy composites containing cellulose nanocrystals
Shanhong Xu; Natalie Girouard; Gregory Schueneman; Meisha L. Shofner; J. Carson Meredith
2013-01-01
Cellulose nanocrystals (CNCs) are reinforcing fillers of emerging interest for polymers due to their high modulus and potential for sustainable production. In this study, CNC-based composites with a waterborne epoxy resin matrix were prepared and characterized to determine morphology, water content, and thermal and mechanical properties. While some CNC aggregation was...
USDA-ARS?s Scientific Manuscript database
In the U.S., concerns over the long-term sustainability of peat, perlite, and other media components have led to searches for alternative materials. FiberFill, a synthetic fiber made of recyclable polyethylene terephthalate, and Tencel, a cellulose fiber, are new materials with potential as substra...
21 CFR 177.1400 - Hydroxyethyl cellulose film, water-insoluble.
Code of Federal Regulations, 2011 CFR
2011-04-01
... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Hydroxyethyl cellulose film, water-insoluble. 177.1400 Section 177.1400 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single and...
2013-01-01
Background Second-generation biofuels are generally produced from the polysaccharides in the lignocellulosic plant biomass, mainly cellulose. However, because cellulose is embedded in a matrix of other polysaccharides and lignin, its hydrolysis into the fermentable glucose is hampered. The senesced inflorescence stems of a set of 20 Arabidopsis thaliana mutants in 10 different genes of the lignin biosynthetic pathway were analyzed for cell wall composition and saccharification yield. Saccharification models were built to elucidate which cell wall parameters played a role in cell wall recalcitrance. Results Although lignin is a key polymer providing the strength necessary for the plant’s ability to grow upward, a reduction in lignin content down to 64% of the wild-type level in Arabidopsis was tolerated without any obvious growth penalty. In contrast to common perception, we found that a reduction in lignin was not compensated for by an increase in cellulose, but rather by an increase in matrix polysaccharides. In most lignin mutants, the saccharification yield was improved by up to 88% cellulose conversion for the cinnamoyl-coenzyme A reductase1 mutants under pretreatment conditions, whereas the wild-type cellulose conversion only reached 18%. The saccharification models and Pearson correlation matrix revealed that the lignin content was the main factor determining the saccharification yield. However, also lignin composition, matrix polysaccharide content and composition, and, especially, the xylose, galactose, and arabinose contents influenced the saccharification yield. Strikingly, cellulose content did not significantly affect saccharification yield. Conclusions Although the lignin content had the main effect on saccharification, also other cell wall factors could be engineered to potentially increase the cell wall processability, such as the galactose content. Our results contribute to a better understanding of the effect of lignin perturbations on plant cell wall composition and its influence on saccharification yield, and provide new potential targets for genetic improvement. PMID:23622268
Ansari, Farhan; Berglund, Lars A
2018-04-11
Cellulose nanocomposites can be considered for semistructural load-bearing applications where modulus and strength requirements exceed 10 GPa and 100 MPa, respectively. Such properties are higher than for most neat polymers but typical for molded short glass fiber composites. The research challenge for polymer matrix biocomposites is to develop processing concepts that allow high cellulose nanofibril (CNF) content, nanostructural control in the form of well-dispersed CNF, the use of suitable polymer matrices, as well as molecular scale interface tailoring to address moisture effects. From a practical point of view, the processing concept needs to be scalable so that large-scale industrial processing is feasible. The vast majority of cellulose nanocomposite studies elaborate on materials with low nanocellulose content. An important reason is the challenge to prevent CNF agglomeration at high CNF content. Research activities are therefore needed on concepts with the potential for rapid processing with controlled nanostructure, including well-dispersed fibrils at high CNF content so that favorable properties are obtained. This perspective discusses processing strategies, agglomeration problems, opportunities, and effects from interface tailoring. Specifically, preformed CNF mats can be used to design nanostructured biocomposites with high CNF content. Because very few composite materials combine functional and structural properties, CNF materials are an exception in this sense. The suggested processing concept could include functional components (inorganic clays, carbon nanotubes, magnetic nanoparticles, among others). In functional three-phase systems, CNF networks are combined with functional components (nanoparticles or fibril coatings) together with a ductile polymer matrix. Such materials can have functional properties (optical, magnetic, electric, etc.) in combination with mechanical performance, and the comparably low cost of nanocellulose may facilitate the use of large nanocomposite structures in industrial applications.
Kombucha Multimicrobial Community under Simulated Spaceflight and Martian Conditions.
Podolich, O; Zaets, I; Kukharenko, O; Orlovska, I; Reva, O; Khirunenko, L; Sosnin, M; Haidak, A; Shpylova, S; Rabbow, E; Skoryk, M; Kremenskoy, M; Demets, R; Kozyrovska, N; de Vera, J-P
2017-05-01
Kombucha microbial community (KMC) produces a cellulose-based biopolymer of industrial importance and a probiotic beverage. KMC-derived cellulose-based pellicle film is known as a highly adaptive microbial macrocolony-a stratified community of prokaryotes and eukaryotes. In the framework of the multipurpose international astrobiological project "BIOlogy and Mars Experiment (BIOMEX)," which aims to study the vitality of prokaryotic and eukaryotic organisms and the stability of selected biomarkers in low Earth orbit and in a Mars-like environment, a cellulose polymer structural integrity will be assessed as a biomarker and biotechnological nanomaterial. In a preflight assessment program for BIOMEX, the mineralized bacterial cellulose did not exhibit significant changes in the structure under all types of tests. KMC members that inhabit the cellulose-based pellicle exhibited a high survival rate; however, the survival capacity depended on a variety of stressors such as the vacuum of space, a Mars-like atmosphere, UVC radiation, and temperature fluctuations. The critical limiting factor for microbial survival was high-dose UV irradiation. In the tests that simulated a 1-year mission of exposure outside the International Space Station, the core populations of bacteria and yeasts survived and provided protection against UV; however, the microbial density of the populations overall was reduced, which was revealed by implementation of culture-dependent and culture-independent methods. Reduction of microbial richness was also associated with a lower accumulation of chemical elements in the cellulose-based pellicle film, produced by microbiota that survived in the post-test experiments, as compared to untreated cultures that populated the film. Key Words: BIOlogy and Mars Experiment (BIOMEX)-Kombucha multimicrobial community-Biosignature-Biofilm-Bacterial cellulose. Astrobiology 17, 459-469.
Solubilization of octane in cationic surfactant-anionic polymer complexes: Effect of ionic strength.
Zhang, Hui; Deng, Lingli; Sun, Ping; Que, Fei; Weiss, Jochen
2016-01-01
Polymers may alter the ability of oppositely charged surfactant micelles to solubilize hydrophobic molecules depending on surfactant-polymer interactions. This study was conducted to investigate the effect of ionic strength on the solubilization thermodynamics of an octane oil-in-water emulsion in mixtures of an anionic polymer (carboxymethyl cellulose) and cationic cetyltrimethylammonium bromide (CTAB) surfactant micelles using isothermal titration calorimetry (ITC). Results indicated that the CTAB binding capacity of carboxymethyl cellulose increased with increasing NaCl concentrations up to 100 mM, and the thermodynamic behavior of octane solubilization in CTAB micelles, either in the absence or presence of polymer, was found to have a strong dependence on ionic strength. The increasing ionic strength caused the solubilization in CTAB micelles to be less endothermic or even exothermic, but increased the solubilization capacity. Based on the phase separation model, the solubilization was suggested to be driven by enthalpy. It is indicated that increasing ionic strength gave rise to a larger Gibbs energy decrease but a smaller unfavorable entropy increase for octane solubilization in cationic surfactant micelles. Copyright © 2015 Elsevier Inc. All rights reserved.
DeFrates, Kelsey; Markiewicz, Theodore; Callaway, Kayla; Xue, Ye; Stanton, John; Salas-de la Cruz, David; Hu, Xiao
2017-11-01
Biomaterials made from natural proteins and polysaccharides have become increasingly popular in the biomedical field due to their good biocompatibility and tunable biodegradability. However, the low miscibility of polysaccharides with proteins presents challenges in the creation of protein-polysaccharide composite materials. In this study, neat 1-allyl-3-methylimidazolium chloride (AMIMCl) ionic liquid was used to regenerate Thailand gold Bombyx mori silk and microcrystalline cellulose blended films. This solvent was found to not only effectively dissolve both natural polymers, but also preserve the structure and integrity of the polymers. A single glass transition temperature for each blend was found in DSC curves, indicating good miscibility between the Thai silk and cellulose molecules. The structural composition as well as the morphology and thermal stability of blend films were then determined using FTIR, SEM and TGA. It was found that by varying the ratio of Thai silk to cellulose, the thermal and physical properties of the material could be tuned. Blended films tended to be more thermally stable which could be due to the presence of hydrophobic-hydrophobic or electrostatic interactions between the silk and cellulose. These studies offered a new pathway to understand the tunable properties of protein-polysaccharide composite biomaterials with controllable physical and biological properties. Copyright © 2017 Elsevier B.V. All rights reserved.
Degradation mechanism of polysaccharides on irradiated sugarcane bagasse
NASA Astrophysics Data System (ADS)
Ribeiro, M. A.; Oikawa, H.; Mori, M. N.; Napolitano, C. M.; Duarte, C. L.
2013-03-01
Sugarcane bagasse is composed of cellulose, hemicelluloses, lignin, and a minor amount of protein and inorganic materials. Cellulose consists of linear macromolecular chains of glucose, linked by β-1,4-glucosidic bonds between the number one and the number four carbon atoms of the adjacent glucose units. Hemicelluloses are heterogeneous polymers, unlike cellulose, and are usually composed of 50-200 monomer units of pentose such as xylose and arabinose. Lignin is a complex polymer of p-hydroxyphenylpropanoid units connected by CC and COC links. Radiation-induced reactions in the macromolecules of the cellulose materials are known to be initiated through fast distribution of the absorbed energy within the molecules to produce long- and short-lived radicals. The present study was carried out using sugarcane bagasse samples irradiated by a Radiation Dynamics electron beam accelerator with 1.5 MeV and 37 kW, with the objective to evaluate the cleavage of the polysaccharides and the by-products formed as a result of the absorbed dose. The electron beam processing in 30 kGy of absorbed dose changed the sugarcane bagasse structure and composition, causing some cellulose and hemicelluloses cleavage. These cleavages were partial, forming oligosaccharides and liberating the sugars glucose and arabinose. The main by-product was acetic acid, originated from the de-acetylating of hemicelluloses.
NASA Astrophysics Data System (ADS)
Fortunati, E.; Torre, L.
2016-05-01
The need to both avoid wastes and find new renewable resources has led to a new and promising research based on the possibility to revalorize the biomass producing sustainable chemicals and/or materials which may play a major role in replacing systems traditionally obtained from non-renewable sources. Most of the low-value biomass is termed lignocellulosic, referring to its main constituent biopolymers: cellulose, hemicelluloses and lignin. In this context, nanocellulose, and in particular cellulose nanocrystals (CNC), have gain considerable attention as nanoreinforcement for polymer matrices, mainly biodegradable. Derived from the most abundant polymeric resource in nature and with inherent biodegradability, nanocellulose is an interesting nanofiller for the development of nanocomposites for industrial, biomedical and agricultural applications. Due to the high amount of hydroxyl groups on their surface, cellulose nanocrystals are easy to functionalize. Well dispersed CNC are able, in fact, to enhance several properties of polymers, i.e.: thermal, mechanical, barrier, surface wettability, controlled of active compound and/or drug release. The main objective here is to give a general overview of CNC applications, summarizing our recent developments of bio-based nanocomposite formulations reinforced with cellulose nanocrystals extracted from different natural sources and/or wastes for food packaging, medical and agricultural sectors.
Zhang, Jianjun; Yue, Liping; Hu, Pu; Liu, Zhihong; Qin, Bingsheng; Zhang, Bo; Wang, Qingfu; Ding, Guoliang; Zhang, Chuanjian; Zhou, Xinhong; Yao, Jianhua; Cui, Guanglei; Chen, Liquan
2014-01-01
Inspired by Taichi, we proposed rigid-flexible coupling concept and herein developed a highly promising solid polymer electrolyte comprised of poly (ethylene oxide), poly (cyano acrylate), lithium bis(oxalate)borate and robust cellulose nonwoven. Our investigation revealed that this new class solid polymer electrolyte possessed comprehensive properties in high mechanical integrity strength, sufficient ionic conductivity (3 × 10−4 S cm−1) at 60°C and improved dimensional thermostability (up to 160°C). In addition, the lithium iron phosphate (LiFePO4)/lithium (Li) cell using such solid polymer electrolyte displayed superior rate capacity (up to 6 C) and stable cycle performance at 80°C. Furthermore, the LiFePO4/Li battery could also operate very well even at an elevated temperature of 160°C, thus improving enhanced safety performance of lithium batteries. The use of this solid polymer electrolyte mitigates the safety risk and widens the operation temperature range of lithium batteries. Thus, this fascinating study demonstrates a proof of concept of the use of rigid-flexible coupling solid polymer electrolyte toward practical lithium battery applications with improved reliability and safety. PMID:25183416
Crystallographic snapshot of cellulose synthesis and membrane translocation.
Morgan, Jacob L W; Strumillo, Joanna; Zimmer, Jochen
2013-01-10
Cellulose, the most abundant biological macromolecule, is an extracellular, linear polymer of glucose molecules. It represents an essential component of plant cell walls but is also found in algae and bacteria. In bacteria, cellulose production frequently correlates with the formation of biofilms, a sessile, multicellular growth form. Cellulose synthesis and transport across the inner bacterial membrane is mediated by a complex of the membrane-integrated catalytic BcsA subunit and the membrane-anchored, periplasmic BcsB protein. Here we present the crystal structure of a complex of BcsA and BcsB from Rhodobacter sphaeroides containing a translocating polysaccharide. The structure of the BcsA-BcsB translocation intermediate reveals the architecture of the cellulose synthase, demonstrates how BcsA forms a cellulose-conducting channel, and suggests a model for the coupling of cellulose synthesis and translocation in which the nascent polysaccharide is extended by one glucose molecule at a time.
Structure and transformation of tactoids in cellulose nanocrystal suspensions
NASA Astrophysics Data System (ADS)
Wang, Pei-Xi; Hamad, Wadood Y.; MacLachlan, Mark J.
2016-05-01
Cellulose nanocrystals obtained from natural sources are of great interest for many applications. In water, cellulose nanocrystals form a liquid crystalline phase whose hierarchical structure is retained in solid films after drying. Although tactoids, one of the most primitive components of liquid crystals, are thought to have a significant role in the evolution of this phase, they have evaded structural study of their internal organization. Here we report the capture of cellulose nanocrystal tactoids in a polymer matrix. This method allows us to visualize, for the first time, the arrangement of cellulose nanocrystals within individual tactoids by electron microscopy. Furthermore, we can follow the structural evolution of the liquid crystalline phase from tactoids to iridescent-layered films. Our insights into the early nucleation events of cellulose nanocrystals give important information about the growth of cholesteric liquid crystalline phases, especially for cellulose nanocrystals, and are crucial for preparing photonics-quality films.
Iurian, Sonia; Turdean, Luana; Tomuta, Ioan
2017-01-01
This study focuses on the development of a drug product based on a risk assessment-based approach, within the quality by design paradigm. A prolonged release system was proposed for paliperidone (Pal) delivery, containing Kollidon ® SR as an insoluble matrix agent and hydroxypropyl cellulose, hydroxypropyl methylcellulose (HPMC), or sodium carboxymethyl cellulose as a hydrophilic polymer. The experimental part was preceded by the identification of potential sources of variability through Ishikawa diagrams, and failure mode and effects analysis was used to deliver the critical process parameters that were further optimized by design of experiments. A D-optimal design was used to investigate the effects of Kollidon SR ratio ( X 1 ), the type of hydrophilic polymer ( X 2 ), and the percentage of hydrophilic polymer ( X 3 ) on the percentages of dissolved Pal over 24 h ( Y 1 - Y 9 ). Effects expressed as regression coefficients and response surfaces were generated, along with a design space for the preparation of a target formulation in an experimental area with low error risk. The optimal formulation contained 27.62% Kollidon SR and 8.73% HPMC and achieved the prolonged release of Pal, with low burst effect, at ratios that were very close to the ones predicted by the model. Thus, the parameters with the highest impact on the final product quality were studied, and safe ranges were established for their variations. Finally, a risk mitigation and control strategy was proposed to assure the quality of the system, by constant process monitoring.
Development and optimization of buspirone oral osmotic pump tablet
Derakhshandeh, K.; berenji, M. Ghasemnejad
2014-01-01
The aim of the current study was to design a porous osmotic pump–based drug delivery system for controlling the release of buspirone from the delivery system. The osmotic pump was successfully developed using symmetric membrane coating. The core of the tablets was prepared by direct compression technique and coated using dip-coating technique. Drug release from the osmotic system was studied using USP paddle type apparatus. The effect of various processing variables such as the amount of osmotic agent, the amount of swellable polymer, concentration of the core former, concentration of the plasticizer, membrane thickness, quantum of orifice on drug release from osmotic pump were evaluated. Different kinetic models (zero order, first order and Higuchi model) were applied to drug release data in order to establish the kinetics of drug release. It was found that the drug release was mostly affected by the amount of NaCl as osmotic agent, the swellable polymer; hydroxy propyl methyl cellulose (HPMC), the amount of PEG-400 and cellulose acetate in the coating solution and thickness of the semipermeable membrane. The optimized formulation released buspirone independent of pH and orifice quantum at the osmogen amount of 42%, hydrophilic polymer of 13% and pore size of 0.8 mm on the tablet surface. The drug release of osmotic formulation during 24 h showed zero order kinetics and could be suggested that this formulation as a once-daily regimen improves pharmacokinetic parameters of the drug and enhances patient compliance. PMID:25657794
Development and optimization of buspirone oral osmotic pump tablet.
Derakhshandeh, K; Berenji, M Ghasemnejad
2014-01-01
The aim of the current study was to design a porous osmotic pump-based drug delivery system for controlling the release of buspirone from the delivery system. The osmotic pump was successfully developed using symmetric membrane coating. The core of the tablets was prepared by direct compression technique and coated using dip-coating technique. Drug release from the osmotic system was studied using USP paddle type apparatus. The effect of various processing variables such as the amount of osmotic agent, the amount of swellable polymer, concentration of the core former, concentration of the plasticizer, membrane thickness, quantum of orifice on drug release from osmotic pump were evaluated. Different kinetic models (zero order, first order and Higuchi model) were applied to drug release data in order to establish the kinetics of drug release. It was found that the drug release was mostly affected by the amount of NaCl as osmotic agent, the swellable polymer; hydroxy propyl methyl cellulose (HPMC), the amount of PEG-400 and cellulose acetate in the coating solution and thickness of the semipermeable membrane. The optimized formulation released buspirone independent of pH and orifice quantum at the osmogen amount of 42%, hydrophilic polymer of 13% and pore size of 0.8 mm on the tablet surface. The drug release of osmotic formulation during 24 h showed zero order kinetics and could be suggested that this formulation as a once-daily regimen improves pharmacokinetic parameters of the drug and enhances patient compliance.
Kombucha Multimicrobial Community under Simulated Spaceflight and Martian Conditions
NASA Astrophysics Data System (ADS)
Podolich, O.; Zaets, I.; Kukharenko, O.; Orlovska, I.; Reva, O.; Khirunenko, L.; Sosnin, M.; Haidak, A.; Shpylova, S.; Rabbow, E.; Skoryk, M.; Kremenskoy, M.; Demets, R.; Kozyrovska, N.; de Vera, J.-P.
2017-05-01
Kombucha microbial community (KMC) produces a cellulose-based biopolymer of industrial importance and a probiotic beverage. KMC-derived cellulose-based pellicle film is known as a highly adaptive microbial macrocolony—a stratified community of prokaryotes and eukaryotes. In the framework of the multipurpose international astrobiological project "BIOlogy and Mars Experiment (BIOMEX)," which aims to study the vitality of prokaryotic and eukaryotic organisms and the stability of selected biomarkers in low Earth orbit and in a Mars-like environment, a cellulose polymer structural integrity will be assessed as a biomarker and biotechnological nanomaterial. In a preflight assessment program for BIOMEX, the mineralized bacterial cellulose did not exhibit significant changes in the structure under all types of tests. KMC members that inhabit the cellulose-based pellicle exhibited a high survival rate; however, the survival capacity depended on a variety of stressors such as the vacuum of space, a Mars-like atmosphere, UVC radiation, and temperature fluctuations. The critical limiting factor for microbial survival was high-dose UV irradiation. In the tests that simulated a 1-year mission of exposure outside the International Space Station, the core populations of bacteria and yeasts survived and provided protection against UV; however, the microbial density of the populations overall was reduced, which was revealed by implementation of culture-dependent and culture-independent methods. Reduction of microbial richness was also associated with a lower accumulation of chemical elements in the cellulose-based pellicle film, produced by microbiota that survived in the post-test experiments, as compared to untreated cultures that populated the film.
Electrical study on Carboxymethyl Cellulose-Polyvinyl alcohol based bio-polymer blend electrolytes
NASA Astrophysics Data System (ADS)
Saadiah, M. A.; Samsudin, A. S.
2018-04-01
The present work deals with the formulation of bio-materials namely carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA) for bio-polymer blend electrolytes (BBEs) system which was successfully carried out with different ratio of polymer blend. The biopolymer blend was prepared via economical & classical technique that is solution casting technique and was characterized by using impedance spectroscopy (EIS). The ionic conductivity was achieved to optimum value 9.12 x 10-6 S/cm at room temperature for sample containing ratio 80:20 of CMC:PVA. The highest conducting sample was found to obey the Arrhenius behaviour with a function of temperature. The electrical properties were analyzed using complex permittivity ε* and complex electrical modulus M* for BBEs system and it shows the non-Debye characteristics where no single relaxation time has observed.
Redox-Active Nitroxide Radical Polymers: From Green Catalysts to Energy Storage Devices
NASA Astrophysics Data System (ADS)
Waskitoaji, Wihatmoko; Suga, Takeo; Nishide, Hiroyuki
2009-09-01
Robust but redox-active radical polymers bearing 2, 2, 6, 6-tetramethylpiperidin-N-oxy (TEMPO) were investigated as a metal-free, green mediator/catalyst for the oxidation of alcohol derivatives, and as a new electrode-active and charge-storage material. The TEMPO-mediated oxidation of the primary alcohol group of the natural cellulose improved the water-dispersivity of cellulose, and the polymer-supported catalysts or redox resins allow facile removal of catalysts from products by simple filtration. Other radical molecule (e.g. galvinoxyl) was also used as a mediator, which is coupled with the molecular oxygen. A reversible one-electron redox reaction of TEMPO allowed its application as an electrode-active material featuring high cyclability (>500 cycles), relatively high battery electrode capacity (100-135 mAh/g), and fast electrode kinetics, leading to the high power rate capability of the battery. The radical polymer-based electrodes also provided good processability and shape flexibility, which promised the paper-like and wearable energy-storage devices.
Rane, Ashish Babulal; Gattani, Surendra Ganeshlal; Kadam, Vinayak Dinkar; Tekade, Avinash Ramrao
2009-11-01
The aim of present investigation was to develop press coated tablet for pulsatile drug delivery of ketoprofen using hydrophilic and hydrophobic polymers. The drug delivery system was designed to deliver the drug at such a time when it could be most needful to patient of rheumatoid arthritis. The press coated tablets containing ketoprofen in the inner core was formulated with an outer shell by different weight ratio of hydrophobic polymer (micronized ethyl cellulose powder) and hydrophilic polymers (glycinemax husk or sodium alginate). The release profile of press coated tablet exhibited a lag time followed by burst release, in which outer shell ruptured into two halves. Authors also investigated factors influencing on lag time such as particle size and viscosity of ethyl cellulose, outer coating weight and paddle rpm. The surface morphology of the tablet was examined by a scanning electron microscopy. Differential scanning calorimeter and Fourier transformed infrared spectroscopy study showed compatibility between ketoprofen and coating material.
Cheng, Lizhen; Gai, Xiumei; Wen, Haoyang; Liu, Dandan; Tang, Xin; Wang, Yanyan; Wang, Tuanjie; Pan, Weisan; Yang, Xinggang
2018-01-01
The objective of this study was to investigate the fundamental properties of propranolol hydrochloride osmotic pump tablets coated by aqueous polymer dispersion, simultaneously exploring the in vitro and in vivo correlation of the tablet. The physicochemical properties and parameters of aqueous polymer dispersion membranes (SEM, water uptake, and water vapor transmission coefficient) were investigated. In addition, the release behavior and the in vitro release and in vivo absorption profiles of the tablets coated by aqueous polymer dispersion were investigated by comparing with propranolol hydrochloride osmotic pump tablets coated by an organic solvent. Results showed that the similarity factor (f 2 ) between cellulose acetate-coated tablet and Eudragit-coated tablet was 78.1, and f 2 between cellulose acetate-coated tablet and Kollicoat-coated tablet was 77.6. The linear IVIVC of Eudragit-coated and Kollicoat-coated osmotic pump tablets was determined, which confirmed excellent correlation between the absorption in vivo and the drug release in vitro. Consequently, the membrane coated by aqueous polymer dispersion or organic solvent has similar in vitro release rates of controlled release. Also, compared with organic solvent coating, aqueous polymer dispersion has numerous advantages, such as reduced toxicity and no environmental damage. Therefore, the aqueous polymer dispersion technology has enormous potential as a replacement of organic solvent coating.
Novel antimicrobial and biofilm-controlling cellulosic polymers
NASA Astrophysics Data System (ADS)
Padmanabhuni, Revathi V.
Cotton and cellulose acetate (CA) are cellulosic polymers with versatile applications. Like any other polymeric materials, cellulosic materials are also susceptible to microbial contamination and cause serious nosocomial infections. Hence, there is a definite need to develop antimicrobial cellulosic materials to prevent microbial colonization. Henceforth, we prepared a suitable polycation to treat cotton fabrics and CA films by LbL self-assembly process to achieve potent antimicrobial functions. The treated fabrics demonstrated total kill against E. coli and S. aureus in 2 h contact time whereas treated CA films, even after 6 h, could inactivate only 98 % of bacteria. Since CA films are more hydrophobic, have less surface charge, and surface area than cotton fabrics, LbL procedure was not much effective for CA films to achieve potent antimicrobial functions. Yet, CA is another very important cellulosic polymer with various applications in which antimicrobial activity is often desired. So, to improve the antimicrobial activity of CA films, we designed a novel strategy to coat the surface of CaCO3 fillers with quaternary ammonium salts (QAS)based fatty acids to make the filler surface organophilic and accomplish antibacterial activity concurrently, rendering the resulting polymer-filler composites antimicrobial. Thus, a series of QAS-based fatty acids (C8-C16) were synthesized, coated onto CaCO 3, and used as antimicrobial additives (5 %) in CA films. Although C8-quat-CaCO 3 could only provide 94 % of reduction of bacteria, both C12- and C16- quats and their corresponding quat-coated CaCO3 provided a total kill of S. aureus and E. coli in 2 h. These findings suggested that it is feasible to use QAS-based fatty acids to coat CaCO3 and use them as antimicrobial additives of CA films to achieve potent antimicrobial effects. Building on these results, to further evaluate the applicability of the antimicrobial filler strategy, we synthesized an N-halamine based fatty acid, coated onto CaCO3 and used as antimicrobial additives in CA films; the resulting samples provided excellent antimicrobial and biofilm-controlling effects, confirming that the antimicrobial filler approach could be an effective strategy for the antimicrobial treatments of CA and potentially other related hydrophobic polymeric materials.
Cellulose microfibrils in plants: biosynthesis, deposition, and integration into the cell wall.
Brett, C T
2000-01-01
Cellulose occurs in all higher plants and some algae, fungi, bacteria, and animals. It forms microfibrils containing the crystalline allomorphs, cellulose I alpha and I beta. Cellulose molecules are 500-15,000 glucose units long. What controls molecular size is unknown. Microfibrils are elongated by particle rosettes in the plasma membrane (cellulose synthase complexes). The precursor, UDP-glucose, may be generated from sucrose at the site of synthesis. The biosynthetic mechanism may involve lipid-linked intermediates. Cellulose synthase has been purified from bacteria, but not from plants. In plants, disrupted cellulose synthase may form callose. Cellulose synthase genes have been isolated from bacteria and plants. Cellulose-deficient mutants have been characterised. The deduced amino acid sequence suggests possible catalytic mechanisms. It is not known whether synthesis occurs at the reducing or nonreducing end. Endoglucanase may play a role in synthesis. Nascent cellulose molecules associate by Van der Waals and hydrogen bonds to form microfibrils. Cortical microtubules control microfibril orientation, thus determining the direction of cell growth. Self-assembly mechanisms may operate. Microfibril integration into the wall occurs by interactions with matrix polymers during microfibril formation.
Cellulose Electro-Active Paper: From Discovery to Technology Applications
NASA Astrophysics Data System (ADS)
Abas, Zafar; Kim, Heung Soo; Kim, Jaehwan; Kim, Joo-Hyung
2014-09-01
Cellulose electro-active paper (EAPap) is an attractive material of electro-active polymers (EAPs) family due to its smart characteristics. EAPap is thin cellulose film coated with metal electrodes on both sides. Its large displacement output, low actuation voltage and low power consumption can be used for biomimetic sensors/actuators and electromechanical system. Because cellulose EAPap is ultra-lightweight, easy to manufacture, inexpensive, biocompatible, and biodegradable, it has been employed for many applications such as bending actuator, vibration sensor, artificial muscle, flexible speaker, and can be advantageous in areas such as micro-insect robots, micro-flying objects, microelectromechanical systems, biosensors, and flexible displays.
In efforts to apply a polymer-based aqueous biphasic system (ABS) extraction to the paper pulping process, the study of the distribution of various lignin and cellulosic fractions in ABS and the effects of temperature on system composition and solute partitioning have been inv...
Multiphase materials with lignin. IV. Blends of hydroxypropyl cellulose with lignin
Timothy G. Rials; Wolfgang G. Glasser
1989-01-01
Polymer blends of hydroxypropyl cellulose (HPC) and organosolv lignin (OSL) were prepared by mixing in solutions of both pyridine and dioxane, and casting as films, and by mixing in the melt followed by extrusion. All preparations exhibited partial miscibility as evidenced by a single Tg up to a composition of 40 wt % lignin above which phase...
Krishnan A. Iyer; Gregory T. Schueneman; John M. Torkelson
2015-01-01
Cellulose nanocrystals (CNCs), a class of renewable bionanomaterials with excellent mechanical properties, have gained major interest as filler for polymers. However, challenges associated with effective CNC dispersion have hindered the production of composites with desired property enhancements. Here, composites of polypropylene (PP) and low density polyethylene (LDPE...
Anju Gupta; William Simmons; Gregory T. Schueneman; Donald Hylton; Eric A. Mintz
2017-01-01
Improving the processability and physical properties of sustainable biobased polymers and biobased fillers is essential to preserve its biodegradability and make them suitable for different end user applications. Herein, we report the use of spray-dried lignin-coated cellulose nanocrystals (L-CNCs), a biobased filler, to modify the rheological and thermos-mechanical...
Amber J. Vanden Wymelenberg; Grzegorz Sabat; Diego Martinez; Alex S. Rajangam; Tuula T. Teeri; Jill A. Gaskell; Philip J. Kersten; Daniel Cullen
2005-01-01
The white rot basidiomycete, Phanerochaete chrysosporium, employs an array of extracellular enzymes to completely degrade the major polymers of wood : cellulose, hemicellulose and lignin. Towards the identification of participating enzymes, 268 likely secreted proteins were predicted using SignalP and TargetP algorithms. To assess the reliability of secretome...
Mariko Ago; Joseph E. Jakes; Leena-Sisko Johansson; Sunkyu Park; Orlando J. Rojas
2012-01-01
Sub-100 nm resolution local thermal analysis, X-ray photoelectron spectroscopy (XPS), and water contact angle (WCA) measurements were used to relate surface polymer distribution with the composition of electrospun fiber mats and spin coated films obtained from aqueous dispersions of lignin, polyvinyl alcohol (PVA), and cellulose nanocrystal (CNC). Defect-free lignin/...
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hiras, Jennifer; Wu, Yu-Wei; Deng, Kai
ABSTRACT Glycoside hydrolases (GHs) are key enzymes in the depolymerization of plant-derived cellulose, a process central to the global carbon cycle and the conversion of plant biomass to fuels and chemicals. A limited number of GH families hydrolyze crystalline cellulose, often by a processive mechanism along the cellulose chain. During cultivation of thermophilic cellulolytic microbial communities, substantial differences were observed in the crystalline cellulose saccharification activities of supernatants recovered from divergent lineages. Comparative community proteomics identified a set of cellulases from a population closely related to actinobacteriumThermobispora bisporathat were highly abundant in the most active consortium. Among the cellulases fromT. bispora,more » the abundance of a GH family 12 (GH12) protein correlated most closely with the changes in crystalline cellulose hydrolysis activity. This result was surprising since GH12 proteins have been predominantly characterized as enzymes active on soluble polysaccharide substrates. Heterologous expression and biochemical characterization of the suite ofT. bisporahydrolytic cellulases confirmed that the GH12 protein possessed the highest activity on multiple crystalline cellulose substrates and demonstrated that it hydrolyzes cellulose chains by a predominantly random mechanism. This work suggests that the role of GH12 proteins in crystalline cellulose hydrolysis by cellulolytic microbes should be reconsidered. IMPORTANCECellulose is the most abundant organic polymer on earth, and its enzymatic hydrolysis is a key reaction in the global carbon cycle and the conversion of plant biomass to biofuels. The glycoside hydrolases that depolymerize crystalline cellulose have been primarily characterized from isolates. In this study, we demonstrate that adapting microbial consortia from compost to grow on crystalline cellulose generated communities whose soluble enzymes exhibit differential abilities to hydrolyze crystalline cellulose. Comparative proteomics of these communities identified a protein of glycoside hydrolase family 12 (GH12), a family of proteins previously observed to primarily hydrolyze soluble substrates, as a candidate that accounted for some of the differences in hydrolytic activities. Heterologous expression confirmed that the GH12 protein identified by proteomics was active on crystalline cellulose and hydrolyzed cellulose by a random mechanism, in contrast to most cellulases that act on the crystalline polymer in a processive mechanism.« less
Leonaviciute, Gintare; Bonengel, Sonja; Mahmood, Arshad; Ahmad Idrees, Muneeb; Bernkop-Schnürch, Andreas
2016-06-25
The aim of this study was the design of novel S-protected thiolated hydroxyethyl cellulose (HEC) and the assessment of its mucoadhesive properties and biodegradability compared to the corresponding unmodified polymer. Thiolated HEC was S-protected via disulfide bond formation between 6-mercaptonicotinamide (6-MNA) and the thiol substructures of the polymer. In vitro screening of mucoadhesive properties was accomplished using two different methods: rotating cylinder studies and viscosity measurements. Moreover, biodegradability of these polymers by cellulase, xylanase and lysozyme was evaluated. MTT and LDH assays were performed on Caco-2 cells to determine the cytotoxicity of S-protected thiolated HEC. Thiolated HEC displayed 280.09±1.70μmol of free thiol groups per gram polymer. S-protected thiolated HEC exhibiting 270.8±21.11μmol immobilized 6-MNA ligands per gram of polymer was shown being 2.4-fold more mucoadhesive compared to thiolated HEC. No mucoadhesion was observed in case of unmodified HEC. Results were in a good agreement with rheological studies. The presence of free thiol moieties likely caused lower degree of hydrolysis by xylanase, whereas the degradation by both enzymes cellulase and xylanase was more hampered when 6-MNA was introduced as ligand for thiol group's protection. Findings in cell viability revealed that all three conjugates were non-toxic. S-protection of thiolated hydroxyethyl cellulose improved mucoadhesive properties and provided pronounced stability towards enzymatic attack, that makes this excipient superior for non-invasive drug administration over thiolated and unmodified forms. Copyright © 2016 Elsevier Ltd. All rights reserved.
Water in polymer membranes. 4. Raman scattering from cellulose acetate films
DOE Office of Scientific and Technical Information (OSTI.GOV)
Scherer, J.R.; Bailey, G.F.; Kint, S.
Raman scattering was observed from thin film optical waveguides of cellulose acetate exposed to water vapor from 0% to 100% relative humidity (RH), and from dilute solutions of water in methyl acetate. Spectra of cellulose acetate (CA398, 39.8% acetyl) at low RH and cellulose triacetate (CTA) at low and high RH are consistent with the presence of water monomers that are weakly hydrogen bonded to acetyl C=O groups. Differences between the spectra of water in CA398 and CTA at low RH are attributed to sequential hydrogen bonding involving OH groups in CA398. At high RH, CA398 and CTA (to amore » lesser extent) show bands attributed to water/water interactions that are similar to those found in sequentially hydrogen-bonded hydrates. CA398 films that are annealed at high temperatures exhibit decreased water/water interactions at high RH. Exposure of CA398 films to D/sub 2/O converts > 90% of all polymer OH groups to OD groups. This indicates that water is accessible to nearly all regions of the polymer containing OH groups. Annealing does not alter this accessibility but does reduce the total water content by roughly half, at 100% RH. Hydrogen-bonded C=O groups are associated with a band centered at 1731 cm/sup -1/ which increases in intensity with increasing water content in the film but does not shift in frequency. 38 references, 16 figures, 1 table.« less
2-Hydroxypropyltrimethylammonium xylan adsorption onto rod-like cellulose nanocrystal.
Sim, Jae Hyun; Dong, Shuping; Röemhild, Katrin; Kaya, Abdulaziz; Sohn, Daewon; Tanaka, Keiji; Roman, Maren; Heinze, Thomas; Esker, Alan R
2015-02-15
Chemical incompatibility and relatively weak interaction between lignocellulosic fibers and synthetic polymers have made studies of wood fiber-thermoplastic composite more challenging. In this study, adsorption of 2-hydroxypropyltrimethylammonium xylans onto rod-like cellulose nanocrystals are investigated by zeta-potential measurements, and polarized and depolarized dynamic light scattering as a factor for better understanding of lignocellulosic fibers and cellulose nanocrystals. Zeta-potential measurements show xylan derivative adsorption onto cellulose nanocrystals. Decay time distributions of the ternary system and binary system from dynamic light scattering show that aggregates exist in the binary system and they disappear in the ternary system. At low 2-hydroxypropyltrimethylammonium xylan concentrations relative to that of cellulose nanocrystal, xylan derivatives adsorbed onto some of the cellulose nanocrystal. Hence, more xylan derivatives adsorbed onto cellulose nanocrystal increased with increasing xylan derivative concentration. Also, the concentration dependence of the ratio of the rotational diffusion coefficient to the translational diffusion coefficient revealed a strong adsorptive interaction between xylan derivatives and the cellulose nanocrystals. Copyright © 2014 Elsevier Inc. All rights reserved.
Paukszta, Dominik; Borysiak, Slawomir
2013-01-01
Cellulose is the most important and the most abundant plant natural polymer. It shows a number of interesting properties including those making it attractive as a filler of composite materials with a thermoplastic polymer matrix. Production of such composite materials, meeting the standards of green technology, has increased from 0.36 million tons in 2007 to 2.33 million tons in 2012. It is predicted that by 2020 their production will reach 3.45 million tons. Production of biocomposites with lignocellulosic components poses many problems that should be addressed. This paper is a review of the lignocellulosic materials currently used as polymer fillers. First, the many factors determining the macroscopic properties of such composites are described, with particular attention paid to the poor interphase adhesion between the polymer matrix and a lignocellulosic filler and to the effects of cellulose occurrence in polymorphic varieties. The phenomenon of cellulose polymorphism is very important from the point of view of controlling the nucleation abilities of the lignocellulosic filler and hence the mechanical properties of composites. Macroscopic properties of green composites depend also on the parameters of processing which determine the magnitude and range of shearing forces. The influence of shearing forces appearing upon processing the supermolecular structure of the polymer matrix is also discussed. An important problem from the viewpoint of ecology is the possibility of composite recycling which should be taken into account at the design stage. The methods for recycling of the composites made of thermoplastic polymers filled with renewable lignocellulosic materials are presented and discussed. This paper is a review prepared on the basis of currently available literature which describes the many aspects of the problems related to the possibility of using lignocellulosic components for production of composites with polymers. PMID:28811406
The Synthesis of Cellulose Graft Copolymers Using Cu(0)-Mediated Polymerization
NASA Astrophysics Data System (ADS)
Donaldson, Jason L.
Cellulose is the most abundant renewable polymer on the planet and there is great interest in expanding its use beyond its traditional applications. However, its hydrophilicity and insolubility in most common solvent systems are obstacles to its widespread use in advanced materials. One way to counteract this is to attach hydrophobic polymer chains to cellulose: this allows the properties of the copolymer to be tailored by the molecular weight, density, and physical properties of the grafts. Two methods were used here to synthesize the graft copolymers: a 'grafting-from' approach, where synthetic chains were grown outward from bromoester moieties on cellulose (Cell-BiB) via Cu(0)-mediated polymerization; and a 'grafting-to' approach, where fully formed synthetic chains with terminal sulfide functionality were added to cellulose acetate with methacrylate functionality (CA-MAA) via thiol-ene Michael addition. The Cell-BiB was synthesized in the ionic liquid 1-butyl-3-methylimidazolium chloride and had a degree of substitution of 1.13. Polymerization from Cell-BiB proceeded at similar but slightly slower rate than an analogous non-polymeric initiator (EBiB). The average graft density of poly(methyl acrylate) chains was 0.71 chains/ring, with a maximum of 1.0 obtained. The graft density when grafting poly(methyl methacrylate) was only 0.15, and this appeared to be due to the slow initiation of BiB groups. Using EBiB to model the reaction and improve the design should allow this to be overcome. Chain extension experiments demonstrated the living behaviour of the polymer. The CA-MAA was synthesized by esterification with methacrylic acid. Reactions of CA-MAA with thiophenol and dodecanethiol resulted in quantitative addition of the thiol to the alkene. The grafts were synthesized by Cu(0)-mediated polymerization from a bifunctional initiator containing a disulfide bond, followed by reduction to sulfides. The synthetic polymers were successfully grafted to CA-MAA but the grafting yield was limited by the low sulfide functionality. Better retention of sulfide functionality is necessary for more efficient grafting.
Synthesis and characterization of graphene/cellulose nanocomposite
NASA Astrophysics Data System (ADS)
Kafy, Abdullahil; Yadav, Mithilesh; Kumar, Kishor; Kumar, Kishore; Mun, Seongcheol; Gao, Xiaoyuan; Kim, Jaehwan
2014-04-01
Cellulose is one of attractive natural polysaccharides in nature due to its good chemical stability, mechanical strength, biocompatibility, hydrophilic, and biodegradation properties [1-2]. The main disadvantages of biopolymer films like cellulose are their poor mechanical properties. Modification of polymers with inorganic materials is a new way to improve polymer properties such as mechanical strength [3-4]. Presently, the use of graphene/graphene oxide (GO) in materials research has attracted tremendous attention in the past 40 years in various fields including biomedicine, information technology and nanotechnology[5-7]. Graphene, a single sheet of graphite, has an ideal 2D structure with a monolayer of carbon atoms packed into a honeycomb crystal plane. Using both experimental and theoretical scientific research, researchers including Geim, Rao and Stankovich [8-10] have described the attractiveness of graphene in the materials research field. Due to its sp2 hybrid carbon network as well as extraordinary mechanical, electronic, and thermal properties, graphene has opened new pathways for developing a wide range of novel functional materials. Perfect graphene does not exist naturally, but bulk and solution processable functionalized graphene materials including graphene oxide (GO) can now be prepared [11-13].The large surface area of GO has a number of functional groups, such as -OH, -COOH, -O- , and C=O, which make GO hydrophilic and readily dispersible in water as well as some organic solvents[14] , thereby providing a convenient access to fabrication of graphene-based materials by solution casting. According to several reports [15-17], GO can be dispersed throughout a selected polymer matrix to make GO-based nanocomposites with excellent mechanical and thermal properties. Since GO is prepared from low-cost graphite, it has an outstanding price advantage over CNTs, which has encouraged studies of GO/synthetic polymer composites [18-20]. In some reported papers, graphene oxide has also been used to reinforce polysaccharide matrices such as carboxymethyl cellulose-starch[21]. Here, we report a simple and environmentally benign preparation of GO/cellulose nanocomposite films by a simple solution mixing-curing method.
Ponomarev, Nikolai; Repo, Eveliina; Srivastava, Varsha; Sillanpää, Mika
2017-11-15
Synthesis of nanocomposites was performed using microcrystalline cellulose (MCC), MgCl 2 in PEG/NaOH solvent by a thermal-assisted method at different temperatures by varying time and the amount of MCC. Results of XRD, FTIR, and EDS mapping showed that the materials consisted of only cellulose (CL) and magnesium hydroxide (MH). According to FTIR and XRD, it was found that crystallinity of MH in cellulose nanocomposites is increased with temperature and heating time and decreased with increasing of cellulose amount. The PEG/NaOH solvent has a significant effect on cellulose and Mg(OH) 2 morphology. BET and BJH results demonstrated the effects of temperature and cellulose amount on the pore size corresponding to mesoporous materials. TG and DTG analyses showed the increased thermal stability of cellulose nanocomposites with increasing temperature. TEM and SEM analyses showed an even distribution of MH nanostructures with various morphology in the cellulose matrix. The cellulose presented as the polymer matrix in the nanocomposites. It was supposed the possible interaction between cellulose and Mg(OH) 2 . The novel synthesis method used in this study is feasible, cost-efficient and environmentally friendly. Copyright © 2017 Elsevier Ltd. All rights reserved.
Unexplored possibilities of all-polysaccharide composites.
Simkovic, Ivan
2013-06-20
Composites made solely from polysaccharides are mostly ecological because they can degrade without leaving behind ecologically harmful residues, in contrast to composites which contain synthetic polymers. Herein, the following groups of all-polysaccharide composites (APCs) are discussed: an all-cellulose group that includes cotton composites, cellulose combined with other polysaccharides, as well as those based on chitin/chitosan, heparin, hyaluronan, xylan, glucomannan, pectin, xyloglucan, arabinan, starch, carrageenan, alginate, galactan as one of the components in combination with other polysaccharides. They can be used in medical, paper, food, packing, textile, electronic, mechanical engineering and other applications. The composites were tested for absorptivity, biodegradability, crystallinity, rheology, and mechanical, optical, separation, gelling, pasting, film-forming, adhesive, antimicrobial properties, as well as water vapor permeability, water repellency, dye uptake, and fire-retardancy. Except for food applications, composites based on more than two types of polysaccharides have rarely been used and many possible combinations remain unexplored. Copyright © 2013 Elsevier Ltd. All rights reserved.
Impact of CCR1 silencing on the assembly of lignified secondary walls in Arabidopsis thaliana.
Ruel, Katia; Berrio-Sierra, Jimmy; Derikvand, Mohammad Mir; Pollet, Brigitte; Thévenin, Johanne; Lapierre, Catherine; Jouanin, Lise; Joseleau, Jean-Paul
2009-01-01
A cinnamoyl-CoA reductase 1 knockout mutant in Arabidopsis thaliana was investigated for the consequences of lignin synthesis perturbation on the assembly of the cell walls. The mutant displayed a dwarf phenotype and a strong collapse of its xylem vessels corresponding to lower lignin content and a loss of lignin units of the noncondensed type. Transmission electron microscopy revealed that the transformation considerably impaired the capacity of interfascicular fibers and vascular bundles to complete the assembly of cellulose microfibrils in the S(2) layer, the S(1) layer remaining unaltered. Such disorder in cellulose was correlated with X-ray diffraction showing altered organization. Semi-quantitative immunolabeling of lignins showed that the patterns of distribution were differentially affected in interfascicular fibers and vascular bundles, pointing to the importance of noncondensed lignin structures for the assembly of a coherent secondary wall. The use of laser capture microdissection combined with the microanalysis of lignins and polysaccharides allowed these polymers to be characterized into specific cell types. Wild-type A. thaliana displayed a two-fold higher syringyl to guaiacyl ratio in interfascicular fibers compared with vascular bundles, whereas this difference was less marked in the cinnamoyl-CoA reductase 1 knockout mutant.
Caveats when Analyzing Ultra-high Molar Mass Polymers by SEC
USDA-ARS?s Scientific Manuscript database
The analysis of ultra-high molar mass (M > 1 million g/mol) polymers via size-exclusion chromatography (SEC) presents a number of non-trivial challenges. Dissolution and full solvation may take days, as is the case for cellulose dissolution in non-complexing non degrading solvents; very low concent...
Cloning and characterization of alpha-glucuronidase enzymes from mixed cultures
USDA-ARS?s Scientific Manuscript database
Hemicellulose is second to cellulose as the most common carbohydrate source on the planet. Efficient utilization of this resource is essential to the economic viability of biomass refineries. Xylan, a primary component of hemicellulose, is a polymer of beta-1,4-linked xylose sugars. This polymer ...
Kajihara, Ryusuke; Noguchi, Shuji; Iwao, Yasunori; Suzuki, Yoshio; Terada, Yasuko; Uesugi, Kentaro; Itai, Shigeru
2015-03-15
Multiple-unit tablets consisting of polymer-coated microgranules and excipients have a number of advantageous pharmaceutical properties. Polymer-coated microgranules are known to often lose their functionality because of damage to the polymer coating caused by tableting, and the mechanism of polymer coating damage as well as the structural changes of excipients upon tableting had been investigated but without in-situ visualization and quantitative analysis. To elucidate the mechanism of coating damage, the internal structures of multiple-unit tablets were investigated by X-ray computed microtomography using synchrotron X-rays. Cross sectional images of the tablets with sub-micron spatial resolution clearly revealed that void spaces remained around the compressed excipient particles in the tablets containing an excipient composed of cellulose and lactose (Cellactose(®) 80), whereas much smaller void spaces remained in the tablets containing an excipient made of sorbitol (Parteck(®) SI 150). The relationships between the void spaces and the physical properties of the tablets such as hardness and disintegration were investigated. Damage to the polymer coating in tablets was found mainly where polymer-coated microgranules were in direct contact with each other in both types of tablets, which could be attributed to the difference in hardness of excipient particles and the core of the polymer-coated microgranules. Copyright © 2015 Elsevier B.V. All rights reserved.
Yinhua Zhou; Talha M. Khan; Jen-Chieh Liu; Canek Fuentes-Hernandez; Jae Won Shim; Ehsan Najafabadi; Jeffrey P. Youngblood; Robert J. Moon; Bernard Kippelen
2014-01-01
We report on efficient solar cells on recyclable cellulose nanocrystal (CNC) substrates with a new device structure wherein polyethylenimine-modified Ag is used as the bottom electron-collecting electrode and high-conductivity poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS, PH1000) is used as the semitransparent top holecollecting electrode. The...
Chiaki Hori; Jill Gaskell; Kiyohiko Igarashi; Phil Kersten; Michael Mozuch; Masahiro Samejima; Dan Cullen
2014-01-01
The white-rot basidiomycetes efficiently degrade all wood cell wall polymers. Generally, these fungi simultaneously degrade cellulose and lignin, but certain organisms, such as Ceriporiopsis subvermispora, selectively remove lignin in advance of cellulose degradation. However, relatively little is known about themechanismof selective ligninolysis. To...
Aqueous alkali metal hydroxide insoluble cellulose ether membrane
NASA Technical Reports Server (NTRS)
Hoyt, H. E.; Pfluger, H. L. (Inventor)
1969-01-01
A membrane that is insoluble in an aqueous alkali metal hydroxide medium is described. The membrane is a resin which is a water-soluble C2-C4 hydroxyalkyl cellulose ether polymer and an insolubilizing agent for controlled water sorption, a dialytic and electrodialytic membrane. It is particularly useful as a separator between electrodes or plates in an alkaline storage battery.
UV-Induced [2+2] Grafting-To Reactions for Polymer Modification of Cellulose.
Conradi, Matthias; Ramakers, Gijs; Junkers, Thomas
2016-01-01
Benzaldehyde-functional cellulose paper sheets have been synthesized via tosylation of cellulose (Whatman No 5) followed by addition of p-hydroxy benzaldehyde. Via UV-induced Paterno-Büchi [2+2] cycloaddition reactions, these aldehyde functional surfaces are grafted with triallylcyanurate, trimethylolpropane allyl ether, and vinyl chloroacetate. In the following, allyl-functional polymers (poly(butyl acrylate), pBA, Mn = 6990 g mol(-1) , Đ = 1.12 and poly(N-isopropyl acrylamide), pNIPAAm, Mn = 9500 g mol(-1) , Đ = 1.16) synthesized via reversible addition fragmentation chain transfer polymerization are conjugated to the celloluse surface in a UV-induced grafting-to approach. With pBA, hydrophobic cellulose sheets are obtained (water contact angle 116°), while grafting of pNIPAAm allows for generation of "smart" surfaces, which are hydrophilic at room temperature, but that become hydrophobic when heated above the characteristic lower critical solution temperature (93° contact angle). The Paterno-Büchi reaction has been shown to be a versatile synthetic tool that also performs well in grafting-to approaches whereby its overall performance seems to be close to that of radical thiol-ene reactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Large-scale additive manufacturing with bioinspired cellulosic materials.
Sanandiya, Naresh D; Vijay, Yadunund; Dimopoulou, Marina; Dritsas, Stylianos; Fernandez, Javier G
2018-06-05
Cellulose is the most abundant and broadly distributed organic compound and industrial by-product on Earth. However, despite decades of extensive research, the bottom-up use of cellulose to fabricate 3D objects is still plagued with problems that restrict its practical applications: derivatives with vast polluting effects, use in combination with plastics, lack of scalability and high production cost. Here we demonstrate the general use of cellulose to manufacture large 3D objects. Our approach diverges from the common association of cellulose with green plants and it is inspired by the wall of the fungus-like oomycetes, which is reproduced introducing small amounts of chitin between cellulose fibers. The resulting fungal-like adhesive material(s) (FLAM) are strong, lightweight and inexpensive, and can be molded or processed using woodworking techniques. We believe this first large-scale additive manufacture with ubiquitous biological polymers will be the catalyst for the transition to environmentally benign and circular manufacturing models.
Filling in the voids of electrospun hydroxypropyl cellulose network: Dielectric investigations
NASA Astrophysics Data System (ADS)
Maximean, Doina Manaila; Danila, Octavian; Ganea, Constantin Paul; Almeida, Pedro L.
2018-04-01
Here we describe an organic electro-optic device, obtained using electrospun hydroxypropyl cellulose (HPC) polymer fibres and nematic liquid crystals (LC). Its working mechanism is similar to that of a classic polymer-dispersed liquid crystal (PDLC) device. The scanning electron microscopy of the HPC deposited fibres shows a mat of fibres with diameters in the nano and micron size range. Dielectric spectroscopy measurements allow the determination of the dependence of the dielectric constant and electric energy loss on frequency and temperature as well as the determination of the activation energy. The electro-optic study shows a very good optical transmission curve, with an "on"-"off" switching voltage of less than 1V/μ m.
[Chemical modification on the surface of nano-particles of ZnO and its characterization].
Yu, Hai-yin; Du, Jun; Gu, Jia-shan; Guan, Ming-yun; Wu, Zheng-cui; Ling, Qing; Sun, Yi-min
2004-02-01
After nano-particles (ZnO) had been encapsulated by a kind of water-soluble cellulose Hydoxyl-Propyl-Methyl Cellulose (HPMC), then methyl methacrylate was grafted onto the surface of them. Thus the surface of nano-ZnO had been successfully modified. FTIR, DTA and TEM were utilized to confirm the results. FTIR shows that HPMC was adsorbed onto the surface of ZnO, and PMMA was also grafted onto its surface, DTA says that the heat stability of HPMC, HPMC-g-PMMA and ZnO/HPMC-g-PMMA increased greatly, TEM photo demonstrates that polymer adhered onto the surface of nano-ZnO which was encapsulated by a layer of film-like polymer.
Wegiel, Lindsay A; Mauer, Lisa J; Edgar, Kevin J; Taylor, Lynne S
2013-01-01
The objective of this study was to investigate intermolecular interactions between resveratrol and polymers in amorphous blends and to study the potential correlations between compound-polymer interactions, manufacturability, and stability of the amorphous system to crystallization during storage. Polymers included two grades of poly (vinylpyrrolidone) (PVP), Eudragit E100 (E100), hydroxypropyl methylcellulose (HPMC), hydroxypropyl methylcellulose acetate succinate (HPMCAS), carboxymethyl cellulose acetate butyrate, and poly (acrylic acid) (PAA). Amorphous blends ("solid dispersions") were prepared by dissolving both resveratrol and polymer in a solvent followed by rotary evaporation. Crystallinity was evaluated using X-ray powder diffraction and was studied as a function of time. Mid-infrared (IR) spectroscopy was used to investigate resveratrol-polymer interactions. Polymer influence on the crystallization behavior of resveratrol varied and could be correlated to the polymer structure, whereby polymers with good hydrogen bond acceptor groups performed better as crystallization inhibitors. Resveratrol-polymer hydrogen bonding interactions could be inferred from the IR spectra. Somewhat surprisingly, E100 and resveratrol showed evidence of an acid-base reaction, in addition to intermolecular hydrogen bonding interactions. PVP K29/32 appeared to form stronger hydrogen bond interactions with resveratrol relative to HPMC, HPMCAS, and PAA, consistent with acceptor group chemistry. Long-term stability of the systems against crystallization suggested that stability is linked to the type and strength of intermolecular interactions present. whereby resveratrol blended with E100 and PVP K29/32 showed the greatest stability to crystallization. In conclusion, amorphous resveratrol is unstable and difficult to form, requiring the assistance of a polymeric crystallization inhibitor to facilitate the formation of an amorphous solid dispersion. Polymers effective at inhibiting crystallization were identified, and it is rationalized that their effectiveness is based on the type and strength of their intermolecular interactions with resveratrol. Copyright © 2012 Wiley Periodicals, Inc.
Sun, Mingyun; Lin, Jennifer S.
2012-01-01
Double-stranded (ds) DNA fragments over a wide size range were successfully separated in blended polymer matrices by microfluidic chip electrophoresis. Novel blended polymer matrices composed of two types of polymers with three different molar masses were developed to provide improved separations of large dsDNA without negatively impacting the separation of small dsDNA. Hydroxyethyl celluloses (HECs) with average molar masses of ~27 kDa and ~1 MDa were blended with a second class of polymer, high-molar mass (~7 MDa) linear polyacrylamide (LPA). Fast and highly efficient separations of commercially available DNA ladders were achieved on a borosilicate glass microchip. A distinct separation of a 1 Kb DNA extension ladder (200 bp to 40,000 bp) was completed in 2 minutes. An orthogonal Design of Experiments (DOE) was used to optimize experimental parameters for DNA separations over a wide size range. We find that the two dominant factors are the applied electric field strength and the inclusion of a high concentration of low-molar mass polymer in the matrix solution. These two factors exerted different effects on the separations of small dsDNA fragments below 1 kbp, medium dsDNA fragments between 1 kbp and 10 kbp, and large dsDNA fragments above 10 kbp. PMID:22009451
Composite fabrication and polymer modification using neoteric solvents
NASA Astrophysics Data System (ADS)
Eastman, Scott A.
This thesis is divided into two research initiatives: The fabrication and study of bulk, co-continuous, cellulosic-polymer composites with the aid of supercritical CO2 (SC CO2); and the study of poly(vinyl alcohol) (PVOH) modification and surface activity in ionic liquids. The first part of this thesis utilizes the tunable solubility, gas-like diffusivity, and omniphilic wettability of SC CO2 to incorporate and subsequently polymerize silicone and poly(enemer) prepolymer mixtures throughout various cellulosic substrates. Chapters two and three investigate the mechanical properties of these composites and demonstrate that nearly every resulting composite demonstrates an improved flexural modulus and energy release rate upon splitting. Fire resistance of these composites was also investigated and indicates that the heat release rate, total heat released, and char yield were significantly improved upon for all silicone composites compared to the untreated cellulosic material. Chapter four looks specifically at aspen-silicone composites for thermo-oxidative studies under applied loads in order to study the effect of silicone incorporation on the failure kinetics of aspen. The aspen-silicone composites tested under these conditions demonstrated significantly longer lifetimes under the same loading and heating conditions compared with untreated aspen. The second part of this thesis focuses on studying ionic liquids as potentially useful solvents and reaction media for poly(vinyl alcohol). Two ionic liquids (1-Butyl-3-methylimidizolium chloride and tributylethylphosphonium diethylphosphate) were found to readily dissolve PVOH. More importantly, we have demonstrated that these solvents can be used as inert reaction media for PVOH modification. Both ionic liquids were found to facilitate the quantitative esterification of PVOH, while only the phosphonium ionic liquid supports the quantitative urethanation of the polymer. In an attempt to tune the surface properties of ionic liquid/polymer solutions, PVOH was also partially esterified with low surface energy substituents. Both surface tension and surface composition of the ionic liquid/polymer solutions can be manipulated by the stoichiometric addition of low surface energy acid chlorides. This work on the modification of PVOH can be directly applied to the modification of polysaccharides such as cellulose which could have important implications from a sustainability and energy standpoint.
2013-01-01
Background Wheat and rice are important food crops with enormous biomass residues for biofuels. However, lignocellulosic recalcitrance becomes a crucial factor on biomass process. Plant cell walls greatly determine biomass recalcitrance, thus it is essential to identify their key factors on lignocellulose saccharification. Despite it has been reported about cell wall factors on biomass digestions, little is known in wheat and rice. In this study, we analyzed nine typical pairs of wheat and rice samples that exhibited distinct cell wall compositions, and identified three major factors of wall polymer features that affected biomass digestibility. Results Based on cell wall compositions, ten wheat accessions and three rice mutants were classified into three distinct groups each with three typical pairs. In terms of group I that displayed single wall polymer alternations in wheat, we found that three wall polymer levels (cellulose, hemicelluloses and lignin) each had a negative effect on biomass digestibility at similar rates under pretreatments of NaOH and H2SO4 with three concentrations. However, analysis of six pairs of wheat and rice samples in groups II and III that each exhibited a similar cell wall composition, indicated that three wall polymer levels were not the major factors on biomass saccharification. Furthermore, in-depth detection of the wall polymer features distinctive in rice mutants, demonstrated that biomass digestibility was remarkably affected either negatively by cellulose crystallinity (CrI) of raw biomass materials, or positively by both Ara substitution degree of non-KOH-extractable hemicelluloses (reverse Xyl/Ara) and p-coumaryl alcohol relative proportion of KOH-extractable lignin (H/G). Correlation analysis indicated that Ara substitution degree and H/G ratio negatively affected cellulose crystallinity for high biomass enzymatic digestion. It was also suggested to determine whether Ara and H monomer have an interlinking with cellulose chains in the future. Conclusions Using nine typical pairs of wheat and rice samples having distinct cell wall compositions and wide biomass saccharification, Ara substitution degree and monolignin H proportion have been revealed to be the dominant factors positively determining biomass digestibility upon various chemical pretreatments. The results demonstrated the potential of genetic modification of plant cell walls for high biomass saccharification in bioenergy crops. PMID:24341349
Water adsorption on surface-modified cellulose nanocrystals
NASA Astrophysics Data System (ADS)
Wei, Zonghui; Sinko, Robert; Keten, Sinan; Luijten, Erik
Cellulose nanocrystals (CNCs) have attracted much attention as a filler phase for polymer nanocomposites due to their impressive mechanical properties, low cost, and environmental sustainability. Despite their promise for this application, there are still numerous obstacles that prevent optimal performance of CNC-polymer nanocomposites, such as poor filler dispersion and high levels of water absorption. One way to mitigate these negative effects is to modify CNC surfaces. Computational approaches can be utilized to obtain direct insight into the properties of modified CNC surfaces and probe the interactions of CNCs with other materials to facilitate the experimental design of nanocomposites. We use atomistic grand-canonical Monte Carlo simulations to study how surface modification of ion-exchanged sulfated cellulose nanocrystals (Na-CNCs) impacts water adsorption. We find that methyl(triphenyl)phosphonium-exchanged CNCs adsorb less water than Na-CNCs at the same relative humidity, supporting recent experimental dynamic vapor sorption measurements. By characterizing the distribution and configuration of water molecules near the modified CNC surfaces we determine how surface modifications disrupt CNC-water interactions.
Sarode, Ashish L; Malekar, Swapnil A; Cote, Catherine; Worthen, David R
2014-11-04
Overcoming the low oral bioavailability of many drugs due to their poor aqueous solubility is one of the major challenges in the pharmaceutical industry. The production of amorphous solid dispersions (ASDs) of these drugs using hydrophilic polymers may significantly improve their solubility. However, their storage stability and the stability of their supersaturated solutions in the gastrointestinal tract upon administration are unsolved problems. We have investigated the potential of a low viscosity grade of a cellulosic polymer, hydroxypropyl cellulose (HPC-SSL), and compared it with a commonly used vinyl polymer, polyvinylpyrrolidone vinyl acetate (PVP-VA), for stabilizing the ASDs of a poorly water soluble drug, felodipine. The ASDs were produced using hot melt mixing and stored under standard and accelerated stability conditions. The ASDs were characterized using differential scanning calorimetry, powder X-ray diffraction, and Fourier transform infrared spectroscopy. Drug dissolution and partitioning rates were evaluated using single- and biphasic dissolution studies. The ASDs displayed superior drug dissolution and partitioning as compared to the pure crystalline drug, which might be attributed to the formation of a drug-polymer molecular dispersion, amorphous conversion of the drug, and drug-polymer hydrogen bonding interactions. Late phase separation and early re-crystallization occurred at lower and higher storage temperatures, respectively, for HPC-SSL ASDs, whereas early phase separation, even at low storage temperatures, was noted for PVP-VA ASDs. Consequently, the partitioning rates for ASDs dispersed in HPC-SSL were greater than those of PVP-VA at lower and room temperature storage, whereas the performance of both of the ASDs was similar when stored at higher temperatures. Copyright © 2014. Published by Elsevier Ltd.
Role of cellulose ether polymers on ibuprofen release from matrix tablets.
Vueba, M L; Batista de Carvalho, L A E; Veiga, F; Sousa, J J; Pina, Maria Eugénia
2005-08-01
Cellulose derivatives are the most frequently used polymers in formulations of pharmaceutical products for controlled drug delivery. The main aim of the present work was to evaluate the effect of different cellulose substitutions on the release rate of ibuprofen (IBP) from hydrophilic matrix tablets. Thus, the release mechanism of IBP with methylcellulose (MC25), hydroxypropylcellulose (HPC), and hydroxypropylmethylcellulose (HPMC K15M or K100M) was studied. In addition, the influence of the diluents lactose monohydrate (LAC) and beta-cyclodextrin (beta-CD) was evaluated. Distinct test formulations were prepared containing: 57.14% of IBP, 20.00% of polymer, 20.29% of diluent, 1.71% of talc lubricants, and 0.86% of magnesium stearate as lubricants. Although non-negligible drug-excipient interactions were detected from DSC studies, these were found not to constitute an incompatibility effect. Tablets were examined for their drug content, weight uniformity, hardness, thickness, tensile strength, friability, porosity, swelling, and dissolution performance. Polymers MC25 and HPC were found to be unsuitable for the preparation of this kind of solid dosage form, while HPMC K15M and K100M showed to be advantageous. Dissolution parameters such as the area under the dissolution curve (AUC), the dissolution efficiency (DE(20 h)), dissolution time (t 50%), and mean dissolution time (MDT) were calculated for all the formulations, and the highest MDT values were obtained with HPMC indicating that a higher value of MDT signifies a higher drug retarding ability of the polymer and vice-versa. The analysis of the drug release data was performed in the light of distinct kinetic mathematical models-Kosmeyer-Peppas, Higuchi, zero-, and first-order. The release process was also found to be slightly influenced by the kind of diluent used.
Fong, Monica; Berrin, Jean-Guy; Paës, Gabriel
2016-01-01
Enzymes degrading plant biomass polymers are widely used in biotechnological applications. Their efficiency can be limited by non-specific interactions occurring with some chemical motifs. In particular, the lignin component is known to bind enzymes irreversibly. In order to determine interactions of enzymes with their substrates, experiments are usually performed on isolated simple polymers which are not representative of plant cell wall complexity. But when using natural plant substrates, the role of individual chemical and structural features affecting enzyme-binding properties is also difficult to decipher. We have designed and used lignified model assemblies of plant cell walls as templates to characterize binding properties of multi-modular cellulases. These three-dimensional assemblies are modulated in their composition using the three principal polymers found in secondary plant cell walls (cellulose, hemicellulose, and lignin). Binding properties of enzymes are obtained from the measurement of their mobility that depends on their interactions with the polymers and chemical motifs of the assemblies. The affinity of the multi-modular GH45 cellulase was characterized using a statistical analysis to determine the role played by each assembly polymer. Presence of hemicellulose had much less impact on affinity than cellulose and model lignin. Depending on the number of CBMs appended to the cellulase catalytic core, binding properties toward cellulose and lignin were highly contrasted. Model assemblies bring new insights into the molecular determinants that are responsible for interactions between enzymes and substrate without the need of complex analysis. Consequently, we believe that model bioinspired assemblies will provide relevant information for the design and optimization of enzyme cocktails in the context of biorefineries.
Jia, Jun; Yu, Bin; Wu, Leiming; Wang, Hongwu; Wu, Zhiliang; Li, Ming; Huang, Pengyan; Feng, Shengqiu; Chen, Peng; Zheng, Yonglian; Peng, Liangcai
2014-01-01
Corn is a major food crop with enormous biomass residues for biofuel production. Due to cell wall recalcitrance, it becomes essential to identify the key factors of lignocellulose on biomass saccharification. In this study, we examined total 40 corn accessions that displayed a diverse cell wall composition. Correlation analysis showed that cellulose and lignin levels negatively affected biomass digestibility after NaOH pretreatments at p<0.05 & 0.01, but hemicelluloses did not show any significant impact on hexoses yields. Comparative analysis of five standard pairs of corn samples indicated that cellulose and lignin should not be the major factors on biomass saccharification after pretreatments with NaOH and H2SO4 at three concentrations. Notably, despite that the non-KOH-extractable residues covered 12%-23% hemicelluloses and lignin of total biomass, their wall polymer features exhibited the predominant effects on biomass enzymatic hydrolysis including Ara substitution degree of xylan (reverse Xyl/Ara) and S/G ratio of lignin. Furthermore, the non-KOH-extractable polymer features could significantly affect lignocellulose crystallinity at p<0.05, leading to a high biomass digestibility. Hence, this study could suggest an optimal approach for genetic modification of plant cell walls in bioenergy corn.
Wu, Leiming; Wang, Hongwu; Wu, Zhiliang; Li, Ming; Huang, Pengyan; Feng, Shengqiu; Chen, Peng; Zheng, Yonglian; Peng, Liangcai
2014-01-01
Corn is a major food crop with enormous biomass residues for biofuel production. Due to cell wall recalcitrance, it becomes essential to identify the key factors of lignocellulose on biomass saccharification. In this study, we examined total 40 corn accessions that displayed a diverse cell wall composition. Correlation analysis showed that cellulose and lignin levels negatively affected biomass digestibility after NaOH pretreatments at p<0.05 & 0.01, but hemicelluloses did not show any significant impact on hexoses yields. Comparative analysis of five standard pairs of corn samples indicated that cellulose and lignin should not be the major factors on biomass saccharification after pretreatments with NaOH and H2SO4 at three concentrations. Notably, despite that the non-KOH-extractable residues covered 12%–23% hemicelluloses and lignin of total biomass, their wall polymer features exhibited the predominant effects on biomass enzymatic hydrolysis including Ara substitution degree of xylan (reverse Xyl/Ara) and S/G ratio of lignin. Furthermore, the non-KOH-extractable polymer features could significantly affect lignocellulose crystallinity at p<0.05, leading to a high biomass digestibility. Hence, this study could suggest an optimal approach for genetic modification of plant cell walls in bioenergy corn. PMID:25251456
Iurian, Sonia; Turdean, Luana; Tomuta, Ioan
2017-01-01
This study focuses on the development of a drug product based on a risk assessment-based approach, within the quality by design paradigm. A prolonged release system was proposed for paliperidone (Pal) delivery, containing Kollidon® SR as an insoluble matrix agent and hydroxypropyl cellulose, hydroxypropyl methylcellulose (HPMC), or sodium carboxymethyl cellulose as a hydrophilic polymer. The experimental part was preceded by the identification of potential sources of variability through Ishikawa diagrams, and failure mode and effects analysis was used to deliver the critical process parameters that were further optimized by design of experiments. A D-optimal design was used to investigate the effects of Kollidon SR ratio (X1), the type of hydrophilic polymer (X2), and the percentage of hydrophilic polymer (X3) on the percentages of dissolved Pal over 24 h (Y1–Y9). Effects expressed as regression coefficients and response surfaces were generated, along with a design space for the preparation of a target formulation in an experimental area with low error risk. The optimal formulation contained 27.62% Kollidon SR and 8.73% HPMC and achieved the prolonged release of Pal, with low burst effect, at ratios that were very close to the ones predicted by the model. Thus, the parameters with the highest impact on the final product quality were studied, and safe ranges were established for their variations. Finally, a risk mitigation and control strategy was proposed to assure the quality of the system, by constant process monitoring. PMID:28331293
Ikeuchi-Takahashi, Yuri; Ishihara, Chizuko; Onishi, Hiraku
2017-09-01
The purpose of the present work was to evaluate polyvinyl alcohols (PVAs) as a mucoadhesive polymer for mucoadhesive buccal tablets prepared by direct compression. Various polymerization degree and particle diameter PVAs were investigated for their usability. The tensile strength, in vitro adhesive force, and water absorption properties of the tablets were determined to compare the various PVAs. The highest values of the tensile strength and the in vitro adhesive force were observed for PVAs with a medium viscosity and small particle size. The optimal PVA was identified by a factorial design analysis. Mucoadhesive tablets containing the optimal PVA were compared with carboxyvinyl polymer and hydroxypropyl cellulose formulations. The optimal PVA gives a high adhesive force, has a low viscosity, and resulted in relatively rapid drug release. Formulations containing carboxyvinyl polymer had high tensile strengths but short disintegration times. Higher hydroxypropyl cellulose concentration formulations had good adhesion forces and very long disintegration times. We identified the optimal characteristics of PVA, and the usefulness of mucoadhesive buccal tablets containing this PVA was suggested from their formulation properties.
Better together: synergy in nanocellulose blends
NASA Astrophysics Data System (ADS)
Mautner, Andreas; Mayer, Florian; Hervy, Martin; Lee, Koon-Yang; Bismarck, Alexander
2017-12-01
Cellulose nanopapers have gained significant attention in recent years as large-scale reinforcement for high-loading cellulose nanocomposites, substrates for printed electronics and filter nanopapers for water treatment. The mechanical properties of nanopapers are of fundamental importance for all these applications. Cellulose nanopapers can simply be prepared by filtering a suspension of nanocellulose, followed by heat consolidation. It was already demonstrated that the mechanical properties of cellulose nanopapers can be tailored by the fineness of the fibrils used or by modifying nanocellulose fibrils for instance by polymer adsorption, but nanocellulose blends remain underexplored. In this work, we show that the mechanical and physical properties of cellulose nanopapers can be tuned by creating nanopapers from blends of various grades of nanocellulose, i.e. (mechanically refined) bacterial cellulose or cellulose nanofibrils extracted from never-dried bleached softwood pulp by chemical and mechanical pre-treatments. We found that nanopapers made from blends of two or three nanocellulose grades show synergistic effects resulting in improved stiffness, strength, ductility, toughness and physical properties. This article is part of a discussion meeting issue `New horizons for cellulose nanotechnology'.
Habibi, Neda
2015-02-05
The preparation and characterization of functional biocompatible magnetite-cellulose nano-composite fibrous material is described. Magnetite-cellulose nano-composite was prepared by a combination of the solution-based formation of magnetic nano-particles and subsequent coating with amino celluloses. Characterization was accomplished using X-ray powder diffraction (XRD), fourier transformed infrared (FTIR) and field emission scanning electron microscopy (FESEM) analysis. The peaks of Fe3O4 in the XRD pattern of nanocomposite confirm existence of the nanoparticles in the amino cellulose matrix. Magnetite-cellulose particles exhibit an average diameter of roughly 33nm as demonstrated by field emission scanning electron microscopy. Magnetite nanoparticles were irregular spheres dispersed in the cellulose matrix. The vibration corresponding to the NCH3 functional group about 2850cm(-1) is assigned in the FTIR spectra. Functionalized magnetite-cellulose nano-composite polymers have a potential range of application as targeted drug delivery system in biomedical field. Copyright © 2014 Elsevier B.V. All rights reserved.
B. K. Via; C. L. So; T. F. Shupe; L. H. Groom; J. Wikaira
2009-01-01
The composite structure of the S2 layer in the wood cell wall is defined by the angle of the cellulose microfibrils and concentration of polymers and this structure impacts strength and stiffness. The objective of this study was to use near infrared spectroscopy and X-ray diffraction to determine the effect of lignin and cellulose associated wavelengths,...
Mudgil, Deepak; Barak, Sheweta
2013-10-01
In last few decades, indigestible carbohydrates as dietary fiber have attracted interest of food scientists and technologists due to its several physiological benefits. Dietary fibers are generally of two types based on their solubility, i.e. soluble and insoluble dietary fiber. Significant physicochemical properties of dietary fiber include solubility, viscosity, water holding capacity, bulking and fermentability. Some important dietary fibers are celluloses, hemicelluloses, hydrocolloids, resistant starches and non-digestible oligosaccharides. Inclusion of these fibers in daily diet imparts several health benefits such as prevention or reduction of bowel disorders, and decrease risk of coronary heart disease and type 2 diabetes. Copyright © 2013 Elsevier B.V. All rights reserved.
Lee, Christopher M; Kafle, Kabindra; Park, Yong Bum; Kim, Seong H
2014-06-14
This study reports that the noncentrosymmetry and phase synchronization requirements of the sum frequency generation (SFG) process can be used to distinguish the three-dimensional organization of crystalline cellulose distributed in amorphous matrices. Crystalline cellulose is produced as microfibrils with a few nanometer diameters by plants, tunicates, and bacteria. Crystalline cellulose microfibrils are embedded in wall matrix polymers and assembled into hierarchical structures that are precisely designed for specific biological and mechanical functions. The cellulose microfibril assemblies inside cell walls are extremely difficult to probe. The comparison of vibrational SFG spectra of uniaxially-aligned and disordered films of cellulose Iβ nanocrystals revealed that the spectral features cannot be fully explained with the crystallographic unit structure of cellulose. The overall SFG intensity, the alkyl peak shape, and the alkyl/hydroxyl intensity ratio are sensitive to the lateral packing and net directionality of the cellulose microfibrils within the SFG coherence length scale. It was also found that the OH SFG stretch peaks could be deconvoluted to find the polymorphic crystal structures of cellulose (Iα and Iβ). These findings were used to investigate the cellulose crystal structure and mesoscale cellulose microfibril packing in intact plant cell walls, tunicate tests, and bacterial films.
Griffiths, Jonathan S; North, Helen M
2017-05-01
The cell wall defines the shape of cells and ultimately plant architecture. It provides mechanical resistance to osmotic pressure while still being malleable and allowing cells to grow and divide. These properties are determined by the different components of the wall and the interactions between them. The major components of the cell wall are the polysaccharides cellulose, hemicellulose and pectin. Cellulose biosynthesis has been extensively studied in Arabidopsis hypocotyls, and more recently in the mucilage-producing epidermal cells of the seed coat. The latter has emerged as an excellent system to study cellulose biosynthesis and the interactions between cellulose and other cell wall polymers. Here we review some of the major advances in our understanding of cellulose biosynthesis in the seed coat, and how mucilage has aided our understanding of the interactions between cellulose and other cell wall components required for wall cohesion. Recently, 10 genes involved in cellulose or hemicellulose biosynthesis in mucilage have been identified. These discoveries have helped to demonstrate that xylan side-chains on rhamnogalacturonan I act to link this pectin directly to cellulose. We also examine other factors that, either directly or indirectly, influence cellulose organization or crystallization in mucilage. © 2017 INRA. New Phytologist © 2017 New Phytologist Trust.
Formation of wood secondary cell wall may involve two type cellulose synthase complexes in Populus.
Xi, Wang; Song, Dongliang; Sun, Jiayan; Shen, Junhui; Li, Laigeng
2017-03-01
Cellulose biosynthesis is mediated by cellulose synthases (CesAs), which constitute into rosette-like cellulose synthase complexe (CSC) on the plasma membrane. Two types of CSCs in Arabidopsis are believed to be involved in cellulose synthesis in the primary cell wall and secondary cell walls, respectively. In this work, we found that the two type CSCs participated cellulose biosynthesis in differentiating xylem cells undergoing secondary cell wall thickening in Populus. During the cell wall thickening process, expression of one type CSC genes increased while expression of the other type CSC genes decreased. Suppression of different type CSC genes both affected the wall-thickening and disrupted the multilaminar structure of the secondary cell walls. When CesA7A was suppressed, crystalline cellulose content was reduced, which, however, showed an increase when CesA3D was suppressed. The CesA suppression also affected cellulose digestibility of the wood cell walls. The results suggest that two type CSCs are involved in coordinating the cellulose biosynthesis in formation of the multilaminar structure in Populus wood secondary cell walls.
Generation of colloidal granules and capsules from double emulsion drops
NASA Astrophysics Data System (ADS)
Hess, Kathryn S.
Assemblies of colloidal particles are extensively used in ceramic processing, pharmaceuticals, inks and coatings. In this project, the aim was to develop a new technique to fabricate monodispersed colloidal assemblies. The use of microfluidic devices and emulsion processing allows for the fabrication of complex materials that can be used in a variety of applications. A microfluidic device is used to create monodispersed water/oil/water (w/o/w) double emulsions with interior droplets of colloidal silica suspension ranging in size from tens to hundreds of microns. By tailoring the osmotic pressure using glycerol as a solute in the continuous and inner phases of the emulsion, we can control the final volume size of the monodispersed silica colloidal crystals that form in the inner droplets of the double emulsion. Modifying the ionic strength in the colloidal dispersion can be used to affect the particle-particle interactions and crystal formation of the final colloidal particle. This w/o/w technique has been used with other systems of metal oxide colloids and cellulose nanocrystals. Encapsulation of the colloidal suspension in a polymer shell for the generation of ceramic-polymer core-shell particles has also been developed. These core-shell particles have spawned new research in the field of locally resonant acoustic metamaterials. Systems and chemistries for creating cellulose hydrogels within the double emulsions have also been researched. Water in oil single emulsions and double emulsions have been used to create cellulose hydrogel spheres in the sub-100 micron diameter range. Oil/water/oil double emulsions allow us to create stable cellulose capsules. The addition of a second hydrogel polymer, such as acrylate or alginate, further strengthens the cellulose gel network and can also be processed into capsules and particles using the microfluidic device. This work could have promising applications in acoustic metamaterials, personal care products, pharmaceuticals, and agricultural applications, among others.
Supercritical antisolvent co-precipitation of rifampicin and ethyl cellulose.
Djerafi, Rania; Swanepoel, Andri; Crampon, Christelle; Kalombo, Lonji; Labuschagne, Philip; Badens, Elisabeth; Masmoudi, Yasmine
2017-05-01
Rifampicin-loaded submicron-sized particles were prepared through supercritical anti-solvent process using ethyl cellulose as polymeric encapsulating excipient. Ethyl acetate and a mixture of ethyl acetate/dimethyl sulfoxide (70/30 and 85/15) were used as solvents for both drug and polymeric excipient. When ethyl acetate was used, rifampicin was crystallized separately without being embedded within the ethyl cellulose matrix while by using the ethyl acetate/dimethyl sulfoxide mixture, reduced crystallinity of the active ingredient was observed and a simultaneous precipitation of ethyl cellulose and drug was achieved. The effect of solvent/CO 2 molar ratio and polymer/drug mass ratio on the co-precipitates morphology and drug loading was investigated. Using the solvent mixture, co-precipitates with particle sizes ranging between 190 and 230nm were obtained with drug loading and drug precipitation yield from respectively 8.5 to 38.5 and 42.4 to 77.2% when decreasing the ethyl cellulose/rifampicin ratio. Results show that the solvent nature and the initial drug concentrations affect morphology and drug precipitation yield of the formulations. In vitro dissolution studies revealed that the release profile of rifampicin was sustained when co-precipitation was carried out with the solvent mixture. It was demonstrated that the drug to polymer ratio influenced amorphous content of the SAS co-precipitates. Differential scanning calorimetry thermograms and infrared spectra revealed that there is neither interaction between rifampicin and the polymer nor degradation of rifampicin during co-precipitation. In addition, stability stress tests on SAS co-precipitates were carried out at 75% relative humidity and room temperature in order to evaluate their physical stability. SAS co-precipitates were X-ray amorphous and remained stable after 6months of storage. The SAS co-precipitation process using a mixture of ethyl acetate/dimethyl sulfoxide demonstrates that this strategy can be successful for controlling rifampicin delivery. Copyright © 2017 Elsevier B.V. All rights reserved.
Luo, Xiaogang; Zeng, Jian; Liu, Shilin; Zhang, Lina
2015-10-01
Development of highly cost-effective, highly operation-convenient and highly efficient natural polymer-based adsorbents for their biodegradability and biocompatibility, and supply of safe drinking water are the most threatening problems in water treatment field. To tackle the challenges, a new kind of efficient recyclable magnetic chitosan/cellulose hybrid microspheres was prepared by sol-gel method. By embedding magnetic γ-Fe2O3 nanoparticles in chitosan/cellulose matrix drops in NaOH/urea aqueous solution, it combined renewability and biocompatibility of chitosan and cellulose as well as magnetic properties of γ-Fe2O3 to create a hybrid system in heavy metal ions removal. Copyright © 2015 Elsevier Ltd. All rights reserved.
Development of a multilayered association polymer system for sequential drug delivery
NASA Astrophysics Data System (ADS)
Chinnakavanam Sundararaj, Sharath kumar
As all the physiological processes in our body are controlled by multiple biomolecules, comprehensive treatment of certain disease conditions may be more effectively achieved by administration of more than one type of drug. Thus, the primary objective of this research was to develop a multilayered, polymer-based system for sequential delivery of multiple drugs. This particular device was designed aimed at the treatment of periodontitis, a highly prevalent oral inflammatory disease that affects 90% of the world population. This condition is caused by bacterial biofilm on the teeth, resulting in a chronic inflammatory response that leads to loss of alveolar bone and, ultimately, the tooth. Current treatment methods for periodontitis address specific parts of the disease, with no individual treatment serving as a complete therapy. The polymers used for the fabrication of this multilayered device consists of cellulose acetate phthalate (CAP) complexed with Pluronic F-127 (P). After evaluating morphology of the resulting CAPP system, in vitro release of small molecule drugs and a model protein was studied from both single and multilayered devices. Drug release from single-layered CAPP films followed zero-order kinetics related to surface erosion property of the association polymer. Release studies from multilayered CAPP devices showed the possibility of achieving intermittent release of one type of drug as well as sequential release of more than one type of drug. Mathematical modeling accurately predicted the release profiles for both single layer and multilayered devices. After the initial characterization of the CAPP system, the device was specifically modified to achieve sequential release of drugs aimed at the treatment of periodontitis. The four types of drugs used were metronidazole, ketoprofen, doxycycline, and simvastatin to eliminate infection, inhibit inflammation, prevent tissue destruction, and aid bone regeneration, respectively. To obtain different erosion times and achieve appropriate release profiles specific to the disease condition, the device was modified by increasing the number of layers or by inclusion of a slower eroding polymer layer. In all the cases, the device was able to release the four different drugs in the designed temporal sequence. Analysis of antibiotic and antiinflammatory bioactivity showed that drugs released from the devices retained 100% bioactivity. Following extensive studies on the in vitro sequential drug release from these devices, the in vivo drug release profiles were investigated. The CAPP devices with different release rates and dosage formulations were implanted in a rat calvarial onlay model, and the in vivo drug release and erosion was compared with in vitro results. In vivo studies showed sequential release of drugs comparable to those measured in vitro, with some difference in drug release rates observed. The present CAPP association polymer-based multilayer devices can be used for localized, sequential delivery of multiple drugs for the possible treatment of complex disease conditions, and perhaps for tissue engineering applications, that require delivery of more than one type of biomolecule. KEYWORDS: Multiple drug delivery, Periodontitis, Cellulose acetate phthalate, Pluronic F-127, Sequential drug release, in vitro drug release, in vivo drug release.
Sánchez-Rodríguez, Clara; Bauer, Stefan; Hématy, Kian; Saxe, Friederike; Ibáñez, Ana Belén; Vodermaier, Vera; Konlechner, Cornelia; Sampathkumar, Arun; Rüggeberg, Markus; Aichinger, Ernst; Neumetzler, Lutz; Burgert, Ingo; Somerville, Chris; Hauser, Marie-Theres; Persson, Staffan
2012-02-01
Plant cells are encased by a cellulose-containing wall that is essential for plant morphogenesis. Cellulose consists of β-1,4-linked glucan chains assembled into paracrystalline microfibrils that are synthesized by plasma membrane-located cellulose synthase (CESA) complexes. Associations with hemicelluloses are important for microfibril spacing and for maintaining cell wall tensile strength. Several components associated with cellulose synthesis have been identified; however, the biological functions for many of them remain elusive. We show that the chitinase-like (CTL) proteins, CTL1/POM1 and CTL2, are functionally equivalent, affect cellulose biosynthesis, and are likely to play a key role in establishing interactions between cellulose microfibrils and hemicelluloses. CTL1/POM1 coincided with CESAs in the endomembrane system and was secreted to the apoplast. The movement of CESAs was compromised in ctl1/pom1 mutant seedlings, and the cellulose content and xyloglucan structures were altered. X-ray analysis revealed reduced crystalline cellulose content in ctl1 ctl2 double mutants, suggesting that the CTLs cooperatively affect assembly of the glucan chains, which may affect interactions between hemicelluloses and cellulose. Consistent with this hypothesis, both CTLs bound glucan-based polymers in vitro. We propose that the apoplastic CTLs regulate cellulose assembly and interaction with hemicelluloses via binding to emerging cellulose microfibrils.
Sánchez-Rodríguez, Clara; Bauer, Stefan; Hématy, Kian; Saxe, Friederike; Ibáñez, Ana Belén; Vodermaier, Vera; Konlechner, Cornelia; Sampathkumar, Arun; Rüggeberg, Markus; Aichinger, Ernst; Neumetzler, Lutz; Burgert, Ingo; Somerville, Chris; Hauser, Marie-Theres; Persson, Staffan
2012-01-01
Plant cells are encased by a cellulose-containing wall that is essential for plant morphogenesis. Cellulose consists of β-1,4-linked glucan chains assembled into paracrystalline microfibrils that are synthesized by plasma membrane–located cellulose synthase (CESA) complexes. Associations with hemicelluloses are important for microfibril spacing and for maintaining cell wall tensile strength. Several components associated with cellulose synthesis have been identified; however, the biological functions for many of them remain elusive. We show that the chitinase-like (CTL) proteins, CTL1/POM1 and CTL2, are functionally equivalent, affect cellulose biosynthesis, and are likely to play a key role in establishing interactions between cellulose microfibrils and hemicelluloses. CTL1/POM1 coincided with CESAs in the endomembrane system and was secreted to the apoplast. The movement of CESAs was compromised in ctl1/pom1 mutant seedlings, and the cellulose content and xyloglucan structures were altered. X-ray analysis revealed reduced crystalline cellulose content in ctl1 ctl2 double mutants, suggesting that the CTLs cooperatively affect assembly of the glucan chains, which may affect interactions between hemicelluloses and cellulose. Consistent with this hypothesis, both CTLs bound glucan-based polymers in vitro. We propose that the apoplastic CTLs regulate cellulose assembly and interaction with hemicelluloses via binding to emerging cellulose microfibrils. PMID:22327741
Graphene Inks with Cellulosic Dispersants: Development and Applications for Printed Electronics
NASA Astrophysics Data System (ADS)
Secor, Ethan Benjamin
Graphene offers promising opportunities for applications in printed and flexible electronic devices due to its high electrical and thermal conductivity, mechanical flexibility and strength, and chemical and environmental stability. However, scalable production and processing of graphene presents a critical technological challenge preventing the application of graphene for flexible electronic interconnects, electrochemical energy storage, and chemically robust electrical contacts. In this thesis, a promising and versatile platform for the production, patterning, and application of graphene inks is presented based on cellulosic dispersants. Graphene is produced from flake graphite using scalable liquid-phase exfoliation methods, using the polymers ethyl cellulose and nitrocellulose as multifunctional dispersing agents. These cellulose derivatives offer high colloidal stability and broadly tunable rheology for graphene dispersions, providing an effective and tunable platform for graphene ink development. Thermal or photonic annealing decomposes the polymer dispersant to yield high conductivity, flexible graphene patterns for various electronics applications. In particular, the chemical stability of graphene enables robust electrical contacts for ceramic, metallic, organic and electrolytic materials, validating the diverse applicability of graphene in printed electronics. Overall, the strategy for graphene ink design presented here offers a simple, efficient, and versatile method for integrating graphene in a wide range of printed devices and systems, providing both fundamental insight for nanomaterial ink development and realistic opportunities for practical applications.
Zeng, Xiaoliang; Sun, Jiajia; Yao, Yimin; Sun, Rong; Xu, Jian-Bin; Wong, Ching-Ping
2017-05-23
With the current development of modern electronics toward miniaturization, high-degree integration and multifunctionalization, considerable heat is accumulated, which results in the thermal failure or even explosion of modern electronics. The thermal conductivity of materials has thus attracted much attention in modern electronics. Although polymer composites with enhanced thermal conductivity are expected to address this issue, achieving higher thermal conductivity (above 10 W m -1 K -1 ) at filler loadings below 50.0 wt % remains challenging. Here, we report a nanocomposite consisting of boron nitride nanotubes and cellulose nanofibers that exhibits high thermal conductivity (21.39 W m -1 K -1 ) at 25.0 wt % boron nitride nanotubes. Such high thermal conductivity is attributed to the high intrinsic thermal conductivity of boron nitride nanotubes and cellulose nanofibers, the one-dimensional structure of boron nitride nanotubes, and the reduced interfacial thermal resistance due to the strong interaction between the boron nitride nanotubes and cellulose nanofibers. Using the as-prepared nanocomposite as a flexible printed circuit board, we demonstrate its potential usefulness in electronic device-cooling applications. This thermally conductive nanocomposite has promising applications in thermal interface materials, printed circuit boards or organic substrates in electronics and could supplement conventional polymer-based materials.
Nonionic Cellulose Ethers as Potential Drug Delivery Systems for Periodontal Anesthesia.
Scherlund; Brodin; Malmsten
2000-09-15
Nonionic cellulose ethers displaying a lower consolute temperature, or cloud-point, close to body temperature were investigated as potential carrier systems for the delivery of local anesthetic agents to the periodontal pocket. The interaction between the polymers, i.e., ethyl(hydroxyethyl)cellulose (EHEC) and hydrophobically modified EHEC (HM-EHEC), and ionic surfactants was determined in the absence and in the presence of the local anesthetic agents lidocaine and prilocaine. The cloud-point and rheology data indicate interactions between the polymer and both anionic and cationic surfactants. More precisely, a number of ionic surfactants were found to result in an increase in cloud-point at higher surfactant concentrations, a surfactant-concentration-dependent thickening, and a temperature-induced gelation upon heating. Upon addition of the local anesthetic agents lidocaine and prilocaine in their uncharged form to EHEC and HM-EHEC, in the absence of surfactants, only minor interaction with the polymer could be inferred. However, these substances were found to affect the polymer-surfactant interaction. In particular, the drug release rate in vitro as well as the stability and temperature-dependent viscosity were followed for an EHEC/SDS system and EHEC/myristoylcholine bromide system upon addition of lidocaine and prilocaine. The data indicate a possibility of formulating a local anesthetic drug delivery system suitable for administration into the periodontal pocket where at least small amounts of active ingredients can be incorporated into the system without severely affecting the gelation behavior. The results found for the cationic myristoylcholine bromide system are particularly interesting for the application in focus here since this surfactant is antibacterial and readily biodegradable. Copyright 2000 Academic Press.
Biodegradable starch-based polymeric materials
NASA Astrophysics Data System (ADS)
Suvorova, Anna I.; Tyukova, Irina S.; Trufanova, Elena I.
2000-05-01
The effects of low-molecular-weight additives, temperature and mechanical action on the structure and properties of starch are discussed. Special attention is given to mixtures of starch with synthetic polymers, e.g., co-polymers of ethylene with vinyl acetate, vinyl alcohol, acrylic acid, cellulose derivatives and other natural polymers. These mixtures can be used in the development of novel environmentally safe materials (films, coatings, packaging materials) and various articles for short-term use. The bibliography includes 105 references.
Neera; Ramana, Karna Venkata; Batra, Harsh Vardhan
2015-06-01
Cellulose producing bacteria were isolated from fruit samples and kombucha tea (a fermented beverage) using CuSO4 solution in modified Watanabe and Yamanaka medium to inhibit yeasts and molds. Six bacterial strains showing cellulose production were isolated and identified by 16S rRNA gene sequencing as Gluconacetobacter xylinus strain DFBT, Ga. xylinus strain dfr-1, Gluconobacter oxydans strain dfr-2, G. oxydans strain dfr-3, Acetobacter orientalis strain dfr-4, and Gluconacetobacter intermedius strain dfr-5. All the cellulose-producing bacteria were checked for the cellulose yield. A potent cellulose-producing bacterium, i.e., Ga. xylinus strain DFBT based on yield (cellulose yield 5.6 g/L) was selected for further studies. Cellulose was also produced in non- conventional media such as pineapple juice medium and hydrolysed corn starch medium. A very high yield of 9.1 g/L cellulose was obtained in pineapple juice medium. Fourier transform infrared spectrometer (FT-IR) analysis of the bacterial cellulose showed the characteristic peaks. Soft cellulose with a very high water holding capacity was produced using limited aeration. Scanning electron microscopy (SEM) was used to analyze the surface characteristics of normal bacterial cellulose and soft cellulose. The structural analysis of the polymer was performed using (13)C solid-state nuclear magnetic resonance (NMR). More interfibrillar space was observed in the case of soft cellulose as compared to normal cellulose. This soft cellulose can find potential applications in the food industry as it can be swallowed easily without chewing.
Nanoscale analysis of degradation processes of cellulose fibers.
Teodonio, Lorenzo; Missori, Mauro; Pawcenis, Dominika; Łojewska, Joanna; Valle, Francesco
2016-12-01
Mapping the morphological and nano-mechanical properties of cellulose fibers within paper sheets or textile products at the nano-scale level by using atomic force microscopy is a challenging task due to the huge surface level variation of these materials. However this task is fundamental for applications in forensic or cultural heritage sciences and for the industrial characterization of materials. In order to correlate between nano-mechanical properties and local nanometer scale morphology of different layers of cellulose fibers, a new strategy to prepare samples of isolated cellulose fibers was designed. This approach is based on immobilizing isolated fibers onto glass slides chemically pretreated so as to promote cellulose adhesion. The experiments presented here aim at the nano-scale characterization of fibers in paper samples aged under different external agents (relative humidity, temperature) in such a way as to promote hydrolysis and oxidation of polymers. The observed variability of local mechanical properties of paper fibers was related to varying degrees of cellulose polymerization induced by artificial aging. Copyright © 2016 Elsevier Ltd. All rights reserved.
Crépy, Lucie; Monchau, Francine; Chai, Feng; Raoul, Gwénaël; Hivart, Philippe; Hildebrand, Hartmut F; Martin, Patrick; Joly, Nicolas
2012-05-01
The study aims to validate an original bio-based material, obtained by grafting fatty chains, and more especially lauric chains (C12) onto cellulose, for medical applications. The mechanical properties of the synthesized cellulose laurate (C12) are close to those of petrochemical ones such as low density polyethylene. This cellulose-based polymer is transparent, flexible, and hydrophobic. To evaluate the stability of the cellulosic films in biological fluids the samples are soaked in simulated body fluid or blood plasma for a few hours to 6 months, and then submitted to mechanical and chemical analyses. The simultaneously performed cytocompatibility tests were the colony-forming viability, the vitality and cell proliferation tests using NIH 3T3 fibroblasts and MC 3T3 osteoblast-like cells. The results show the stability, the biocompatibility, and the noncytotoxicity of the synthesized cellulose laurate films. This biomaterial may so be considered for surgical applications. Copyright © 2012 Wiley Periodicals, Inc.
Vermerris, Wilfred; Abril, Alejandra
2015-04-01
Cellulose from plant biomass can serve as a sustainable feedstock for fuels, chemicals and polymers that are currently produced from petroleum. In order to enhance economic feasibility, the efficiency of cell wall deconstruction needs to be enhanced. With the use of genetic and biotechnological approaches cell wall composition can be modified in such a way that interactions between the major cell wall polymers—cellulose, hemicellulosic polysaccharides and lignin—are altered. Some of the resulting plants are compromised in their growth and development, but this may be caused in part by the plant's overcompensation for metabolic perturbances. In other cases novel structures have been introduced in the cell wall without negative effects. The first field studies with engineered bioenergy crops look promising, while detailed structural analyses of cellulose synthase offer new opportunities to modify cellulose itself. Copyright © 2014 Elsevier Ltd. All rights reserved.
Combining catalytical and biological processes to transform cellulose into high value-added products
NASA Astrophysics Data System (ADS)
Gavilà, Lorenc; Güell, Edgar J.; Maru, Biniam T.; Medina, Francesc; Constantí, Magda
2017-04-01
Cellulose, the most abundant polymer of biomass, has an enormous potential as a source of chemicals and energy. However, its nature does not facilitate its exploitation in industry. As an entry point, here, two different strategies to hydrolyse cellulose are proposed. A solid and a liquid acid catalysts are tested. As a solid acid catalyst, zirconia and different zirconia-doped materials are proved, meanwhile liquid acid catalyst is carried out by sulfuric acid. Sulfuric acid proved to hydrolyse 78% of cellulose, while zirconia doped with sulfur converted 22% of cellulose. Both hydrolysates were used for fermentation with different microbial strains depending on the desired product: Citrobacter freundii H3 and Lactobacillus delbrueckii, for H2 or lactic acid production respectively. A measure of 2 mol H2/mol of glucose was obtained from the hydrolysate using zirconia with Citrobacter freundii; and Lactobacillus delbrueckii transformed all glucose into optically pure D-lactic acid.
Shi, Qing Xuan; Xia, Qing; Xiang, Xiao; Ye, Yun Sheng; Peng, Hai Yan; Xue, Zhi Gang; Xie, Xiao Lin; Mai, Yiu-Wing
2017-09-04
Composite polymeric and ionic liquid (IL) electrolytes are some of the most promising electrolyte systems for safer battery technology. Although much effort has been directed towards enhancing the transport properties of polymer electrolytes (PEs) through nanoscopic modification by incorporating nano-fillers, it is still difficult to construct ideal ion conducting networks. Here, a novel class of three-dimensional self-assembled polymeric ionic liquid (PIL)-functionalized cellulose nano-crystals (CNC) confining ILs in surface-grafted PIL polymer chains, able to form colloidal crystal polymer electrolytes (CCPE), is reported. The high-strength CNC nano-fibers, decorated with PIL polymer chains, can spontaneously form three-dimensional interpenetrating nano-network scaffolds capable of supporting electrolytes with continuously connected ion conducting networks with IL being concentrated in conducting domains. These new CCPE have exceptional ionic conductivities, low activation energies (close to bulk IL electrolyte with dissolved Li salt), high Li + transport numbers, low interface resistances and improved interface compatibilities. Furthermore, the CCPE displays good electrochemical properties and a good battery performance. This approach offers a route to leak-free, non-flammable and high ionic conductivity solid-state PE in energy conversion devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Cellulose biosynthesis in Acetobacter xylinum
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lin, F.C.
1988-01-01
Time-lapse video microscopy has shown periodic reversals during the synthesis of cellulose. In the presence of Congo Red, Acetobacter produces a band of fine fibrils. The direction of cell movement is perpendicular to the longitudinal axis of cell, and the rate of movement was decreased. A linear row of particles, presumably the cellulose synthesizing complexes, was found on the outer membrane by freeze-fracture technique. During the cell cycle, the increase of particles in linear row, the differentiation to four linear rows and the separation of the linear rows have been observed. A digitonin-solubilized cellulose synthase was prepared from A. xylinum,more » and incubated under conditions known to lead to active in vitro synthesis of 1,4-{beta}-D-glucan polymer. Electron microscopy revealed that clusters of fibrils were assembled within minutes. Individual fibrils are 17 {plus minus} 2 angstroms in diameter. Evidence for the cellulosic composition of newly synthesized fibrils was based on incorporation of tritium from UDP-({sup 3}H) glucose binding of gold-labeled cellobiohydrolase, and an electron diffraction pattern identified as cellulose II polymorph instead of cellulose I.« less
Mechanics of Cellulose Synthase Complexes in Living Plant Cells
NASA Astrophysics Data System (ADS)
Zehfroosh, Nina; Liu, Derui; Ramos, Kieran P.; Yang, Xiaoli; Goldner, Lori S.; Baskin, Tobias I.
The polymer cellulose is one of the major components of the world's biomass with unique and fascinating characteristics such as its high tensile strength, renewability, biodegradability, and biocompatibility. Because of these distinctive aspects, cellulose has been the subject of enormous scientific and industrial interest, yet there are still fundamental open questions about cellulose biosynthesis. Cellulose is synthesized by a complex of transmembrane proteins called ``Cellulose Synthase A'' (CESA) in the plasma membrane. Studying the dynamics and kinematics of the CESA complex will help reveal the mechanism of cellulose synthesis and permit the development and validation of models of CESA motility. To understand what drives these complexes through the cell membrane, we used total internal reflection fluorescence microscopy (TIRFM) and variable angle epi-fluorescence microscopy to track individual, fluorescently-labeled CESA complexes as they move in the hypocotyl and root of living plants. A mean square displacement analysis will be applied to distinguish ballistic, diffusional, and other forms of motion. We report on the results of these tracking experiments. This work was funded by NSF/PHY-1205989.
Interaction between xanthan gum and cationic cellulose JR400 in aqueous solution.
Li, Haiping; Hou, Wanguo; Li, Xiuzhi
2012-06-05
The electrostatic and hydrogen bonding interactions between xanthan gum (XG) and semisynthetic cationic cellulose (JR400) in aqueous solution are investigated via stability map, FT-IR spectra, thermogravimetric analysis, potentiometric measurement and rheological method. The stability map shows three regions, a stable region with XG as the major component, a flocculated region and another stable region with JR400 as the major component. The stability of mixing system depends on both the concentration fraction of JR400 (fJR) and the overlapping concentrations of these two polymers. In the region near the stoichiometric fJR, the mixture shows stoichiometric flocculation, which is independent of the total polymer concentration. However, in the regions away from the stoichiometric fJR, the mixtures are stable when the concentration of major polymer component is higher than its overlapping concentration. In stable regions, the electrostatic and hydrogen bonding interactions can enhance the viscosity of mixing system at appropriate fJR values. Copyright © 2012 Elsevier Ltd. All rights reserved.
Bohic, S; Weiss, P; Roger, P; Daculsi, G
2001-03-01
Hydroxypropylmethylcellulose (HPMC) is used as a ligand for a bioactive calcium phosphate ceramic (the filler) in a ready-to-use injectable sterilized biomaterial for bone and dental surgery. Light scattering experiments were usually used to study high water-soluble polymers and to determine the basic macromolecular parameters. In order to gain a deeper understanding of polymer/mineral interactions in this type of material, we have investigated the effect of divalent and trivalent ions (Ca(2+), PO(4)(3-)) and steam sterilization on dilute solutions of HPMC and hydroxyethylcellulose (HEC). The sterilization process may cause some degradation of HEC taking into account its high molecular weight and some rigidity of the polymer chain. Moreover, in the case of HPMC, the changes in the conformations rather than degradation process are supposed. These effects of degradation and flocculation are strengthened in alkaline medium. Experimental data suggested the formation of chelate complexes between Ca(2+) and HPMC which improve its affinity to the mineral blend and consolidate the injectable biomaterial even in the case of its hydration by biological fluid. Copyright 2001 Kluwer Academic Publishers
NASA Astrophysics Data System (ADS)
Lorenc-Grabowska, Ewa; Rutkowski, Piotr
2014-10-01
The activated carbons (ACs) produced from solid residue of cellulose and synthetic polymer co-pyrolysis (CACs) and commercial activated carbon from coconut shell (GC) were used for phenol removal. The adsorption kinetics and mechanism were investigated. All studied activated carbons are predominantly microporous and are characterized by basic surface characteristics. Surface area SBET varies between 1235 and 1499 m2/g, whereas the pHPZC changes from 7.70 to 10.63. The bath adsorption of phenol (P) was carried out at ambient temperature. The equilibrium time and equilibrium sorption capacity were determined. It was found that the boundary layer effect is bigger in AC with high basic characteristics of the surface. The rate controlling step is the intraparticle diffusion in CACs only, whereas in ACs with higher amount of acidic functionalities the adsorbate-surface interaction influences the rate of kinetic as well. The equilibrium isotherms are L2 type for commercial AC and L4 for CACs. The CACs are characterized by very high adsorption capacity that vary between 312 and 417 mg/g. The main mechanism of phenol adsorption is micropore filling within pores smaller than 1.4 nm. In the absence of solvent effect further adsorption of phenol on CACs takes place. The enhanced adsorption is due to dispersive/repulsive interaction induced by oxygen functionalities.
Analytical pyrolysis mass spectrometry: new vistas opened by temperature-resolved in-source PYMS
NASA Astrophysics Data System (ADS)
Boon, Jaap J.
1992-09-01
Analytical pyrolysis mass spectrometry (PYMS) is introduced and its applications to the analysis of synthetic polymers, biopolymers, biomacromolecular systems and geomacromolecules are critically reviewed. Analytical pyrolysis inside the ionisation chamber of a mass spectrometer, i.e. in-source PYMS, gives a complete inventory of the pyrolysis products evolved from a solid sample. The temperature-resolved nature of the experiment gives a good insight into the temperature dependence of the volatilisation and pyrolytic dissociation processes. Chemical ionisation techniques appear to be especially suitable for the analysis of oligomeric fragments released in early stages of the pyrolysis of polymer systems. Large oligomeric fragments were observed for linear polymers such as cellulose (pentadecamer), polyhydroxyoctanoic acid (tridecamer) and polyhydroxybutyric acid (heneicosamer). New in-source PYMS data are presented on artists' paints, the plant polysaccharides cellulose and xyloglucan, several microbial polyhydroxyalkanoates, wood and enzyme-digested wood, biodegraded roots and a fossil cuticle of Miocene age. On-line and off-line pyrolysis chromatography mass spectrometric approaches are also discussed. New data presented on high temperature gas chromatography--mass spectrometry of deuterio-reduced permethylated pyrolysates of cellulose lead to a better understanding of polysaccharide dissociation mechanisms. Pyrolysis as an on-line sample pretreatment method for organic macromolecules in combination with MS techniques is a very challenging field of mass spectrometry. Pyrolytic dissociation and desorption is not at all a chaotic process but proceeds according to very specific mechanisms.
Tobella, Lorena M; Bunster, Marta; Pooley, Amalia; Becerra, José; Godoy, Felix; Martínez, Miguel A
2005-09-01
Poly-beta-hydroxyalkanoates (PHA) polymer is synthesized by different bacterial species. There has been considerable interest in the development and production of biodegradable polymers; however, the high cost of PHA production has restricted its applications. Kraft cellulose industry effluents containing 2,4,6-trichlorophenol (10 or 20 microg ml(-1)) were used by the bacteria Sphingopyxis chilensis S37 and Wautersia sp. PZK to synthesize PHA. In this condition, S. chilensis S37 was able to grow and degrade 2,4,6-trichlorophenol (ca. 60%) and 80% of these cells accumulated PHA. Wautersia PZK completely degraded 2,4,6-TCP and more than 90% of the cells accumulated PHA in 72 h. The PHA detection was performed by flow cytometry and polyester composition was characterized by gas chromatography-mass spectroscopy (GC-MS), indicating that these polymers are made by 3-hydroxybutyric acid and 3-hydroxyhexadecanoic acid for S37 and PZK strains, respectively. Results demonstrated that strains' growth and PHA production and composition are not modified in cellulose effluents with or without 2,4,6-TCP (10-20 microg ml(-1)). Therefore, our results indicate that S. chilensis S37 and Wautersia sp. PZK are able to degrade a toxic compound such as a 2,4,6-TCP and simultaneously produce a valuable biopolymer using low-value substrates.
Enhanced cellulose degradation using cellulase-nanosphere complexes.
Blanchette, Craig; Lacayo, Catherine I; Fischer, Nicholas O; Hwang, Mona; Thelen, Michael P
2012-01-01
Enzyme catalyzed conversion of plant biomass to sugars is an inherently inefficient process, and one of the major factors limiting economical biofuel production. This is due to the physical barrier presented by polymers in plant cell walls, including semi-crystalline cellulose, to soluble enzyme accessibility. In contrast to the enzymes currently used in industry, bacterial cellulosomes organize cellulases and other proteins in a scaffold structure, and are highly efficient in degrading cellulose. To mimic this clustered assembly of enzymes, we conjugated cellulase obtained from Trichoderma viride to polystyrene nanospheres (cellulase:NS) and tested the hydrolytic activity of this complex on cellulose substrates from purified and natural sources. Cellulase:NS and free cellulase were equally active on soluble carboxymethyl cellulose (CMC); however, the complexed enzyme displayed a higher affinity in its action on microcrystalline cellulose. Similarly, we found that the cellulase:NS complex was more efficient in degrading natural cellulose structures in the thickened walls of cultured wood cells. These results suggest that nanoparticle-bound enzymes can improve catalytic efficiency on physically intractable substrates. We discuss the potential for further enhancement of cellulose degradation by physically clustering combinations of different glycosyl hydrolase enzymes, and applications for using cellulase:NS complexes in biofuel production.
Enhanced Cellulose Degradation Using Cellulase-Nanosphere Complexes
Blanchette, Craig; Lacayo, Catherine I.; Fischer, Nicholas O.; Hwang, Mona; Thelen, Michael P.
2012-01-01
Enzyme catalyzed conversion of plant biomass to sugars is an inherently inefficient process, and one of the major factors limiting economical biofuel production. This is due to the physical barrier presented by polymers in plant cell walls, including semi-crystalline cellulose, to soluble enzyme accessibility. In contrast to the enzymes currently used in industry, bacterial cellulosomes organize cellulases and other proteins in a scaffold structure, and are highly efficient in degrading cellulose. To mimic this clustered assembly of enzymes, we conjugated cellulase obtained from Trichoderma viride to polystyrene nanospheres (cellulase:NS) and tested the hydrolytic activity of this complex on cellulose substrates from purified and natural sources. Cellulase:NS and free cellulase were equally active on soluble carboxymethyl cellulose (CMC); however, the complexed enzyme displayed a higher affinity in its action on microcrystalline cellulose. Similarly, we found that the cellulase:NS complex was more efficient in degrading natural cellulose structures in the thickened walls of cultured wood cells. These results suggest that nanoparticle-bound enzymes can improve catalytic efficiency on physically intractable substrates. We discuss the potential for further enhancement of cellulose degradation by physically clustering combinations of different glycosyl hydrolase enzymes, and applications for using cellulase:NS complexes in biofuel production. PMID:22870287
Agrawal, Anjali; Dudhedia, Mayur; Deng, Weibin; Shepard, Kevin; Zhong, Li; Povilaitis, Edward; Zimny, Ewa
2016-02-01
The objective of the study was to identify the extragranular component requirements (level and type of excipients) to develop an immediate release tablet of solid dispersions prepared by hot melt extrusion (HME) process using commonly used HME polymers. Solid dispersions of compound X were prepared using polyvinyl pyrrolidone co-vinyl acetate 64 (PVP VA64), Soluplus, and hypromellose acetate succinate (HPMCAS-LF) polymers in 1:2 ratio by HME through 18 mm extruder. A mixture design was employed to study effect of type of polymer, filler (microcrystalline cellulose (MCC), lactose, and dicalcium phosphate anhydrous (DCPA)), and disintegrant (Crospovidone, croscarmellose sodium, and sodium starch glycolate (SSG)) as well as level of extrudates, filler, and disintegrant on tablet properties such as disintegration time (DT), tensile strength (TS), compactibility, and dissolution. Higher extrudate level resulted in longer DT and lower TS so 60-70% was the maximum amount of acceptable extrudate level in tablets. Fast disintegration was achieved with HPMCAS-containing tablets, whereas Soluplus- and PVP VA64-containing tablets had higher TS. Crospovidone and croscarmellose sodium were more suitable disintegrant than SSG to achieve short DT, and MCC was a suitable filler to prepare tablets with acceptable TS for each studied HME polymer. The influence of extragranular components on dissolution from tablets should be carefully evaluated while finalizing tablet composition, as it varies for each HME polymer. The developed statistical models identified suitable level of fillers and disintegrants for each studied HME polymer to achieve tablets with rapid DT (<15 min) and acceptable TS (≥1 MPa at 10-15% tablet porosity), and their predictivity was confirmed by conducting internal and external validation studies.
Youssef, Ahmed M; El-Samahy, Magda Ali; Abdel Rehim, Mona H
2012-08-01
Conducting paper based on natural cellulosic fibers and conductive polymers was prepared using unbleached bagasse and/or rice straw fibers (as cellulosic raw materials) and polyaniline (PANi) as conducting polymer. These composites were synthesized by in situ emulsion polymerization using ammonium persulfate (APS) as oxidant in the presence of dodecylbenzene sulfonic acid (DBSA) as emulsifier. The prepared composites were characterized using Fourier transform infrared (FTIR), thermal gravimetric analysis (TGA), differential scanning calorimeter (DSC), and their morphology was investigated using scanning electron microscope (SEM). Electrical conductivity measurements showed that the conductivity of the paper sheets increases by increasing the ratio of PANi in the composite. Mechanical properties of the paper sheets were also investigated, the results revealed that the values of breaking length, burst factor, and tear factor are decreased with increasing ratio of added PANi, and this effect is more pronounced in bagasse-based composites. The new conductive composites can have potential use as anti-static packaging material or anti-bacterial paper for packaging applications. Copyright © 2012 Elsevier Ltd. All rights reserved.
Cotton-based Cellulose Nanomaterials for Applications in Composites and Electronics
NASA Astrophysics Data System (ADS)
Farahbakhsh, Nasim
A modern society demands development of highly valued and sustainable products via innovative process technologies and utilizing bio-based alternatives for petroleum based materials. Systematic comparative study of nanocellulose particles as a biodegradable and renewable reinforcing agent can help to develop criteria for selecting an appropriate candidate to be incorporated in polymer nanocomposites. Of particular interest has been nanocellulosic materials including cellulose nanocrystal (CNC) and micro/nanofibrilated cellulose (MFC/NFC) which possess a hierarchical structure that permits an ordered structure with unique properties that has served as building blocks for the design of green and novel materials composites for applications in flexible electronics, medicine and composites. Key differences exist in nanocellulosic materials as a result the process by which the material is produced. This research demonstrates the applicability for the use of recycled cotton as promising sustainable material to be utilized as a substrate for electronic application and a reinforcing agent choice that can be produced without any intensive purification process and be applied to synthetic-based polymer nanocomposites in melt-processing. (Abstract shortened by ProQuest.).
Motta, F L; Santana, M H A
2013-01-01
The novelty of this study was to produce humic acids by submerged fermentation of empty fruit bunch (EFB) with Trichoderma viride and to investigate the effects of the cellulosic substrates and the organic sources of nitrogen on the biotechnological production of these acids. The results obtained indicate the potential application of EFB, a waste of oil palm processing, for humic acids production. Because EFB contains cellulose, hemicellulose and lignin, fermentations were also performed using these polymers as carbon sources, separately or in combination. After 120 h of fermentation, significant production of humic acids was observed only in cultures containing either EFB or a mixture of the three polymers. Use of either potato peptone or yeast extract as a nitrogen source yielded nearly identical patterns of fungal growth and production of humic acids. The data obtained from microscopic imaging of T. viride growth and sporulation in EFB, coupled with the determined rates of production of humic acids indicated that the production of these acids is related to T. viride sporulation. © 2013 American Institute of Chemical Engineers.
Photo-Healable Metallosupramolecular Polymers
2014-01-09
doi: 10.1038/nmat2891 Mark Burnworth, Liming Tang , Justin R. Kumpfer, Andrew J. Duncan, Frederick L. Beyer, Gina L. Fiore, Stuart J. Rowan...Mark Burnworth, Liming Tang , Stuart J. Rowan, Christoph Weder. Reinforcement of Self- Healing Polymer Films with Cellulose Nanowhiskers, ACS PMSE...Macromolecules (08 2011) Mark Burnworth, Liming Tang , Justin R. Kumpfer, Andrew J. Duncan, Frederick L. Beyer, Stuart J. Rowan, Christoph Weder
Lecomte, F; Siepmann, J; Walther, M; MacRae, R J; Bodmeier, R
2004-09-14
The aim of this study was to investigate the importance of the type of plasticizer in polymer blends used for the coating of solid dosage forms, comparing a lipophilic and a hydrophilic plasticizer (dibutyl sebacate (DBS) and triethyl citrate (TEC)). In vitro drug release from propranolol hydrochloride (propranolol HCl)-loaded pellets coated with blends of ethyl cellulose (EC) and Eudragit L (100:0, 75:25, 50:50, 25:75 and 0:100 w/w) was investigated at low as well as at high pH. To better understand the underlying mass transport mechanisms, the physicochemical properties of the film coatings (e.g. mechanical resistance, water uptake and dry weight loss behavior) were determined. Interestingly, drug release strongly depended on the type of plasticizer. Importantly, not only the slope but also the shape of the release curves was affected, indicating that the chemical nature of the plasticizer plays a major role for the underlying drug release mechanisms. Diffusion through the intact polymer coatings and/or through water-filled cracks was found to be dominating for the control of drug release. The relative importance of these pathways strongly depended on the polymer blend ratio and type of plasticizer. In contrast to DBS, TEC rapidly leached out of the coatings, resulting in decreasing mechanical resistances of the films and, thus, facilitated crack formation. In addition, the hydrophilicity of the plasticizer significantly affected the water uptake behavior of the film coatings and, hence, changes in the coatings' toughness and drug permeability. Also the relative affinity of the plasticizer to the different polymers was found to be of significance. In contrast to TEC, DBS has a higher affinity to EC than to Eudragit L, resulting in potential redistributions of this plasticizer within the polymeric systems and changes in the release profiles during storage. Importantly, these effects could be avoided with appropriate curing conditions and preparation techniques for the coating dispersions.
Bteich, Joseph; Ernsting, Mark J; Mohammed, Mohammed; Kiyota, Taira; McKee, Trevor D; Trikha, Mohit; Lowman, Henry B; Sokoll, Kenneth K
2018-05-23
Nanoparticles provide a unique opportunity to explore the benefits of selective distribution and release of cancer therapeutics at sites of disease through varying particle sizes and compositions that exploit the enhanced permeability of tumor-associated blood vessels. Though delivery of larger as opposed to smaller and/or actively transported molecules to the brain is prima facie a challenging endeavor, we wondered whether nanoparticles could improve the therapeutic index of existing drugs for use in treating brain tumors via these vascular effects. We therefore selected a family of nanoparticles composed of cabazitaxel-carboxymethyl cellulose amphiphilic polymers to investigate the potential for delivering a brain-penetrant taxane to intracranial brain tumors in mice. Among a small set of nanoparticle formulations, we found evidence for nanoparticle accumulation in the brain, and one such formulation demonstrated activity in an orthotopic model of glioma, suggesting that such nanoparticles could be useful for the treatment of glioma and brain metastases of other tumor types.
Polski, Andrzej; Iwaniak, Karol; Kasperek, Regina; Modrzewska, Joanna; Sobótka-Polska, Karolina; Sławińska, Karolina; Poleszak, Ewa
2015-01-01
The capsule is one of the most important solid dosage forms in the pharmaceutical industry. It is easier and faster to produce than a tablet, because it requires fewer excipients. Generally, capsules are easy to swallow and mask any unpleasant taste of the substances used while their release profiles can be easily modified. Papaverine hydrochloride was used as a model substance to show different release profiles using different excipients. The main aim of the study was to analyze the impact of using different polymers on the release profile of papaverine hydrochloride from hard gelatin capsules. Six series of hard gelatin capsules containing papaverine hydrochloride as a model drug and different excipients were made. Then, the angle of repose, flow rate, mass flow rate and volume flow rate of the powders used for capsule production were analyzed. The uniform weight and disintegration time of the capsules were studied. The dissolution study was performed in a basket apparatus, while the amount of papaverine hydrochloride released was determined spectrophotometrically at 251 nm. Only one formula of powder had satisfactory flow properties, while all formulas had good Hausner ratios. The best properties were from powder containing polyvinylpyrrolidone 10k. The disintegration time of capsules varied from 1:30 min to 2:00 min. As required by Polish Pharmacopoeia X, 80% of the active substance in all cases was released within 15 minutes. The capsules with polyvinylpyrrolidone 10k were characterized by the longest release. On the other hand, capsules containing microcrystalline cellulose had the fastest release profile. Using 10% of different polymers, without changing the other excipients, had a significant impact on the physical properties of the powders and papaverine hydrochloride release profile. The two most preferred capsule formulations contained either polyvinylpyrrolidone 10k or microcrystalline cellulose.
The molecular basis of plant cell wall extension.
Darley, C P; Forrester, A M; McQueen-Mason, S J
2001-09-01
In all terrestrial and aquatic plant species the primary cell wall is a dynamic structure, adjusted to fulfil a diversity of functions. However a universal property is its considerable mechanical and tensile strength, whilst being flexible enough to accommodate turgor and allow for cell elongation. The wall is a composite material consisting of a framework of cellulose microfibrils embedded in a matrix of non-cellulosic polysaccharides, interlaced with structural proteins and pectic polymers. The assembly and modification of these polymers within the growing cell wall has, until recently, been poorly understood. Advances in cytological and genetic techniques have thrown light on these processes and have led to the discovery of a number of wall-modifying enzymes which, either directly or indirectly, play a role in the molecular basis of cell wall expansion.
One-pot biosynthesis of polymer-inorganic nanocomposites
NASA Astrophysics Data System (ADS)
Geng, Jiaqing; Yang, Dong; Zhu, Yong; Cao, Lichao; Jiang, Zhongyi; Sun, Yan
2011-06-01
A biological method is demonstrated to fabricate the polymer-inorganic nanocomposites (PINCs) utilizing bacterium as an efficient and versatile biofactory. Gluconacetobacter xylinum that can produce bacterial cellulose is incubated in the culture medium containing titanium or silica precursor. The PINCs can be acquired under the elaborate control of the culturing condition of G. xylinum, in which the formation of inorganic nanoparticles about several tens of nanometers in size synchronizes the fabrication of reticulated bacterial cellulose membrane composed of dense and finely branched nanofibers about 60-120 nm in diameter. The composition and chemical states, morphology, thermal stability of the inorganic nanoparticles, and nanocomposites were extensively characterized. A tentative mechanism for the formation of PINCs is proposed. It is hoped that this study may establish a generic platform toward facile and green synthesis of nanocomposite materials.
Ahmed, Tarek A; Aljaeid, Bader M
2016-01-01
Naturally occurring polymers, particularly of the polysaccharide type, have been used pharmaceutically for the delivery of a wide variety of therapeutic agents. Chitosan, the second abundant naturally occurring polysaccharide next to cellulose, is a biocompatible and biodegradable mucoadhesive polymer that has been extensively used in the preparation of micro-as well as nanoparticles. The prepared particles have been exploited as a potential carrier for different therapeutic agents such as peptides, proteins, vaccines, DNA, and drugs for parenteral and nonparenteral administration. Therapeutic agent-loaded chitosan micro- or nanoparticles were found to be more stable, permeable, and bioactive. In this review, we are highlighting the different methods of preparation and characterization of chitosan micro- and nanoparticles, while reviewing the pharmaceutical applications of these particles in drug delivery. Moreover, the roles of chitosan derivatives and chitosan metal nanoparticles in drug delivery have been illustrated. PMID:26869768
Ferrocene-decorated nanocrystalline cellulose with charge carrier mobility.
Eyley, Samuel; Shariki, Sara; Dale, Sara E C; Bending, Simon; Marken, Frank; Thielemans, Wim
2012-04-24
Ferrocene-decorated cellulose nanowhiskers were prepared by the grafting of ethynylferrocene onto azide functionalized cotton-derived cellulose nanowhiskers using azide-alkyne cycloaddition. Successful surface modification and retention of the crystalline morphology of the nanocrystals was confirmed by elemental analysis, inductively coupled plasma-atomic emission spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. The coverage with ferrocenyl is high (approximately 1.14 × 10(-3) mol g(-1) or 4.6 × 10(13) mol cm(-2) corresponding to a specific area of 61 Å(2) per ferrocene). Cyclic voltammetry measurements of films formed by deposition of ferrocene-decorated nanowhiskers showed that this small spacing of redox centers along the nanowhisker surface allowed conduction hopping of electrons. The apparent diffusion coefficient for electron (or hole) hopping via Fe(III/II) surface sites is estimated as Dapp = 10(-19) m(2)s(-1) via impedance methods, a value significantly less than nonsolvated ferrocene polymers, which would be expected as the 1,2,3-triazole ring forms a rigid linker tethering the ferrocene to the nanowhisker surface. In part, this is believed to be also due to "bottleneck" diffusion of charges across contact points where individual cellulose nanowhiskers contact each other. However, the charge-communication across the nanocrystal surface opens up the potential for use of cellulose nanocrystals as a charge percolation template for the preparation of conducting films via covalent surface modification (with applications similar to those using adsorbed conducting polymers), for use in bioelectrochemical devices to gently transfer and remove electrons without the need for a solution-soluble redox mediator, or for the fabrication of three-dimensional self-assembled conducting networks.
Recyclable Thermoresponsive Polymer-Cellulase Bioconjugates for Biomass Depolymerization
Mackenzie, Katherine J.; Francis, Matthew B.
2013-01-01
Here we report the construction and characterization of a recoverable, thermoresponsive polymer-endoglucanase bioconjugate that matches the activity of unmodified enzymes on insoluble cellulose substrates. Two copolymers exhibiting a thermoresponsive lower critical solution temperature (LCST) were created through the copolymerization of an aminooxy-bearing methacrylamide with N-isopropylacrylamide (NIPAm) or N-isopropylmethacrylamide (NIPMa). The aminooxy group provided a handle through which the LCST was adjusted through small-molecule quenching. This allowed materials with LCSTs ranging from 20.9 °C to 60.5 °C to be readily obtained after polymerization. The thermostable endoglucanase EGPh from the hypothermophilic Pyrococcus horikoshii was transaminated with pyridoxal-5’-phosphate to produce a ketone-bearing protein, which was then site-selectively modified through oxime linkage with benzylalkoxyamine or 5 kDa-poly(ethylene glycol)-alkoxyamine. These modified proteins showed activity comparable to the controls when assayed on an insoluble cellulosic substrate. Two polymer bioconjugates were then constructed using transaminated EGPh and the aminooxy-bearing copolymers. After twelve hours, both bioconjugates produced an equivalent amount of free reducing sugars as the unmodified control using insoluble cellulose as a substrate. The recycling ability of the NIPAm copolymer-EGPh conjugate was determined through three rounds of activity, maintaining over 60% activity after two cycles of reuse and affording significantly more soluble carbohydrates than unmodified enzyme alone. When assayed on acid-pretreated Miscanthus, this bioconjugate increased the amount of reducing sugars by 2.8-fold over three rounds of activity. The synthetic strategy of this bioconjugate allows the LCST of the material to be changed readily from a common stock of copolymer and the method of attachment is applicable to a variety of proteins, enabling the same approach to be amenable to thermophile-derived cellulases or to the separation of multiple species using polymers with different recovery temperatures. PMID:23270527
Old Cellulose for New Multifunctional Networks
NASA Astrophysics Data System (ADS)
Yong, Geng
Cellulose is considered to be the most abundant and renewable natural polymer on earth. It is the main component of plant cells. The exploration of the utility and applications of this material and its derivatives has never stopped since human's birth. It is well known that cellulose based materials can generate films and fibers, which can be, for instance, produced from cellulosic solutions. The Cellulose rich chemical structure allows different behaviors of the polymer in solution, which is the driving force for diverse films and fibers features. The main goal of this work is the manufacture and characterization of new application of the renewable cellulosic-based materials, which are at the origin of stimuli-responsive and/or functional soft films and fibers. The several materials obtained have in common the main chain cellulose backbone but present different liquid crystalline properties. Firstly rheology coupled to nuclear magnetic resonance techniques (rheo-NMR) were used to characterize a cellulose-water based liquid crystalline solution in order to establish structure/properties relationships, which were the basis to improve the design of films and fibers produced in the framework of this work. The results achieved were at the origin of a paper published in Macromolecules. Then films were produced and due to their structure and enhanced mechanical properties, different applications were realized by producing cellulosic gratings, which mimic the periodic structures that can be found in some petals of plants and a soft cellulose moisture motor was built for the first time. Two manuscripts were published, one related to the grating mimics, in Macromolecular Chemistry and Physics, and the other one dedicated to the mechanical properties and the bending of a cellulosic film controlled by moisture action in Scientific Reports (Nature Publishing Group). Concerning cellulosic fibers, two methods were selected to fabricate micro/nano networks. In order to produce suspended aligned arrays, electrospinning was chosen due to its versatility. On the obtained nano/micro cylinders, nematic and cholesteric droplets were threaded producing necklaces of liquid crystal beads for the first time. The fiber changes not only the topology of the droplet but also distorts its spherical shape to an approximately ellipsoidal droplet. An additional cylindrical surface with planar anchoring along the droplet's long axis was also added. Designing nematic and cholesteric liquid crystal microdroplets on thin long threads opened new routes to produce fiber waveguides decorated with complex microresonators. Two Soft Matter scientific papers were published based on this work (One was chosen as the cover of that issue). Finally, nano-fibers produced by cellulose acid hydrolises were prepared and a new electro-optical sensor was built up and characterized and the results published in Liquid Crystals journal. Throughout this work Landau-de-Gennes theory was used in order to interpret and understand some of the experimental results achieved.
Polymeric materials from renewable resources
NASA Astrophysics Data System (ADS)
Frollini, Elisabete; Rodrigues, Bruno V. M.; da Silva, Cristina G.; Castro, Daniele O.; Ramires, Elaine C.; de Oliveira, Fernando; Santos, Rachel P. O.
2016-05-01
The goals of our studies have been the use of renewable raw materials in the preparation of polymeric materials with diversified properties. In this context, lignosulfonate, which is produced in large scale around the world, but not widely used in the production of polymeric materials, was used to replace phenol and polyols in the preparation of phenolic- (Ligno-PH) and polyurethane-type (Ligno-PU) polymers, respectively. These polymers were used to prepare composites reinforced with sisal lignocellulosic fibers. The use of lignosulfonate in the formulation of both types of polymers was beneficial, because in general composites with improved properties, specially impact strength, were obtained. Composites were also prepared from the so called "biopolyethylene" (HDPE), curaua lignocellulosic fiber, and castor oil (CO). All composites HDBPE/CO/Fiber exhibited higher impact strength, when compared to those of the corresponding HDBPE/Fiber. These results, combined with others (eg SEM images of the fractured surfaces) indicated that, in addition to acting as a plasticizer, this oil may have acted as a compatibilizer of the hydrophilic fiber with the hydrophobic polymer. The set of results indicated that (i) mats with nano (diameter ≤ 100nm) and/or ultrafine (submicron scale) fibers were produced, (ii) hybrid fibers were produced (bio-based mats composites), (iii) cellulosic pulp (CP) and/or lignin (Lig) can be combined with PET matrices to control properties such as stiffness and hydrophilicity of the respective mats. Materials with diversified properties were prepared from high content of renewable raw materials, thus fulfilling the proposed targets.
Federal Register 2010, 2011, 2012, 2013, 2014
2013-11-13
..., lauric acid, potassium sorbate, ethylene brassylate, copper gluconate, octinoxate, phenylenediamine..., cellulose, agarose, polymers, PVC, methyl methacrylate, and ethylene terapthalate (duty rate ranges from...
Method for conversion of carbohydrate polymers to value-added chemical products
Zhang, Zongchao C [Norwood, NJ; Brown, Heather M [Kennewick, WA; Su, Yu [Richland, WA
2012-02-07
Methods are described for conversion of carbohydrate polymers in ionic liquids, including cellulose, that yield value-added chemicals including, e.g., glucose and 5-hydroxylmethylfurfural (HMF) at temperatures below 120.degree. C. Catalyst compositions that include various mixed metal halides are described that are selective for specified products with yields, e.g., of up to about 56% in a single step process.
Ultrastructure Processing of Ordered Polymers
1990-01-18
from regenerated cellulose , then from synthetic polymer consisting of chemical raw materials derived from oils and coal. Since then, some scientists have...ordered crystal- line material, crystallite, throughout the fiber, which is composed of microfibrils and fibrils. The small crystallites are regularly...these flat ribbons appears to consist of smaller " microfibrils " of lateral dimension varying from 50-80 A, as described before(Figs. 15 and 16). These
Low-Cost Nanocellulose-Reinforced High-Temperature Polymer Composites for Additive Manufacturing
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ozcan, Soydan; Tekinalp, Halil L.; Love, Lonnie J.
2016-07-13
ORNL worked with American Process Inc. to demonstrate the potential use of bio-based BioPlus ® lignin-coated cellulose nanofibrils (L-CNF) as a reinforcing agent in the development of polymer feedstock suitable for additive manufacturing. L-CNF-reinforced polylactic acid (PLA) testing coupons were prepared and up to 69% increase in tensile strength and 133% increase in elastic modulus were demonstrated.
Surface Modification of Nanocellulose Substrates
NASA Astrophysics Data System (ADS)
Zoppe, Justin Orazio
Cellulose fibers constitute an important renewable raw material that is utilized in many commercial applications in non-food, paper, textiles and composite materials. Chemical functionalization is an important approach for improving the properties of cellulose based materials. Different approaches are used to graft polymeric chains onto cellulose substrates, which can be classified by two principal routes, namely 'grafting onto' or 'grafting from' methods. Never-dried cellulose nanocrystals (CNCs) or nanowhiskers produced from sulfuric acid hydrolysis of ramie fibers were used as substrates for surface chemical functionalization with various macromolecules. In addition, the use of cellulose nanocrystals to reinforce poly(epsilon-caprolactone) (PCL) nanofibers was studied. Chemical grafting with low molecular weight polycaprolactone diol onto cellulose nanocrystals was carried out in an attempt to improve the interfacial adhesion with the fiber matrix. Significant improvements in the mechanical properties of the nanofibers after reinforcement with unmodified cellulose nanocrystals were confirmed. Fiber webs from PCL reinforced with 2.5% unmodified CNCs showed ca. 1.5-fold increase in Young's modulus and ultimate strength compared to PCL webs. The CNCs were also grafted with poly(N-isopropylacrylamide) (poly(NiPAAm)) brushes via surface-initiated single-electron transfer living radical polymerization (SI-SETLRP) under various conditions at room temperature. The grafting process depended on the initiator and/or monomer concentrations used. No observable damage occurred to the CNCs after grafting, as determined by X-ray diffraction. Size exclusion chromatography analyses of polymer chains cleaved from the cellulose nanocrystals indicated that a higher degree of polymerization was achieved by increasing initiator or monomer loading, most likely caused by local heterogeneities yielding higher rates of polymerization. In addition, the colloidal stability and thermo-responsive behavior of poly(NiPAAm) brushes grafted from nanoparticles of CNCs of varying graft densities and molecular weights was investigated. Halo areas surrounding grafted CNCs that were adsorbed on silica and imaged with an AFM were indicative of the grafted polymer brushes. Aggregation of nanoparticles carrying grafts of high degree of polymerization was observed. The responsiveness of CNCs in liquid medium and as spin-coated films was determined by using light scattering, viscometry and Colloidal Probe Microscopy (CPM). Light transmittance measurements showed temperaturedependent aggregation originating from the different graft densities and molecular weights and a sharp increase in dispersion viscosity as the temperature approached the LCST. The lower critical solution temperature (LCST) of grafted poly(NiPAAm) brushes was found to decrease with the ionic strength as is the case of neat poly(NiPAAm) in aqueous solution. CPM in aqueous media for asymmetric systems consisting of thin films of CNCs and a colloidal silica probe showed the distinctive effects of the grafted polymer brushes on the interaction (repulsive and adhesive) forces. The origin of such forces was mainly electrostatic and steric in the case of bare and grafted CNCs, respectively. A decrease in the onset of attractive and adhesion forces of grafted CNCs films was observed with the ionic strength of the aqueous solution medium. The decreased mobility of polymer brushes upon partial collapse and decreased availability of hydrogen bonding sites with higher electrolyte concentration were hypothesized as main reasons for the less prominent polymer bridging between interacting surfaces. Finally, poly(NiPAAm)-g-CNCs were utilized as a Pickering emulsions stabilizer. All emulsions formed were oil-in-water confirmed by a drop test. Various drop sizes were obtained as characterized by laser scattering particle size analysis and optical microscopy. Anisotropic colloidal assemblies of grafted CNCs at the oil-water interface were observed in freeze-fractured samples via Transmission Electron Microscopy. Emulsions were stable for over three months at the time of writing this thesis, however rapidly broke above the LCST as determined by rheometry.
The impact of alterations in lignin deposition on cellulose organization of the plant cell wall
DOE Office of Scientific and Technical Information (OSTI.GOV)
Liu, Jiliang; Kim, Jeong Im; Cusumano, Joanne C.
Background: Coordination of synthesis and assembly of the polymeric components of cell walls is essential for plant growth and development. Given the degree of co-mingling and cross-linking among cell wall components, cellulose organization must be dependent on the organization of other polymers such as lignin. Here we seek to identify aspects of that codependency by studying the structural organization of cellulose fibrils in stems from Arabidopsis plants harboring mutations in genes encoding enzymes involved in lignin biosynthesis. Plants containing high levels of G-lignin, S-lignin, H-lignin, aldehyde-rich lignin, and ferulic acid-containing lignin, along with plants with very low lignin content weremore » grown and harvested and longitudinal sections of stem were prepared and dried. Scanning X-ray microdiffraction was carried out using a 5-micron beam that moved across the sections in 5-micron steps and complete diffraction patterns were collected at each raster point. Approximately, 16,000 diffraction patterns were analyzed to determine cellulose fibril orientation and order within the tissues making up the stems. Results: Several mutations-most notably those exhibiting (1) down-regulation of cinnamoyl CoA reductase which leads to cell walls deficient in lignin and (2) defect of cinnamic acid 4-hydroxylase which greatly reduces lignin content-exhibited significant decrease in the proportion of oriented cellulose fibrils in the cell wall. Distinctions between tissues were maintained in all variants and even in plants exhibiting dramatic changes in cellulosic order the trends between tissues (where apparent) were generally maintained. The resilience of cellulose to degradative processes was investigated by carrying out the same analysis on samples stored in water for 30 days prior to data collection. This treatment led to significant loss of cellulosic order in plants rich in aldehyde or H-lignin, less change in wild type, and essentially no change in samples with high levels of G-or S-lignin. Conclusions: These studies demonstrate that changes in lignin biosynthesis lead to significant disruption in the orientation and order of cellulose fibrils in all tissues of the stem. These dramatic phenotypic changes, in mutants with lignin rich in aldehyde or H-units, correlate with the impact the mutations have on the enzymatic degradation of the plant cell wall.« less
Pelissari, Franciele Maria; Andrade-Mahecha, Margarita María; Sobral, Paulo José do Amaral; Menegalli, Florencia Cecilia
2017-11-01
Cellulose nanofibers were isolated from banana peel using a combination of chemical and mechanical treatments with different number of passages through the high-pressure homogenizer (0, 3, 5, and 7 passages). New nanocomposites were then prepared from a mixed suspension of banana starch and cellulose nanofibers using the casting method and the effect of the addition of these nanofibers on the properties of the resulting nanocomposites was investigated. The cellulose nanofibers homogeneously dispersed in the starch matrix increased the glass transition temperature, due to the strong intermolecular interactions occurring between the starch and cellulose. The nanocomposites exhibited significantly increased the tensile strength, Young's modulus, water-resistance, opacity, and crystallinity as the number of passages through the homogenizer augmented. However, a more drastic mechanical treatment (seven passages) caused defects in nanofibers, deteriorating the nanocomposite properties. The most suitable mechanical treatment condition for the preparation of cellulose nanofibers and the corresponding nanocomposite was five passages through the high-pressure homogenizer. In general, the cellulose nanofibers improved the features of the starch-based material and are potentially applicable as reinforcing elements in a variety of polymer composites. Copyright © 2017 Elsevier Inc. All rights reserved.
Shen, Tongye; Gnanakaran, S
2009-04-22
A critical roadblock to the production of biofuels from lignocellulosic biomass is the efficient degradation of crystalline microfibrils of cellulose to glucose. A microscopic understanding of how different physical conditions affect the overall stability of the crystalline structure of microfibrils could facilitate the design of more effective protocols for their degradation. One of the essential physical interactions that stabilizes microfibrils is a network of hydrogen (H) bonds: both intrachain H-bonds between neighboring monomers of a single cellulose polymer chain and interchain H-bonds between adjacent chains. We construct a statistical mechanical model of cellulose assembly at the resolution of explicit hydrogen-bond networks. Using the transfer matrix method, the partition function and the subsequent statistical properties are evaluated. With the help of this lattice-based model, we capture the plasticity of the H-bond network in cellulose due to frustration and redundancy in the placement of H-bonds. This plasticity is responsible for the stability of cellulose over a wide range of temperatures. Stable intrachain and interchain H-bonds are identified as a function of temperature that could possibly be manipulated toward rational destruction of crystalline cellulose.
Endoglucanase (EG) Activity Assays.
Rahman, M Shafiqur; Fernando, Sheran; Ross, Brian; Wu, Jiangning; Qin, Wensheng
2018-01-01
Cellulosic biomass, the most common organic compound of primary energy source on earth, is a network of interwoven biopolymers of plant cell walls. Degradation of cellulose is important for global carbon recycling. Moreover, biofuel, a renewable fuel whose energy can be derived from cellulosic biomass by enzymatic hydrolysis of cellulases. Among cellulases are endoglucases that act synergistically for subsequent hydrolytic reactions to break down the polymeric cellulose. However, in cellulolytic enzyme activity endoglucanase plays a prominent role in initiating and sustaining the hydrolytic process. Endoglucanase randomly cleaves the cellulose polymer into smaller sugar and oligomeric polysaccharides. Characterization and quantification of endoglucanase activity is important for industry and in the overall study of cellulose degradation. All assays including those for endoglucanase fall into two broad categories either qualitative or quantitative. Quantitative assays can tell if the enzyme is present, how much and its activity. Measurement can be done indirectly using a secondary colorimetric product like (1) molybdenum blue, (2) 3-amino-5-nitrosalicylic acid, (3) bicinchoninic acid (BCA), and (4) 2-cyanoacetamide or directly using an antibody in an ELISA. In this chapter, we discuss several common protocols for the measurement of endoglucanase activity.
Joshi, Mahesh Kumar; Tiwari, Arjun Prasad; Pant, Hem Raj; Shrestha, Bishnu Kumar; Kim, Han Joo; Park, Chan Hee; Kim, Cheol Sang
2015-09-09
Post-electrospinning treatment is a facile process to improve the properties of electrospun nanofibers for various applications. This technique is commonly used when direct electrospinning is not a suitable option to fabricate a nonwoven membrane of the desired polymer in a preferred morphology. In this study, a representative natural-synthetic hybrid of cellulose acetate (CA) and polycaprolactone (PCL) in different ratios was fabricated using an electrospinning process, and CA in the hybrid fiber was transformed into cellulose (CL) by post-electrospinning treatment via alkaline saponification. Scanning electron microscopy was employed to study the effects of polymer composition and subsequent saponification on the morphology of the nanofibers. Increasing the PCL content in the PCL/CA blend solution caused a gradual decrease in viscosity, resulting in smoother and more uniform fibers. The saponification of fibers lead to pronounced changes in the physicochemical properties. The crystallinity of the PCL in the composite fiber was varied according to the composition of the component polymers. The water contact angle was considerably decreased (from 124° to less than 20°), and the mechanical properties were greatly enhanced (Young's Modulus was improved by ≈20-30 fold, tensile strength by 3-4 fold, and tensile stress by ≈2-4 fold) compared to those of PCL and PCL/CA membranes. Regeneration of cellulose chains in the nanofibers increased the number of hydroxyl groups, which increased the hydrogen bonding, thereby improving the mechanical properties and wettability of the composite nanofibers. The improved wettability and presence of surface functional groups enhanced the ability to nucleate bioactive calcium phosphate crystals throughout the matrix when exposed to a simulated body fluid solution. Experimental results of cell viability assay, confocal microscopy, and scanning electron microscopy imaging showed that the fabricated nanofibrous membranes have excellent ability for MC3T3-E1 cell proliferation and growth. Given the versatility and widespread use of cellulose-synthetic hybrid systems in the construction of tissue-engineered scaffolds, this work provides a novel strategy to fabricate the biopolymer-based materials for applications in tissue engineering and regenerative medicine.
Beaussart, Audrey; Mierczynska-Vasilev, Agnieszka; Beattie, David A
2010-06-15
The adsorption of carboxymethyl cellulose (CMC) on the basal planes of talc and molybdenite has been studied using in situ atomic force microscope (AFM) imaging. These experiments were partnered with quantitative adsorption isotherm determinations on particulate samples. The isotherms revealed a clear increase of the CMC adsorbed amount upon increasing the solution ionic strength for adsorption on both minerals. In addition, the shapes of the isotherms changed in response to the change in the electrolyte concentration, with CMC on talc displaying stepped (10(-3) M KCl), Langmuir (10(-2) M KCl), then Freundlich isotherm shapes (10(-1) M KCl), and CMC on molybdenite displaying stepped (10(-3) M KCl), Freundlich (10(-2) M KCl), then Langmuir isotherm shapes (10(-1) M KCl). AFM imaging of the polymer layer on the mineral surfaces with varying solution conditions mirrored and confirmed the conclusions from the isotherms: as the polymer solution concentration increased, coverage on the basal plane increased; as the ionic strength increased, coverage on the basal plane increased and the morphology of the layer changed from isolated well-distributed polymer domains to extensive adsorption and formation of dense, uneven polymer domains/features. In addition, comparison of the talc and molybdenite datasets points toward the presence of different binding mechanisms for CMC adsorption on the talc and molybdenite basal plane surfaces. 2010 Elsevier Inc. All rights reserved.
Cellulose-Based Nanomaterials for Energy Applications.
Wang, Xudong; Yao, Chunhua; Wang, Fei; Li, Zhaodong
2017-11-01
Cellulose is the most abundant natural polymer on earth, providing a sustainable green resource that is renewable, degradable, biocompatible, and cost effective. Recently, nanocellulose-based mesoporous structures, flexible thin films, fibers, and networks are increasingly developed and used in photovoltaic devices, energy storage systems, mechanical energy harvesters, and catalysts components, showing tremendous materials science value and application potential in many energy-related fields. In this Review, the most recent advancements of processing, integration, and application of cellulose nanomaterials in the areas of solar energy harvesting, energy storage, and mechanical energy harvesting are reviewed. For solar energy harvesting, promising applications of cellulose-based nanostructures for both solar cells and photoelectrochemical electrodes development are reviewed, and their morphology-related merits are discussed. For energy storage, the discussion is primarily focused on the applications of cellulose-based nanomaterials in lithium-ion batteries, including electrodes (e.g., active materials, binders, and structural support), electrolytes, and separators. Applications of cellulose nanomaterials in supercapacitors are also reviewed briefly. For mechanical energy harvesting, the most recent technology evolution in cellulose-based triboelectric nanogenerators is reviewed, from fundamental property tuning to practical implementations. At last, the future research potential and opportunities of cellulose nanomaterials as a new energy material are discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
NASA Astrophysics Data System (ADS)
Tristantini, Dewi; Dewanti, Dian Purwitasari; Sandra, Cindy
2017-11-01
Alpha cellulose is a pure form of cellulose. Cellulose is a natural polymer in the form of carbohydrates (polysaccharides) that has fiber which is white, insoluble in water, renewable, easily decomposes, and non-toxic. Cellulosic sources are abundant in nature even in untapped biomass wastes. In this study, cellulose was isolated from Empty Palm Oil Bunches (EPOB) of 45% and Dry Jackfruit Leaves (DJL) of 21.45%. This study aims to obtain optimum yield of cellulose at NaOH concentration and cellulose characterization with water content, FTIR, and SEM analysis. The optimum α-cellulose yield was determined by alkali process with 8, 10, 12 and 14% (w/v) NaOH variations at 90-100 °C for 3 hours to remove hemicellulose and lignin followed by bleaching process with H2O2 10% (w/v) at 80-90 °C for 1.5 h to obtain pure α-cellulose. The optimum yield of EPOB cellulose was 38,562% in 12% NaOH and DJL was 7.27% in 10% NaOH. The water content in OPB cellulose was 4.38% and DJL was 6.37%. A typical cellulose-forming functional group seen in FTIR (Fourier Transform Infra-Red) and morphological results appears in SEM (Scanning Electron Microscopy) analysis. From FTIR analysis result shows cellulose from EPOB and DJL contains O-H, C-H, and C-O. SEM analysis shows fibers from EPOB and DJL are uniform and have pores. However, DJL fibers have white patches, which suspected to be impurities.
77 FR 61515 - Alkyl Amines Polyalkoxylates; Exemption From the Requirement of a Tolerance
Federal Register 2010, 2011, 2012, 2013, 2014
2012-10-10
... polyoxyethylene polymers and fatty acids; carriers such as clay and diatomaceous earth; thickeners such as carrageenan and modified cellulose; wetting, spreading, and dispersing agents; propellants in aerosol...
Habibi, Neda
2014-10-15
The preparation and characterization of magnetite-carboxymethyl cellulose nano-composite (M-CMC) material is described. Magnetite nano-particles were synthesized by a modified co-precipitation method using ferrous chloride tetrahydrate and ferric chloride hexahydrate in ammonium hydroxide solution. The M-CMC nano-composite particles were synthesized by embedding the magnetite nanoparticles inside carboxymethyl cellulose (CMC) using a freshly prepared mixture of Fe3O4 with CMC precursor. Morphology, particle size, and structural properties of magnetite-carboxymethyl cellulose nano-composite was accomplished using X-ray powder diffraction (XRD), transmission electron microscopy (TEM), Fourier transformed infrared (FTIR) and field emission scanning electron microscopy (FESEM) analysis. As a result, magnetite nano-particles with an average size of 35nm were obtained. The biocompatible Fe3O4-carboxymethyl cellulose nano-composite particles obtained from the natural CMC polymers have a potential range of application in biomedical field. Copyright © 2014 Elsevier B.V. All rights reserved.
Thermal conductivity analysis and applications of nanocellulose materials
Uetani, Kojiro; Hatori, Kimihito
2017-01-01
Abstract In this review, we summarize the recent progress in thermal conductivity analysis of nanocellulose materials called cellulose nanopapers, and compare them with polymeric materials, including neat polymers, composites, and traditional paper. It is important to individually measure the in-plane and through-plane heat-conducting properties of two-dimensional planar materials, so steady-state and non-equilibrium methods, in particular the laser spot periodic heating radiation thermometry method, are reviewed. The structural dependency of cellulose nanopaper on thermal conduction is described in terms of the crystallite size effect, fibre orientation, and interfacial thermal resistance between fibres and small pores. The novel applications of cellulose as thermally conductive transparent materials and thermal-guiding materials are also discussed. PMID:29152020
Pawlik, M; Laskowski, J S; Ansari, A
2003-04-15
The adsorption of sodium carboxymethyl cellulose from aqueous solutions varying in ionic strength from that of distilled water to 50% NaCl/KCl brine (about 3.5 mol/dm(3)) onto illite and dolomite has been studied. The purpose of this work was to investigate the solvency effects in the phenomena underlying the potash flotation process that is carried out in saturated brine. Based on viscosity measurements, the adsorption results were analyzed in terms of a simple model of polymer macromolecules in solution. Suspension stability measurements carried out concomitantly with adsorption tests showed the ranges of carboxymethyl cellulose concentration over which the tested suspensions either were aggregated or were restabilized.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
1986-12-31
The goal of this program is to develop polymer membranes useful in the preparation of hydrogen from coal-derived synthesis gas. During this quarter the first experiment were aimed at developing high performance composite membranes for the separation of hydrogen from nitrogen and carbon monoxide. Three polymers have been selected as materials for these membranes: polyetherimide cellulose acetate and ethylcellulose. This quarter the investigators worked on polyetherimide and cellulose acetate membranes. The overall structure of these membranes is shown schematically in Figure 1. As shown, a microporous support membrane is first coated with a high flux intermediate layer then with anmore » ultrathin permselective layer and finally, if necessary, a thin protective high flux layer. 1 fig., 4 tabs.« less
Bioinspired Nanocellulose Based Hybrid Materials With Novel Interfacial Properties
NASA Astrophysics Data System (ADS)
Keten, Sinan
This talk will overview a simulation-based approach to enhancing the mechanical properties of nanocomposites by utilizing cellulose - the most abundant and renewable structural biopolymer found on our planet. Cellulose nanocrystals (CNCs) exhibit outstanding mechanical properties exceeding that of Kevlar, serving as reinforcing domains in nature's toughest hierarchical nanocomposites such as wood. Yet, weak interfaces at the surfaces of CNCs have so far made it impossible to scale these inherent properties to macroscopic systems. In this work, I will discuss how surface functionalization of CNCs influences their properties in their self-assembled films and nanocomposites with engineered polymer matrices . Specifically, the role of ion exchange based surface modifications and polymer conjugation will be discussed, where atomistic and coarse-grained simulations will reveal new insights into how superior mechanical properties can potentially be attained by hybrid constructs.
Cell wall assembly in fucus zygotes: I. Characterization of the polysaccharide components.
Quatrano, R S; Stevens, P T
1976-08-01
Fertilization triggers the assembly of a cell wall around the egg cell of three brown algae, Fucus vesiculosus, F. distichus, and F. inflatus. New polysaccharide polymers are continually being added to the cell wall during the first 24 hours of synchronous embryo development. This wall assembly involves the extracellular deposition of fibrillar material by cytoplasmic vesicles fusing with the plasma membrane. One hour after fertilization a fragmented wall can be isolated free of cytoplasm and contains equal amounts of cellulose and alginic acid with no fucose-containing polymers (fucans) present. Birefringence of the wall caused by oriented cellulose microfibrils is not detected in all zygotes until 4 hours, at which time intact cell walls can be isolated that retain the shape of the zygote. These walls have a relatively low ratio of fucose to xylose and little sulfate when compared to walls from older embryos. When extracts of walls from 4-hour zygotes are subjected to cellulose acetate electrophoresis at pH 7, a single fucan (F(1)) can be detected. By 12 hours, purified cell walls are composed of fucans containing a relatively high ratio of fucose to xylose and high levels of sulfate, and contain a second fucan (F(2)) which is electrophoretically distinct from F(1). F(2) appears to be deposited in only a localized region of the wall, that which elongates to form the rhizoid cell. Throughout wall assembly, the polyuronide block co-polymer alginic acid did not significantly vary its mannuronic (M) to guluronic (G) acid ratio (0.33-0.55) or its block distribution (MG, 54%; GG, 30%; MM, 16%). From 6 to 24 hours of embryo development, the proportion of the major polysaccharide components found in purified walls is stable. Alginic acid is the major polymer and comprises about 60% of the total wall, while cellulose and the fucans each make-up about 20% of the remainder. During the extracellular assembly of this wall, the intracellular levels of the storage glucan laminaran decreases. A membrane-bound beta-1, 3-exoglucanase is found in young zygotes which degrades laminaran to glucose. It is postulated that hydrolysis of laminaran by this glucanase accounts, at least in part, for glucose availability for wall biosynthesis and the increase in respiration triggered by fertilization. The properties and function of alginic acid, the fucans, and cellulose are discussed in relation to changes in wall structure and function during development.
Petti, Carloalberto; Hirano, Ko; Stork, Jozsef; DeBolt, Seth
2015-09-01
Here, we show a mechanism for expansion regulation through mutations in the green revolution gene gibberellin20 (GA20)-oxidase and show that GAs control biosynthesis of the plants main structural polymer cellulose. Within a 12,000 mutagenized Sorghum bicolor plant population, we identified a single cellulose-deficient and male gametophyte-dysfunctional mutant named dwarf1-1 (dwf1-1). Through the Sorghum propinquum male/dwf1-1 female F2 population, we mapped dwf1-1 to a frameshift in GA20-oxidase. Assessment of GAs in dwf1-1 revealed ablation of GA. GA ablation was antagonistic to the expression of three specific cellulose synthase genes resulting in cellulose deficiency and growth dwarfism, which were complemented by exogenous bioactive gibberellic acid application. Using quantitative polymerase chain reaction, we found that GA was positively regulating the expression of a subset of specific cellulose synthase genes. To cross reference data from our mapped Sorghum sp. allele with another monocotyledonous plant, a series of rice (Oryza sativa) mutants involved in GA biosynthesis and signaling were isolated, and these too displayed cellulose deficit. Taken together, data support a model whereby suppressed expansion in green revolution GA genes involves regulation of cellulose biosynthesis. © 2015 American Society of Plant Biologists. All Rights Reserved.
Li, Yongfu; Meunier, David M; Partain, Emmett M
2014-09-12
Size-exclusion chromatography (SEC) of hydrophobe-modified hydroxyethyl cellulose (HmHEC) is challenging because polymer chains are not isolated in solution due to association of hydrophobic groups and hydrophobic interaction with column packing materials. An approach to neutralize these hydrophobic interactions was developed by adding β-cyclodextrin (β-CD) to the aqueous eluent. SEC mass recovery, especially for the higher molecular weight chains, increased with increasing concentration of β-CD in the eluent. A β-CD concentration of 0.75wt% in the eluent was determined to be optimal for the HmHEC polymers studied. These conditions enabled precise determinations of apparent molecular weight distributions exhibiting less than 2% relative standard deviation in the measured weight-average molecular weight (MW) for five injections on three studied samples and showed no significant differences in MW determined on two different days. The developed technology was shown to be very robust for characterizing HmHEC having MW from 500kg/mol to 2000kg/mol, and it can be potentially applied to other hydrophobe-modified polymers. Copyright © 2014 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Stoica-Guzun, Anicuta; Stroescu, Marta; Tache, Florin; Zaharescu, Traian; Grosu, Elena
2007-12-01
Ionizing radiation is an effective energetic source for polymer surfaces modification in order to obtain transdermal systems with different controlled release properties. In this work, gamma rays have been applied to induce changes in bacterial cellulose membranes. Permeation of drug (tetracycline) was theoretically and experimentally investigated starting from the effect of γ-irradiation on membranes permeability. Release and permeation of drug from irradiated and non-irradiated membranes have been performed using a diffusion cell.
Taki, Moeko; Tagami, Tatsuaki; Ozeki, Tetsuya
2017-05-01
The development of taste-masking technologies for foods and drugs is essential because it would enable people to consume and receive healthy and therapeutic effect without distress. In the current study, in order to develop a novel method to prepare nanocomposite particles (microparticles containing bitter nanoparticles) in only one step, by using spray drying, a two-solution mixing nozzle-equipped spray dryer that we previously reported was used. The nanocomposite particles with or without poorly water-soluble polymers prepared using our spray-drying technique were characterized. (1) The organic solution containing quinine, a model of bitter compound and poorly water-soluble polymers and (2) sugar alcohol (mannitol) aqueous solution were separately flown in tubes and two solutions were spray dried through two-solution type spray nozzle to prepare polymer-blended quinine nanocomposite particles. Mean diameters of nanoparticles, taste-masking effect and dissolution rate of quinine were evaluated. The results of taste masking by taste sensor suggested that the polymer (Eudragit EPO, Eudragit S100 or Ethyl cellulose)-blended quinine nanocomposite particles exhibited marked masking of instrumental quinine bitterness compared with the quinine nanocomposite particles alone. Quinine nanocomposite formulations altered the quinine dissolution rate, indicating that they can control intestinal absorption of quinine. These results suggest that polymer-blended quinine composite particles prepared using our spray-drying technique are useful for masking bitter tastes in the field of food and pharmaceutical industry.
Sabir, Aneela; Shafiq, Muhammad; Islam, Atif; Sarwar, Afsheen; Dilshad, Muhammad Rizwan; Shafeeq, Amir; Zahid Butt, Muhammad Taqi; Jamil, Tahir
2015-11-05
In this study pristine multi-walled carbon nanotubes (MWCNTs) were surface engineered (SE) in strong acidic medium by oxidation purification method to form SE-MWCNT. Five different amount of SE-MWCNT ranging from 0.1 to 0.5 wt% were thoroughly and uniformly dispersed in cellulose acetate/polyethylene glycol (CA/PEG400) polymer matrix during synthesis of membrane by dissolution casting method. The structural analysis, surface morphology and roughness was carried out by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and atomic force microscopy (AFM), respectively, which showed that the dispersed SE-MWCNT was substantially tethered in CA/PEG400 polymer matrix membrane. The thermogravimetric analysis (TGA) of membranes also suggested some improvement in thermal properties with the addition of SE-MWCNT. Finally, the performance of these membranes was assessed for suitability in drinking water treatment. The permeation flux and salt rejection were determined by using indigenously fabricated reverse osmosis pilot plant with 1000 ppm NaCl feed solution. The results showed that the tethered SE-MWCNT/CA/PEG400 polymer matrix membrane, with strong SE-MWCNTs/polymer matrix interaction, improved the salt rejection performance of the membrane with the salt rejection of 99.8% for the highest content of SE-MWCNT. Copyright © 2015 Elsevier Ltd. All rights reserved.
O'Connell, Michael A; de Cuendias, Anne; Gayet, Florence; Shirley, Ian M; Mackenzie, Stuart R; Haddleton, David M; Unwin, Patrick R
2012-05-01
Evanescent wave cavity ring-down spectroscopy (EW-CRDS) has been employed to study the interfacial adsorption kinetics of coumarin-tagged macromolecules onto a range of functionalized planar surfaces. Such studies are valuable in designing polymers for complex systems where the degree of interaction between the polymer and surface needs to be tailored. Three tagged synthetic polymers with different functionalities are examined: poly(acrylic acid) (PAA), poly(3-sulfopropyl methacrylate, potassium salt) (PSPMA), and a mannose-modified glycopolymer. Adsorption transients at the silica/water interface are found to be characteristic for each polymer, and kinetics are deduced from the initial rates. The chemistry of the adsorption interfaces has been varied by, first, manipulation of silica surface chemistry via the bulk pH, followed by surfaces modified by poly(L-glutamic acid) (PGA) and cellulose, giving five chemically different surfaces. Complementary atomic force microscopy (AFM) imaging has been used for additional surface characterization of adsorbed layers and functionalized interfaces to allow adsorption rates to be interpreted more fully. Adsorption rates for PSPMA and the glycopolymer are seen to be highly surface sensitive, with significantly higher rates on cellulose-modified surfaces, whereas PAA shows a much smaller rate dependence on the nature of the adsorption surface.
Wang, Yanting; Fan, Chunfen; Hu, Huizhen; Li, Ying; Sun, Dan; Wang, Youmei; Peng, Liangcai
2016-01-01
Plant cell walls represent an enormous biomass resource for the generation of biofuels and chemicals. As lignocellulose property principally determines biomass recalcitrance, the genetic modification of plant cell walls has been posed as a powerful solution. Here, we review recent progress in understanding the effects of distinct cell wall polymers (cellulose, hemicelluloses, lignin, pectin, wall proteins) on the enzymatic digestibility of biomass under various physical and chemical pretreatments in herbaceous grasses, major agronomic crops and fast-growing trees. We also compare the main factors of wall polymer features, including cellulose crystallinity (CrI), hemicellulosic Xyl/Ara ratio, monolignol proportion and uronic acid level. Furthermore, the review presents the main gene candidates, such as CesA, GH9, GH10, GT61, GT43 etc., for potential genetic cell wall modification towards enhancing both biomass yield and enzymatic saccharification in genetic mutants and transgenic plants. Regarding cell wall modification, it proposes a novel groove-like cell wall model that highlights to increase amorphous regions (density and depth) of the native cellulose microfibrils, providing a general strategy for bioenergy crop breeding and biofuel processing technology. Copyright © 2016 Elsevier Inc. All rights reserved.
The Early Days of Polymer Science
ERIC Educational Resources Information Center
Mark, H.
1973-01-01
Summarizes research studies made early in this century in the fields of cellulose, starch, proteins, and rubber. Included is a description of factors which give rise to the concept of very long, chain-like molecules. (CC)
DOE Office of Scientific and Technical Information (OSTI.GOV)
Suvorova, E. I., E-mail: suvorova@ns.crys.ras.ru; Klechkovskaya, V. V.
2010-12-15
Transmission electron microscopy and X-ray energy dispersive microanalysis study of the structure of particles formed during the reduction of Se(IV) to Se(0) in aqueous solutions in the presence of amphiphilic polymers showed the formation of Se/polymer composite particles. The content of carbon inside the particles can be as large as 80 at %. Polymers deeply influence the structure of particles. Depending on polymers, the composite particles may be unstable with time and they spontaneously evolve from Se/polymer composite particles to crystalline particles of monoclinic Se. For the stable ones, addition of bacterial cellulose Acetobacter xylinum gel-film can induce crystallization inmore » the particles which expel the polymeric material. The Se/polymer composite particles and Se crystalline particles exhibit different sensitivity to electron irradiation and stiffness.« less
Lee, Christopher M; Chen, Xing; Weiss, Philip A; Jensen, Lasse; Kim, Seong H
2017-01-05
Vibrational sum-frequency-generation (SFG) spectroscopy is capable of selectively detecting crystalline biopolymers interspersed in amorphous polymer matrices. However, the spectral interpretation is difficult due to the lack of knowledge on how spatial arrangements of crystalline segments influence SFG spectra features. Here we report time-dependent density functional theory (TD-DFT) calculations of cellulose crystallites in intimate contact with two different polarities: parallel versus antiparallel. TD-DFT calculations reveal that the CH/OH intensity ratio is very sensitive to the polarity of the crystallite packing. Theoretical calculations of hyperpolarizability tensors (β abc ) clearly show the dependence of SFG intensities on the polarity of crystallite packing within the SFG coherence length, which provides the basis for interpretation of the empirically observed SFG features of native cellulose in biological systems.
Co-electrospun poly(ɛ-caprolactone)/cellulose nanofibers-fabrication and characterization.
Ahmed, Farooq; Saleemi, Sidra; Khatri, Zeeshan; Abro, Muhammad Ishaque; Kim, Ick-Soo
2015-01-22
We report fabrication of poly (ɛ-caprolactone) (PCL)/cellulose (CEL) nanofiber blends via co-electrospinning for the possible use as biofilters and biosensor strips. Five different ratios of PCL to CEL were fabricated to investigate the wicking behavior. The cellulose acetate (CA) was taken as precursor to make cellulose nanofibers. Double nozzles were employed for jetting constituent polymers toward collector drum independently and resultant nanofibers webs were deacetylated in aqueous alkaline solution to convert CA into CEL as confirmed by FTIR spectra. FTIR further revealed that there is no effect of deacetylation on PCL nanofiber. The morphology of each blend webs under SEM showed uniform and bead-free nanofibers. Wicking behavior for five different ratios of PCL/CEL suggested that increasing CEL ratio in the blend enhanced the wicking front height; however, X-ray diffraction patterns of PCL/CEL showed a slight decrease in crystallinity. Copyright © 2014 Elsevier Ltd. All rights reserved.
Yassine, Fatima; Bassil, Nathalie; Flouty, Roula; Chokr, Ali; Samrani, Antoine El; Boiteux, Gisèle; Tahchi, Mario El
2016-08-01
Gluconacetobacter genera are valued for bacterial cellulose (BC) and acetic acid production. BC is produced at optimal yields in classical microbiological media that are expensive for a large scale of production. In addition, BC usage for industrial purposes is limited due to low conversion rate into cellulose and to long incubation duration. In this paper, Gluconacetobacter isolated from apple vinegar was kinetically studied to evaluate cellulose production in presence of different carbon sources. Acetic and citric acid effect on Gluconacetobacter metabolism is clarified. It was shown that Gluconacetobacter uses glucose as a primary carbon source for cells growth and products formation. Acetic acid employment as a co-carbon source in Hestrin Schramm medium showed an increase of 17% in BC yield with a moderate decrease in the crystallite size of the resulting polymer. Copyright © 2016 Elsevier Ltd. All rights reserved.
Development of the metrology and imaging of cellulose nanocrystals
NASA Astrophysics Data System (ADS)
Postek, Michael T.; Vladár, András; Dagata, John; Farkas, Natalia; Ming, Bin; Wagner, Ryan; Raman, Arvind; Moon, Robert J.; Sabo, Ronald; Wegner, Theodore H.; Beecher, James
2011-02-01
The development of metrology for nanoparticles is a significant challenge. Cellulose nanocrystals (CNCs) are one group of nanoparticles that have high potential economic value but present substantial challenges to the development of the measurement science. Even the largest trees owe their strength to this newly appreciated class of nanomaterials. Cellulose is the world's most abundant natural, renewable, biodegradable polymer. Cellulose occurs as whisker-like microfibrils that are biosynthesized and deposited in plant material in a continuous fashion. The nanocrystals are isolated by hydrolyzing away the amorphous segments leaving the acid resistant crystalline fragments. Therefore, the basic raw material for new nanomaterial products already abounds in nature and is available to be utilized in an array of future materials. However, commercialization requires the development of efficient manufacturing processes and nanometrology to monitor quality. This paper discusses some of the instrumentation, metrology and standards issues associated with the ramping up for production and use of CNCs.
Enhanced enzymatic saccharification of pretreated biomass using glycerol thermal processing (GTP).
Zhang, Wei; Sathitsuksanoh, Noppadon; Barone, Justin R; Renneckar, Scott
2016-01-01
Biomass was heated (200-240°C) in the presence of glycerol, for 4-12 min, under shear to disrupt the native cell wall architecture. The impact of this method, named glycerol thermal processing (GTP), on saccharification efficiency of the hardwood Liquidambar styraciflua, and a control cellulose sample was studied as a function of treatment severity. Furthermore, the enzymatic conversion of samples with varying compositions was studied after extraction of the structural polymers. Interestingly, the sweet gum processed materials crystallinity index increased by 10% of the initial value. The experiments revealed that the residual lignin was not a barrier to limiting the digestibility of cellulose after pretreatment yielding up to 70% glucose based on the starting wood material. Further xylan removal greatly improved the cellulose hydrolysis rate, converting nearly 70% of the cellulose into glucose within 24h, and reaching 78% of ultimate glucan digestibility after 72 h. Copyright © 2015 Elsevier Ltd. All rights reserved.
Andonova, Velichka; Peneva, Petya; Georgiev, George S; Toncheva, Vencislava T; Apostolova, Elisaveta; Peychev, Zhivko; Dimitrova, Stela; Katsarova, Mariana; Petrova, Nadia; Kassarova, Margarita
2017-01-01
The purpose of the study was to investigate the stability and biopharmaceutical characteristics of ketoprofen, loaded in polymeric carriers, which were included into a bigel in a semisolid dosage form. The polymer carriers with in situ-included ketoprofen were obtained by emulsifier-free emulsion polymerization of the monomers in aqueous medium or a solution of the polymers used. The morphological characteristics of the carriers, the in vitro release and the photochemical stability of ketoprofen were evaluated. The model with optimal characteristics was included in a bigel formulation. The bigel was characterized in terms of pH, rheological behavior, spreadability, and in vitro drug release. Acute skin toxicity, antinociceptive activity, anti-inflammatory activity, and antihyperalgesic effects of the prepared bigel with ketoprofen-loaded polymer carrier were evaluated. The carriers of ketoprofen were characterized by a high yield and drug loading. The particle size distribution varied widely according to the polymer used, and a sustained release was provided for up to 6 hours. The polymer mixture poly(vinyl acetate) and hydroxypropyl cellulose as a drug carrier, alone or included in the bigel composition, improved the photostability of the drug compared with unprotected ketoprofen. The bigel with ketoprofen-loaded particles provided sustained release of the drug and had optimal rheological parameters. In vivo experiments on the bigel showed no skin inflammation or irritation. Four hours after its application, a well-defined analgesic, anti-inflammatory, and antihyperalgesic effect was registered. The polymer mixture of poly(vinyl acetate) and hydroxypropyl cellulose as a carrier of ketoprofen and the bigel in which it was included provided an enhanced photostability and sustained drug release. PMID:28894363
Andonova, Velichka; Peneva, Petya; Georgiev, George S; Toncheva, Vencislava T; Apostolova, Elisaveta; Peychev, Zhivko; Dimitrova, Stela; Katsarova, Mariana; Petrova, Nadia; Kassarova, Margarita
2017-01-01
The purpose of the study was to investigate the stability and biopharmaceutical characteristics of ketoprofen, loaded in polymeric carriers, which were included into a bigel in a semisolid dosage form. The polymer carriers with in situ-included ketoprofen were obtained by emulsifier-free emulsion polymerization of the monomers in aqueous medium or a solution of the polymers used. The morphological characteristics of the carriers, the in vitro release and the photochemical stability of ketoprofen were evaluated. The model with optimal characteristics was included in a bigel formulation. The bigel was characterized in terms of pH, rheological behavior, spreadability, and in vitro drug release. Acute skin toxicity, antinociceptive activity, anti-inflammatory activity, and antihyperalgesic effects of the prepared bigel with ketoprofen-loaded polymer carrier were evaluated. The carriers of ketoprofen were characterized by a high yield and drug loading. The particle size distribution varied widely according to the polymer used, and a sustained release was provided for up to 6 hours. The polymer mixture poly(vinyl acetate) and hydroxypropyl cellulose as a drug carrier, alone or included in the bigel composition, improved the photostability of the drug compared with unprotected ketoprofen. The bigel with ketoprofen-loaded particles provided sustained release of the drug and had optimal rheological parameters. In vivo experiments on the bigel showed no skin inflammation or irritation. Four hours after its application, a well-defined analgesic, anti-inflammatory, and antihyperalgesic effect was registered. The polymer mixture of poly(vinyl acetate) and hydroxypropyl cellulose as a carrier of ketoprofen and the bigel in which it was included provided an enhanced photostability and sustained drug release.
Raman spectroscopy in the analysis of cellulose nanomaterials
Umesh P. Agarwal
2017-01-01
Cellulose nanomaterials (CNs) are new types of materials derived from celluloses and offer unique challenges and opportunities for Raman spectroscopic investigations. CNs can be classified into the categories of cellulose nanocrystals (CNCs, also known as cellulose whisker) and cellulose nanofibrils (CNFs, also known as nanofibrillated cellulose or NFCs) which when...
Dupraz, A; Nguyen, T P; Richard, M; Daculsi, G; Passuti, N
1999-04-01
An injectable composite material based on biphasic calcium phosphate (BCP) and a nonionic cellulose ether has been elaborated for use in percutaneous surgery for spine fusion. This paper reports the characterization results of this material by spectroscopic techniques including X-ray diffraction (XRD), infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) fitted with an energy dispersive X-Ray analysis system and high-resolution transmission electron microscopy (HR-TEM). From FTIR and XPS results, it was observed that the adhesion between the polymer and the ceramic might be insured by oxygen bridging developed through an ionic bonding between calcium ions and (C-O) groups of the polymer. Moreover, XPS showed attraction of Ca2+ ions in the polymer matrix, while the ceramic surface was modified in a HPO4(2-) -rich layer. These results suggest a possible dissolution/precipitation process at the interface ceramic/polymer. HR-TEM observations supported this hypothesis, showing a light contrasted fringe at the surface of the ceramic grains in the composite paste. As well, changes in the XRD spectra could indicate a small decrease in the crystal size of the BCP powder through the contact to polymer solution. In addition, SEM observation showed a decrease of the initial BCP granulometry. Aggregates of 80-200 microm seemed to be mostly dissociated in micrograins. The ceramic grains were coated with and bonded between each other by the polymer matrix, which acted as spacer in between the ceramic grains, creating a macroporous-like material structure.
Cellulose whisker/epoxy resin nanocomposites.
Tang, Liming; Weder, Christoph
2010-04-01
New nanocomposites composed of cellulose nanofibers or "whiskers" and an epoxy resin were prepared. Cellulose whiskers with aspect ratios of approximately 10 and approximately 84 were isolated from cotton and sea animals called tunicates, respectively. Suspensions of these whiskers in dimethylformamide were combined with an oligomeric difunctional diglycidyl ether of bisphenol A with an epoxide equivalent weight of 185-192 and a diethyl toluenediamine-based curing agent. Thin films were produced by casting these mixtures and subsequent curing. The whisker content was systematically varied between 4 and 24% v/v. Electron microscopy studies suggest that the whiskers are evenly dispersed within the epoxy matrix. Dynamic mechanical thermoanalysis revealed that the glass transition temperature (T(g)) of the materials was not significantly influenced by the incorporation of the cellulose filler. Between room temperature and 150 degrees C, i.e., below T(g), the tensile storage moduli (E') of the nanocomposites increased modestly, for example from 1.6 GPa for the neat polymer to 4.9 and 3.6 GPa for nanocomposites comprising 16% v/v tunicate or cotton whiskers. The relative reinforcement was more significant at 185 degrees C (i.e., above T(g)), where E' was increased from approximately 16 MPa (neat polymer) to approximately 1.6 GPa (tunicate) or approximately 215 MPa (cotton). The mechanical properties of the new materials are well-described by the percolation model and are the result of the formation of a percolating whisker network in which stress transfer is facilitated by strong interactions between the whiskers.
de Castro, María; Miller, Janice G; Acebes, José Luis; Encina, Antonio; García-Angulo, Penélope; Fry, Stephen C
2015-04-01
Cell-suspension cultures (Zea mays L., Black Mexican sweet corn) habituated to 2,6-dichlorobenzonitrile (DCB) survive with reduced cellulose owing to hemicellulose network modification. We aimed to define the hemicellulose metabolism modifications in DCB-habituated maize cells showing a mild reduction in cellulose at different stages in the culture cycle. Using pulse-chase radiolabeling, we fed habituated and non-habituated cultures with [(3)H]arabinose, and traced the distribution of (3)H-pentose residues between xylans, xyloglucans and other polymers in several cellular compartments for 5 h. Habituated cells were slower taking up exogenous [(3)H]arabinose. Tritium was incorporated into polysaccharide-bound arabinose and xylose residues, but habituated cells diverted a higher proportion of their new [(3)H]xylose residues into (hetero) xylans at the expense of xyloglucan synthesis. During logarithmic growth, habituated cells showed slower vesicular trafficking of polymers, especially xylans. Moreover, habituated cells showed a decrease in the strong wall-binding of all pentose-containing polysaccharides studied; correspondingly, especially in log-phase cultures, habituation increased the proportion of (3)H-hemicelluloses ([(3)H]xylans and [(3)H]xyloglucan) sloughed into the medium. These findings could be related to the cell walls' cellulose-deficiency, and consequent reduction in binding sites for hemicelluloses; the data could also reflect the habituated cells' reduced capacity to integrate arabinoxylans by extra-protoplasmic phenolic cross-linking, as well as xyloglucans, during wall assembly. © 2015 Institute of Botany, Chinese Academy of Sciences.
Garside, Paul; Wyeth, Paul
2007-05-01
Textile artifacts form a vital part of our cultural heritage. In order to determine appropriate methods of conservation, storage, and display, it is important to understand the current physical state of an artifact, as effected by the microstructure of the component fibers. The semi-crystalline nature of the constituent polymer aggregates, the degree of crystallinity, and the crystallite orientation have a significant influence on mechanical properties. The value of polarized Fourier transform infrared (FT-IR) spectroscopy in probing these aspects of cellulosic fibers has been assessed. A variety of representative fibers (both natural plant fibers and regenerated materials) were examined by polarized attenuated total reflection spectroscopy (Pol-ATR) and polarized infrared microspectroscopy (Pol-microIR); the former is a surface sampling technique and the latter is a transmission technique. The introduction of a polarizer into the system allows the alignment as well as the nature of bonds to be determined, and thus the presence and extent of crystallinity or long range ordering can be investigated. Using the data from the Pol-ATR experiments, it was found to be possible to derive the principle alignment of the cellulose polymer with respect to the fiber axis, along with an indication of the total cellulose crystallinity of the material, as measured by a crystallinity parameter, Chi. The Pol-microIR spectra, on the other hand, yielded more limited information, particularly when considering plant fibers with more complex microstructures.
Torrefied biomass-polypropylene composites
USDA-ARS?s Scientific Manuscript database
Torrefied almond shells and wood chips were incorporated into polypropylene as fillers to produce torrefied biomass-polymer composites. Response surface methodology was used to examine the effects of filler concentration, filler size, and lignin factor (relative lignin to cellulose concentration) on...
Membranes and Films from Polymers.
ERIC Educational Resources Information Center
Blumberg, Avrom A.
1986-01-01
Provides background information on polymeric films and membranes including production methods, special industrial and medical applications, laboratory preparation, and an experimental investigation of a porous cellulose acetate membrane. Presents a demonstration to distinguish between high- and low-density polyethylene. (JM)
Progress in bacterial cellulose matrices for biotechnological applications.
Cacicedo, Maximiliano L; Castro, M Cristina; Servetas, Ioannis; Bosnea, Loulouda; Boura, Konstantina; Tsafrakidou, Panagiota; Dima, Agapi; Terpou, Antonia; Koutinas, Athanasios; Castro, Guillermo R
2016-08-01
Bacterial cellulose (BC) is an extracellular polymer produced by many microorganisms. The Komagataeibacter genus is the best producer using semi-synthetic media and agricultural wastes. The main advantages of BC are the nanoporous structure, high water content and free hydroxyl groups. Modification of BC can be made by two strategies: in-situ, during the BC production, and ex-situ after BC purification. In bioprocesses, multilayer BC nanocomposites can contain biocatalysts designed to be suitable for outside to inside cell activities. These nanocomposites biocatalysts can (i) increase productivity in bioreactors and bioprocessing, (ii) provide cell activities does not possess without DNA cloning and (iii) provide novel nano-carriers for cell inside activity and bioprocessing. In nanomedicine, BC matrices containing therapeutic molecules can be used for pathologies like skin burns, and implantable therapeutic devices. In nanoelectronics, semiconductors BC-based using salts and synthetic polymers brings novel films showing excellent optical and photochemical properties. Copyright © 2016 Elsevier Ltd. All rights reserved.
Yue, Yiying; Han, Jingquan; Han, Guangping; French, Alfred D; Qi, Yadong; Wu, Qinglin
2016-08-20
Core-shell structured hydrogels consisting of a flexible interpenetrating polymer network (IPN) core and a rigid semi-IPN shell were prepared through chemical crosslinking of polyvinyl alcohol (PVA) and sodium alginate (SA) with Ca(2+) and glutaraldehyde. Short cellulose nanofibers (CNFs) extracted from energycane bagasse were incorporated in the hydrogel. The shell was micro-porous and the core was macro-porous. The hydrogels could be used in multiple adsorption-desorption cycles for dyes, and the maximum methyl blue adsorption capacity had a 10% increase after incorporating CNFs. The homogeneous distribution of CNFs in PVA-SA matrix generated additional hydrogen bonds among the polymer molecular chains, resulting in enhanced density, viscoelasticity, and mechanical strength for the hydrogel. Specifically, the compressive strength of the hydrogel reached 79.5kPa, 3.2 times higher than that of the neat hydrogel. Copyright © 2016 Elsevier Ltd. All rights reserved.
Role of Cellulose Nanocrystals on the Microstructure of Maleic Anhydride Plasma Polymer Thin Films.
Brioude, Michel M; Roucoules, Vincent; Haidara, Hamidou; Vonna, Laurent; Laborie, Marie-Pierre
2015-07-01
Recently, it was shown that the microstructure of a maleic anhydride plasma polymer (MAPP) could be tailored ab initio by adjusting the plasma process parameters. In this work, we aim to investigate the ability of cellulose nanocrystals (CNCs) to induce topographical structuration. Thus, a new approach was designed based on the deposition of MAPP on CNCs model surfaces. The nanocellulosic surfaces were produced by spin-coating the CNC suspension on a silicon wafer substrate and on a hydrophobic silicon wafer substrate patterned with circular hydrophilic microsized domains (diameter of 86.9 ± 4.9 μm), resulting in different degrees of CNC aggregation. By depositing the MAPP over these surfaces, it was possible to observe that the surface fraction of nanostructures increased from 20% to 35%. This observation suggests that CNCs can act as nucleation points resulting in more structures, although a critical density of the CNCs is required.
NASA Astrophysics Data System (ADS)
Hemvichian, Kasinee; Chanthawong, Auraruk; Suwanmala, Phiriyatorn
2014-10-01
Superabsorbent polymer (SAP) was synthesized by radiation-induced grafting of acrylamide (AM) onto carboxymethyl cellulose (CMC) in the presence of a crosslinking agent, N,N‧-methylenebisacrylamide (MBA). The effects of various parameters, such as dose, the amount of CMC, AM, MBA and ionic strength on the swelling ratio were investigated. In order to evaluate its controlled release potential, SAP was loaded with potassium nitrate (KNO3) as an agrochemical model and its potential for controlled release of KNO3 was studied. The amount of released KNO3 was analyzed by an inductively coupled plasma mass spectrometry (ICP-MS). The results from controlled release experiment agreed very well with the results from swelling experiment. The synthesized SAP was characterized by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The obtained SAP exhibited a swelling ratio of 190 g/g of dry gel.
Studies on cellulose nanocrystals isolated from groundnut shells.
Bano, Saleheen; Negi, Yuvraj Singh
2017-02-10
Today, various renewable biomass resources are accepted as waste material and are mostly burnt or used as cattle feed. The commercial value of these wastes can be increased by utilising them in production of nanomaterials. So, the present work was conducted for isolation of cellulose nanocrystals (CNCs) from groundnut shells which are produced annually as waste in large quantity (∼7 million tons). The structural, thermal, morphological & elemental analyses were assessed through corresponding techniques. Light Scattering studies were performed to analyse more likely weight average molecular weight (M w ) & radius of radius (R g ). The high M w ∼10 5 g/mol obtained for CNCs in lithium chloride (LiCl)/N,N-dimethylacetamide (DMAc) system, was an interesting feature which gets affected by LiCl and polymer concentrations. Solution with high polymer and low LiCl concentration was found to show higher values of M w & R g . Copyright © 2016 Elsevier Ltd. All rights reserved.
Effect of cellulose nanowhiskers functionalization with polyaniline for epoxy coatings
NASA Astrophysics Data System (ADS)
Borsoi, C.; Zattera, A. J.; Ferreira, C. A.
2016-02-01
Functionalization of cellulose nanowhiskers (CNW) was performed by means of chemical synthesis involving polymerization of polyaniline in emeraldine salt form (PAni SE) in the presence of CNW. Thermal, chemical and morphological samples properties were evaluated. Polymeric coatings were obtained with epoxy, aminopropyltriethoxysilane (APS), CNW and CNW/PAni SE applied on carbon steel with a conversion coating of zirconia (Zr) and the mechanical properties were evaluated. With regard to CNW functionalization the sample was encapsulated with PAni SE as observed by FTIR and morphologic analysis, with decreased thermal stability. Regarding the mechanical properties of CNW and CNW/PAni SE polymeric coatings, improvements in flexibility and hardness properties using the APS and Zr layer were observed. The adherence of polymer coatings improved by the incorporation of CNW and CNW/PAni SE. Through morphological analysis it was observed that CNW shows good dispersion in the polymer matrix without agglomerates formation.
Utilization of biocatalysts in cellulose waste minimization
DOE Office of Scientific and Technical Information (OSTI.GOV)
Woodward, J.; Evans, B.R.
1996-09-01
Cellulose, a polymer of glucose, is the principal component of biomass and, therefore, a major source of waste that is either buried or burned. Examples of biomass waste include agricultural crop residues, forestry products, and municipal wastes. Recycling of this waste is important for energy conservation as well as waste minimization and there is some probability that in the future biomass could become a major energy source and replace fossil fuels that are currently used for fuels and chemicals production. It has been estimated that in the United States, between 100-450 million dry tons of agricultural waste are produced annually,more » approximately 6 million dry tons of animal waste, and of the 190 million tons of municipal solid waste (MSW) generated annually, approximately two-thirds is cellulosic in nature and over one-third is paper waste. Interestingly, more than 70% of MSW is landfilled or burned, however landfill space is becoming increasingly scarce. On a smaller scale, important cellulosic products such as cellulose acetate also present waste problems; an estimated 43 thousand tons of cellulose ester waste are generated annually in the United States. Biocatalysts could be used in cellulose waste minimization and this chapter describes their characteristics and potential in bioconversion and bioremediation processes.« less
Mild and modular surface modification of cellulose via hetero Diels-Alder (HDA) cycloaddition.
Goldmann, Anja S; Tischer, Thomas; Barner, Leonie; Bruns, Michael; Barner-Kowollik, Christopher
2011-04-11
A combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and hetero Diels-Alder (HDA) cycloaddition was used to effect, under mild (T ≈ 20 °C), fast, and modular conditions, the grafting of poly(isobornyl acrylate) (M(n) = 9800 g mol(-1), PDI = 1.19) onto a solid cellulose substrate. The active hydroxyl groups expressed on the cellulose fibers were converted to tosylate leaving groups, which were subsequently substituted by a highly reactive cyclopentadienyl functionality (Cp). By employing the reactive Cp-functionality as a diene, thiocarbonyl thio-capped poly(isobornyl acrylate) synthesized via RAFT polymerization (mediated by benzyl pyridine-2-yldithioformiate (BPDF)) was attached to the surface under ambient conditions by an HDA cycloaddition (reaction time: 15 h). The surface-modified cellulose samples were analyzed in-depth by X-ray photoelectron spectroscopy, scanning electron microscopy, elemental analysis, Fourier transform infrared (FT-IR) spectroscopy as well as Fourier transform infrared microscopy employing a focal plane array detector for imaging purposes. The analytical results provide strong evidence that the reaction of suitable dienophiles with Cp-functional cellulose proceeds under mild reaction conditions (T ≈ 20 °C) in an efficient fashion. In particular, the visualization of individual modified cellulose fibers via high-resolution FT-IR microscopy corroborates the homogeneous distribution of the polymer film on the cellulose fibers.
NASA Astrophysics Data System (ADS)
Misenan, Muhammad Syukri Mohamad; Ali, Ernie Suzana; Khiar, Azwani Sofia Ahmad
2018-06-01
In this study, the effect of adding cellulose nanocrystal (CNC) on the conductivity of biopolymer electrolyte (BPE) based on chitosan-methylcellulose-BMIMTFSI has been studied. The samples were prepared via solution casting technique. The film was characterized by impedance spectroscopy HIOKI 3531- 01 LCR Hi-Tester to measure its ionic conductivity at room temperatures over a wide range of frequency between 50Hz-5MHz. Sample with 15 wt% of CNC shows the highest conductivity of 4.82 x 10-6 Scm-1 at room temperature. Dielectric and modulus studies were carried out to further understands the conductivity behavior of the samples. The increase in conductivity is mainly due to the increase in number of charge carriers.
Fundamental Characteristics of the Newly Developed ATA™ Membrane Dialyzer.
Sunohara, Takashi; Masuda, Toshiaki
2017-01-01
Dialysis membranes are often made from synthetic polymers, such as polysulfone. However, membranes made from cellulose triacetate have superior biocompatibility and have been used since the 1980s. On-line hemodiafiltration treatment accompanied by massive fluid replacement is increasingly being used in Europe and Japan, but cellulose triacetate is not suitable for this treatment. Our newly developed asymmetric triacetate membrane, the ATA™ membrane, substantially improved the filtration properties and blood compatibility because of the asymmetric structure and smooth surface of this cellulose acetate membrane. Key Message: The ATA membrane maintains its high permeability even after massive filtration and shows less temporal variation in its permeation performance, lower protein adsorption, and superior biocompatibility compared with conventional membranes. © 2017 S. Karger AG, Basel.
Noiray, M.; Briand, E.; Woodward, A. M.; Argüeso, P.; Molina Martínez, I. T.; Herrero-Vanrell, R.; Ponchel, G.
2013-01-01
Purpose Development of the first in vitro method based on biosensor chip technology designed for probing the interfacial interaction phenomena between transmembrane ocular mucins and adhesive polymers and dendrimers intended for ophthalmic administration. Methods The surface plasmon resonance (SPR) technique was used. A transmembrane ocular mucin surface was prepared on the chip surface and characterized by QCM-D (Quartz Crystal Microbalance with Dissipation) and XPS (X-ray photoelectron spectroscopy). The mucoadhesive molecules tested were: hyaluronic acid (HA), carboxymethyl cellulose (CMC), hydroxypropylmethyl cellulose (HPMC), chitosan (Ch) and polyamidoamine dendrimers (PAMAM). Results While Ch originated interfacial interaction with ocular transmembrane mucins, for HA, CMC and HPMC, chain interdiffusion seemed to be mandatory for bioadherence at the concentrations used in ophthalmic clinical practise. Interestingly, PAMAM dendrimers developed permanent interfacial interactions with transmembrane ocular mucins whatever their surface chemical groups, showing a relevant importance of co-operative effect of these multivalent systems. Polymers developed interfacial interactions with ocular membrane-associated mucins in the following order: Ch(1 %) > G4PAMAM-NH2(2 %) = G4PAMAM-OH(2 %) > G3.5PAMAM-COOH(2 %)≫ CMC(0.5 %) = HA(0.2 %) = HPMC(0.3 %). Conclusions The method proposed is useful to discern between the mucin-polymer chemical interactions at molecular scale. Results reinforce the usefulness of chitosan and den-drimers as polymers able to increase the retention time of drugs on the ocular surface and hence their bioavailability. PMID:22565639
Ryan Wagner; Robert J. Moon; Arvind Raman
2016-01-01
Quantification of the mechanical properties of cellulose nanomaterials is key to the development of new cellulose nanomaterial based products. Using contact resonance atomic force microscopy we measured and mapped the transverse elastic modulus of three types of cellulosic nanoparticles: tunicate cellulose nanocrystals, wood cellulose nanocrystals, and wood cellulose...
Non-cellulosic polysaccharides from cotton fibre are differently impacted by textile processing.
Runavot, Jean-Luc; Guo, Xiaoyuan; Willats, William G T; Knox, J Paul; Goubet, Florence; Meulewaeter, Frank
2014-01-01
Cotton fibre is mainly composed of cellulose, although non-cellulosic polysaccharides play key roles during fibre development and are still present in the harvested fibre. This study aimed at determining the fate of non-cellulosic polysaccharides during cotton textile processing. We analyzed non-cellulosic cotton fibre polysaccharides during different steps of cotton textile processing using GC-MS, HPLC and comprehensive microarray polymer profiling to obtain monosaccharide and polysaccharide amounts and linkage compositions. Additionally, in situ detection was used to obtain information on polysaccharide localization and accessibility. We show that pectic and hemicellulosic polysaccharide levels decrease during cotton textile processing and that some processing steps have more impact than others. Pectins and arabinose-containing polysaccharides are strongly impacted by the chemical treatments, with most being removed during bleaching and scouring. However, some forms of pectin are more resistant than others. Xylan and xyloglucan are affected in later processing steps and to a lesser extent, whereas callose showed a strong resistance to the chemical processing steps. This study shows that non-cellulosic polysaccharides are differently impacted by the treatments used in cotton textile processing with some hemicelluloses and callose being resistant to these harsh treatments.
Integrated optics ring-resonator chemical sensor with polymer transduction layer
NASA Technical Reports Server (NTRS)
Ksendzov, A.; Homer, M. L.; Manfreda, A. M.
2004-01-01
An integrated optics chemical sensor based on a ring resonator with an ethyl cellulose polymer coating has been demonstrated. The measured sensitivity to isopropanol in air is 50 ppm-the level immediately useful for health-related air quality monitoring. The resonator was fabricated using SiO2 and SixNy materials. The signal readout is based on tracking the wavelength of a resonance peak. The resonator layout optimisation for sensing applications is discussed.
Pircher, Nicole; Fischhuber, David; Carbajal, Leticia; Strauß, Christine; Nedelec, Jean‐Marie; Kasper, Cornelia; Rosenau, Thomas
2015-01-01
1 Biocompatible cellulose‐based aerogels composed of nanoporous struts, which embed interconnected voids of controlled micron‐size, have been prepared employing temporary templates of fused porogens, reinforcement by interpenetrating PMMA networks and supercritical carbon dioxide drying. Different combinations of cellulose solvent (Ca(SCN)2/H2O/LiCl or [EMIm][OAc]/DMSO) and anti‐solvent (EtOH), porogen type (paraffin wax or PMMA spheres) and porogen size (various fractions in the range of 100–500 μm) as well as intensity of PMMA reinforcement have been investigated to tailor the materials for cell scaffolding applications. All aerogels exhibited an open and dual porosity (micronporosity >100 μm and nanoporosity extending to the low micrometer range). Mechanical properties of the dual‐porous aerogels under compressive stress were considerably improved by introduction of interpenetrating PMMA networks. The effect of the reinforcing polymer on attachment, spreading, and proliferation of NIH 3T3 fibroblast cells, cultivated on selected dual‐porous aerogels to pre‐evaluate their biocompatibility was similarly positive. PMID:26941565
Pesticidal seed coats based on azadirachtin-A: release kinetics, storage life and performance.
Nisar, Keyath; Kumar, Jitendra; Arun Kumar, M B; Walia, Suresh; Shakil, Najam A; Parsad, Rajender; Parmar, Balraj S
2009-02-01
Infestation of seeds by pests during storage leads to deterioration in quality. Seed coating is an effective option to overcome the menace. Unlike synthetic fungicidal seed coats, little is known of those based on botanicals. This study aims at developing azadirachtin-A-based pesticidal seed coats to maintain seed quality during storage. Polymer- and clay-based coats containing azadirachtin-A were prepared and evaluated for quality maintenance of soybean seed during storage. Gum acacia, gum tragacanth, rosin, ethyl cellulose, hydroxyethyl cellulose, polyethyl methacrylate, methyl cellulose, polyethylene glycol, polyvinyl chloride, polyvinyl acetate, polyvinyl pyrrolidone and Agrimer VA 6 polymers and the clay bentonite were used as carriers. The time for 50% release (t(1/2)) of azadirachtin-A into water from the seeds coated with the different coats ranged from 8.02 to 21.36 h. The half-life (T(1/2)) of azadirachtin-A in the coats on seed ranged from 4.37 to 11.22 months, as compared with 3.45 months in azadirachtin-A WP, showing an increase by a factor of nearly 1.3-3.3 over the latter. The coats apparently acted as a barrier to moisture to reduce azadirachtin-A degradation and prevented proliferation of storage fungi. Polyethyl methacrylate, polyvinyl acetate and polyvinyl pyrrolidone were significantly superior to the other polymers. Azadirachtin-A showed a significant positive correlation with seed germination and vigour, and negative correlation with moisture content. Effective polymeric carriers for seed coats based on azadirachtin-A are reported. These checked seed deterioration during storage by acting as a barrier to moisture and reduced the degradation of azadirachtin-A.
Malho, Jani-Markus; Ouellet-Plamondon, Claudiane; Rüggeberg, Markus; Laaksonen, Päivi; Ikkala, Olli; Burgert, Ingo; Linder, Markus B
2015-01-12
Biological composites are typically based on an adhesive matrix that interlocks rigid reinforcing elements in fiber composite or brick-and-mortar assemblies. In nature, the adhesive matrix is often made up of proteins, which are also interesting model systems, as they are unique among polymers in that we know how to engineer their structures with atomic detail and to select protein elements for specific interactions with other components. Here we studied how fusion proteins that consist of cellulose binding proteins linked to proteins that show a natural tendency to form multimer complexes act as an adhesive matrix in combination with nanofibrillated cellulose. We found that the fusion proteins are retained with the cellulose and that the proteins mainly affect the plastic yield behavior of the cellulose material as a function of water content. Interestingly, the proteins increased the moisture absorption of the composite, but the well-known plastifying effect of water was clearly decreased. The work helps to understand the functional basis of nanocellulose composites as materials and aims toward building model systems for molecular biomimetic materials.
Fortunati, E; Luzi, F; Jiménez, A; Gopakumar, D A; Puglia, D; Thomas, S; Kenny, J M; Chiralt, A; Torre, L
2016-09-20
Novel gluten based bionanocomposites reinforced with cellulose nanofibrils (CNF) and cellulose nanocrystals (CNC) extracted from sunflower stalks by respectively a steam explosion treatment and a hydrolysis procedure, were prepared by casting/evaporation. The extracted cellulose nanomaterials, both CNC and CNF, were embedded in gluten matrix and their effect was investigated. Morphological investigations highlighted that gluten based bionanocomposites showed a homogenous morphology, the absence of visible cellulose nanoreinforcements, and the presence of holes for Gluten_CNF nanocomposites. Gluten_CNF showed a reduction of water vapour permeability coefficients but the values are higher respect to gluten reinforced with CNC. This behaviour could be related to the ability of CNC to increase the tortuous path of gas molecules. Moreover, the results from thermal, mechanical and barrier properties confirmed the strong interactions obtained between CNC and gluten matrix during the process. The study suggested the possibility to re-valorise agricultural wastes with potential applications as reinforcement in polymer matrix bionanocomposites. Copyright © 2016 Elsevier Ltd. All rights reserved.
Tang, Yanjun; Hu, Xiulan; Zhang, Xinqi; Guo, Daliang; Zhang, Junhua; Kong, Fangong
2016-10-20
Incorporation of nanofillers into a polymeric matrix has received much attention as a route to reinforced polymer nanocomposites. In the present work, an environmentally friendly chitosan (CTS)/titanium dioxide (TiO2) nanocomposite coating was designed/prepared and subsequently employed for imparting antibacterium and improved mechanical properties to cellulosic paper via surface coating. Effect of TiO2 nanoparticle loadings on the rheological behavior of nanocomposite coatings was investigated. Surface application of CTS/TiO2 nanocomposite coatings to cellulosic paper was performed, and the antibacterial activity and mechanical properties of surface-coated cellulosic paper were examined. Results showed that the increased TiO2 nanoparticle loadings decreased the viscosity and dynamic viscoelasticity of the as-prepared coatings, and improved the antibacterial activity and mechanical properties of surface-coated cellulosic paper. The optimum loading of TiO2 nanoparticles was identified at 10%. This work suggested that CTS/TiO2 nanocomposite coatings may have the potential to be used as a promising antibacterial protective coating for paper packaging. Copyright © 2016 Elsevier Ltd. All rights reserved.
Co-processing as a tool to improve aqueous dispersibility of cellulose ethers.
Sharma, Payal; Modi, Sameer R; Bansal, Arvind K
2015-01-01
Cellulose ethers are important materials with numerous applications in pharmaceutical industry. They are widely employed as stabilizers and viscosity enhancers for dispersed systems, binders in granulation process and as film formers for tablets. These polymers, however, exhibit challenge during preparation of their aqueous dispersions. Rapid hydration of their surfaces causes formation of a gel that prevents water from reaching the inner core of the particle. Moreover, the surfaces of these particles become sticky, thus leading to agglomeration, eventually reducing their dispersion kinetics. Numerous procedures have been tested to improve dispersibility of cellulose ethers. These include the use of cross-linking agents, alteration in the synthesis process, adjustment of water content of cellulose ether, modification by attaching hydrophobic substituents and co-processing using various excipients. Among these, co-processing has provided the most encouraging results. This review focuses on the molecular mechanisms responsible for the poor dispersibility of cellulose ethers and the role of co-processing technologies in overcoming the challenge. An attempt has been made to highlight various co-processing techniques and specific role of excipients used for co-processing.
Jahn, Courtney E; Selimi, Dija A; Barak, Jeri D; Charkowski, Amy O
2011-10-01
Dickeya dadantii is a plant-pathogenic bacterium that produces cellulose-containing biofilms, called pellicles, at the air-liquid interface of liquid cultures. D. dadantii pellicle formation appears to be an emergent property dependent upon at least three gene clusters, including cellulose synthesis, type III secretion system (T3SS) and flagellar genes. The D. dadantii cellulose synthesis operon is homologous to that of Gluconacetobacter xylinus, which is used for industrial cellulose production, and the cellulose nanofibres produced by D. dadantii were similar in diameter and branching pattern to those produced by G. xylinus. Salmonella enterica, an enterobacterium closely related to D. dadantii, encodes a second type of cellulose synthesis operon, and it produced biofilm strands that differed in width and branching pattern from those of D. dadantii and G. xylinus. Unlike any previously described cellulose fibre, the D. dadantii cellulose nanofibres were decorated with bead-like structures. Mutation of the cellulose synthesis operon genes resulted in loss of cellulose synthesis and production of a cellulase-resistant biofilm. Mutation of other genes required for pellicle formation, including those encoding FliA (a sigma factor that regulates flagella production), HrpL (a sigma factor that regulates the T3SS), and AdrA, a GGDEF protein, affected both biofilm and cell morphology. Mutation of the cellulose synthase bcsA or of bcsC resulted in decreased accumulation of the T3SS-secreted protein HrpN.
Kenawy, I M; Ismail, M A; Hafez, M A H; Hashem, M A
2018-04-21
The new ion-imprinted guanyl-modified cellulose (II.Gu-MC) was prepared for the separation and determination of Cu (II) ions in different real samples. Several techniques such as Fourier Transform Infrared (FT-IR), scanning electron microscope (SEM), thermal analysis, potentiograph and elemental analysis have been utilized for the characterization of II.Gu-MC. The adsorption behavior of the ion imprinted polymer (II.Gu-MC) was evaluated and compared to the non ion-imprinted polymer (NII.Gu-MC) at the optimum conditions. The selectivity and the adsorption capacity were greatly enhanced by using the ion-imprinted polymer, indicating its validation for the separation and determination of Cu 2+ ions in different matrices. The adsorption capacity by chelating fibers II.Gu-MC & NII.Gu-MC agreed with the second-order model, and the sorption-isotherm experiments revealed best agreement with Langmuir model. The adsorption capacity of II.Gu-MC and NII.Gu-MC were 115 and 55 mg·g -1 , respectively. The II.Gu-MC was successfully employed for the selective separation and determination of Cu(II) ions with high accuracy. Copyright © 2018 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Kasa, Siti Norbaya; Omar, Mohd Firdaus; Ismail, Ismarul Nizam
2017-12-01
Nanocrystalline cellulose (NCC) was synthesized from banana stem through strong acid hydrolysis with measured length of approximately 287.0 ± 56.4 nm and diameter of 26.6 ± 4.8 nm. Modification of NCC was carried by acetylation reaction in order to increase the compatibility during reinforcement with polylactic acid (PLA) polymer. The reinforcing effect towards morphology, crystallinity, mechanical and thermal properties of bio-nanocomposites was investigated. Scanning Electron Microscope (SEM) micrograph reveals the uniform dispersion achieved at 1 %, 3 % and 5% aNC loading while agglomeration was found at 7 % aNC loading. Disappearance of crystallinity peak at 2θ = 22.7⁰ for low aNC loading during elemental analysis using X-Ray Diffraction (XRD) indicates the proper dispersion of aNC in PLA polymer. From the tensile test, 1 % aNC loading gives the highest mechanical properties of bio-nanocomposite film with 82.71 %, 118.7 % and 24.18 % increment in tensile strength, tensile modulus and elongation at break. However, 7 % aNC loading gives the highest increment in TGA of aNC-PLA nanocomposites which is from 310 °C to 320 °C.
Shedletzky, Esther; Shmuel, Miri; Trainin, Tali; Kalman, Sara; Delmer, Deborah
1992-01-01
Our previous work (E. Shedletzky, M. Shmuel, D.P. Delmer, D.T.A. Lamport [1990] Plant Physiol 94:980-987) showed that suspension-cultured tomato cells adapted to growth on the cellulose synthesis inhibitor 2,6-dichlorobenzonitrile (DCB) have a markedly altered cell wall composition, most notably a markedly reduced level of the cellulose-xyloglucan network. This study compares the adaptation to DCB of two cell lines from dicots (tomato [Lycopersicon esculentum] and tobacco [Nicotiana tabacum]) and a Graminaceous monocot (barley [Hordeum bulbosum] endosperm). The difference in wall structures between the dicots and the monocot is reflected in the very different types of wall modifications induced by growth on DCB. The dicots, having reduced levels of cellulose and xyloglucan, possess walls the major integrity of which is provided by Ca2+-bridged pectates because protoplasts can be prepared from these cells simply by treatment with divalent cation chelator and a purified endopolygalacturonase. The tensile strength of these walls is considerably less than walls from nonadapted cells, but wall porosity is not altered. In contrast, walls from adapted barley cells contain very little pectic material and normal to elevated levels of noncellulosic polysaccharides compared with walls from nonadapted cells. Surprisingly, they have tensile strengths higher than their nonadapted counterpart, although cellulose levels are reduced by 70%. Evidence is presented that these walls obtain their additional strength by an altered pattern of cross-linking of polymers involving phenolic components. Such cross-linking may also explain the observation that the porosity of these walls is also considerably reduced. Cells of adapted lines of both the dicots and barley are resistant to plasmolysis, suggesting that they possess very strong connections between the wall and the plasma membrane. Images Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 PMID:16652933
DEMONSTRATION BULLETIN: FORAGER™ SPONGE TECHNOLOGY - DYNAPHORE, INC.
The Forager™ Sponge is an open-celled cellulose sponge incorporating an amine-containing chelating polymer that has selective affinity for dissolved heavy metals in both cationic and anionic states. The Forager™ Sponge technology can be utilized to remove and concentrate heavy me...
Zeisler, Viktoria; Schreiber, Lukas
2016-01-01
Epicuticular wax of cherry laurel does not contribute to the formation of the cuticular transpiration barrier, which must be established by intracuticular wax. Barrier properties of cuticles are established by cuticular wax deposited on the outer surface of the cuticle (epicuticular wax) and in the cutin polymer (intracuticular wax). It is still an open question to what extent epi- and/or intracuticular waxes contribute to the formation of the transpiration barrier. Epicuticular wax was mechanically removed from the surfaces of isolated cuticles and intact leaf disks of cherry laurel (Prunus laurocerasus L.) by stripping with different polymers (collodion, cellulose acetate and gum arabic). Scanning electron microscopy showed that two consecutive treatments with all three polymers were sufficient to completely remove epicuticular wax since wax platelets disappeared and cuticle surfaces appeared smooth. Waxes in consecutive polymer strips and wax remaining in the cuticle after treatment with the polymers were determined by gas chromatography. This confirmed that two treatments of the polymers were sufficient for selectively removing epicuticular wax. Water permeability of isolated cuticles and cuticles covering intact leaf disks was measured using (3)H-labelled water before and after selectively removing epicuticular wax. Cellulose acetate and its solvent acetone led to a significant increase of cuticular permeability, indicating that the organic solvent acetone affected the cuticular transpiration barrier. However, permeability did not change after two subsequent treatments with collodion and gum arabic or after treatment with the corresponding solvents (diethyl ether:ethanol or water). Thus, in the case of P. laurocerasus the epicuticular wax does not significantly contribute to the formation of the cuticular transpiration barrier, which evidently must be established by the intracuticular wax.
Gierlinger, Notburga; Luss, Saskia; König, Christian; Konnerth, Johannes; Eder, Michaela; Fratzl, Peter
2010-01-01
The functional characteristics of plant cell walls depend on the composition of the cell wall polymers, as well as on their highly ordered architecture at scales from a few nanometres to several microns. Raman spectra of wood acquired with linear polarized laser light include information about polymer composition as well as the alignment of cellulose microfibrils with respect to the fibre axis (microfibril angle). By changing the laser polarization direction in 3 degrees steps, the dependency between cellulose and laser orientation direction was investigated. Orientation-dependent changes of band height ratios and spectra were described by quadratic linear regression and partial least square regressions, respectively. Using the models and regressions with high coefficients of determination (R(2) > 0.99) microfibril orientation was predicted in the S1 and S2 layers distinguished by the Raman imaging approach in cross-sections of spruce normal, opposite, and compression wood. The determined microfibril angle (MFA) in the different S2 layers ranged from 0 degrees to 49.9 degrees and was in coincidence with X-ray diffraction determination. With the prerequisite of geometric sample and laser alignment, exact MFA prediction can complete the picture of the chemical cell wall design gained by the Raman imaging approach at the micron level in all plant tissues.
Biosynthesis and Characterization of Nanocellulose-Gelatin Films
Taokaew, Siriporn; Seetabhawang, Sutasinee; Siripong, Pongpun; Phisalaphong, Muenduen
2013-01-01
A nanocellulose-gelatin (bacterial cellulose gelatin (BCG)) film was developed by a supplement of gelatin, at a concentration of 1%–10% w/v, in a coconut-water medium under the static cultivation of Acetobacter xylinum. The two polymers exhibited a certain degree of miscibility. The BCG film displayed dense and uniform homogeneous structures. The Fourier transform infrared spectroscopy (FTIR) results demonstrated interactions between the cellulose and gelatin. Incorporation of gelatin into a cellulose nanofiber network resulted in significantly improved optical transparency and water absorption capacity of the films. A significant drop in the mechanical strengths and a decrease in the porosity of the film were observed when the supplement of gelatin was more than 3% (w/v). The BCG films showed no cytotoxicity against Vero cells. PMID:28809339
Simple green approach to reinforce natural rubber with bacterial cellulose nanofibers.
Trovatti, Eliane; Carvalho, Antonio J F; Ribeiro, Sidney J L; Gandini, Alessandro
2013-08-12
Natural rubber (NR) is a renewable polymer with a wide range of applications, which is constantly tailored, further increasing its utilizations. The tensile strength is one of its most important properties susceptible of being enhanced by the simple incorporation of nanofibers. The preparation and characterization of natural-rubber based nanocomposites reinforced with bacterial cellulose (BC) and bacterial cellulose coated with polystyrene (BCPS), yielded high performance materials. The nanocomposites were prepared by a simple and green process, and characterized by tensile tests, dynamical mechanical analysis (DMA), scanning electron microscopy (SEM), and swelling experiments. The effect of the nanofiber content on morphology, static, and dynamic mechanical properties was also investigated. The results showed an increase in the mechanical properties, such as Young's modulus and tensile strength, even with modest nanofiber loadings.
Phyo, Pyae; Wang, Tuo; Yang, Yu; O'Neill, Hugh; Hong, Mei
2018-05-14
In contrast to the well-studied crystalline cellulose of microbial and animal origins, cellulose in plant cell walls is disordered due to its interactions with matrix polysaccharides. Plant cell wall (PCW) is an undisputed source of sustainable global energy; therefore, it is important to determine the molecular structure of PCW cellulose. The most reactive component of cellulose is the exocyclic hydroxymethyl group: when it adopts the tg conformation, it stabilizes intrachain and interchain hydrogen bonding, while gt and gg conformations destabilize the hydrogen-bonding network. So far, information about the hydroxymethyl conformation in cellulose has been exclusively obtained from 13 C chemical shifts of monosaccharides and oligosaccharides, which do not reflect the environment of cellulose in plant cell walls. Here, we use solid-state Nuclear Magnetic Resonance (ssNMR) spectroscopy to measure the hydroxymethyl torsion angle of cellulose in two model plants, by detecting distance-dependent polarization transfer between H4 and H6 protons in 2D 13 C- 13 C correlation spectra. We show that the interior crystalline portion of cellulose microfibrils in Brachypodium and Arabidopsis cell walls exhibits H4-H6 polarization transfer curves that are indicative of a tg conformation, whereas surface cellulose chains exhibit slower H4-H6 polarization transfer that is best fit to the gt conformation. Joint constraints by the H4-H6 polarization transfer curves and 13 C chemical shifts indicate that it is unlikely for interior cellulose to have a significant population of the gt and gg conformation mixed with the tg conformation, while surface cellulose may adopt a small percentage of the gg conformation. These results provide new constraints to the structure and matrix interactions of cellulose in plant cell walls, and represent the first direct determination of a torsion angle in an important noncrystalline carbohydrate polymer.
Li, Yan; Liu, Hongyi; Song, Junlong; Rojas, Orlando J; Hinestroza, Juan P
2011-07-01
The association of a symmetric polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO(19)-PPO(29)-PEO(19)) triblock copolymer adsorbed from aqueous solutions onto polypropylene (PP), polyethylene (PE), and cellulose surfaces was probed using Atomic Force Microscopy (AFM). Significant morphological differences between the polyolefin substrates (PP and PE) and the cellulose surfaces were observed after immersion of the films in the PEO(19)-PPO(29)-PEO(19) solutions. When the samples were scanned, while immersed in solutions of the triblock copolymer, it was revealed that the structures adsorbed on the polyolefin surfaces were smoothed by the adsorbed PEO(19)-PPO(29)-PEO(19). In contrast, those structures on the hydrophilic cellulose surfaces were sharpened. These observations were related to the roughness of the substrate and the energy of interaction between the surfaces and the PEO and PPO polymer segments. The interaction energy between each of the blocks and the surface was calculated using molecular dynamics simulations. It is speculated that the associative structures amply reported in aqueous solution at concentrations above the critical micelle concentration, CMC, are not necessarily preserved upon adsorption; instead, it appears that molecular arrangements of the anchor-buoy type and hemimicelles prevail. The reported data suggests that the roughness of the surface, as well as its degree of hydrophobicity, have a large influence on the nature of the resulting adsorbed layer. The reported observations are valuable in explaining the behavior of finishing additives and lubricants commonly used in textile and fiber processing, as well as the effect of the morphology of the boundary layers on friction and wear, especially in the case of symmetric triblock copolymers, which are commonly used as antifriction, antiwear additives.
Enhanced cellulose orientation analysis in complex model plant tissues.
Rüggeberg, Markus; Saxe, Friederike; Metzger, Till H; Sundberg, Björn; Fratzl, Peter; Burgert, Ingo
2013-09-01
The orientation distribution of cellulose microfibrils in the plant cell wall is a key parameter for understanding anisotropic plant growth and mechanical behavior. However, precisely visualizing cellulose orientation in the plant cell wall has ever been a challenge due to the small size of the cellulose microfibrils and the complex network of polymers in the plant cell wall. X-ray diffraction is one of the most frequently used methods for analyzing cellulose orientation in single cells and plant tissues, but the interpretation of the diffraction images is complex. Traditionally, circular or square cells and Gaussian orientation of the cellulose microfibrils have been assumed to elucidate cellulose orientation from the diffraction images. However, the complex tissue structures of common model plant systems such as Arabidopsis or aspen (Populus) require a more sophisticated approach. We present an evaluation procedure which takes into account the precise cell geometry and is able to deal with complex microfibril orientation distributions. The evaluation procedure reveals the entire orientation distribution of the cellulose microfibrils, reflecting different orientations within the multi-layered cell wall. By analyzing aspen wood and Arabidopsis stems we demonstrate the versatility of this method and show that simplifying assumptions on geometry and orientation distributions can lead to errors in the calculated microfibril orientation pattern. The simulation routine is intended to be used as a valuable tool for nanostructural analysis of plant cell walls and is freely available from the authors on request. Copyright © 2013 Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Adair, Ajaman; Klinpituksa, Pairote; Kaesaman, Azizon
2017-08-01
In this research, superabsorbent hydrogels were synthesized by graft copolymerization of hydroxyethyl cellulose (HEC) and polyacrylamide (PAM) under the initiation of potassium persulfate (KPS). The polymer networks were constructed using N,N'-methylenebisacrylamide (MBA), and the reaction was performed in an aqueous solution. The extent of grafting products was evaluated form grafting efficiency (%GE) and percentage of add-ons at HEC/AM ratios of 1: 10. The water swelling capacities, in terms of swelling capacity and weight loss, of resultant superabsorbent polymers (SAPs) after solvent extraction were determined for swelling behaviors. The result showed that the SAP had poor water absorption of approximately up to 23 g/g. To enhance swelling capacity of SAPs, an alkaline hydrolysis was done by using two types of alkaline bases, i.e., 2 M NaOH and 2 M KOH solution. The obtained treatment SAPs were neutralized by washing with distilled water and 0.5 M HCl until the liquors pH was nearly 7. They were found that the treatment SAPs showed the highest water absorption up to 317 g/g. Influences of various fluids pH values ranging between 4 and 10, on water swelling capacities of SAPs were also investigated. Under optimal pH value, the highest water absorptions of SAP was 382 g/g. To confirm the grafting reaction of PAM onto HEC backbone, FT-IR analysis was used. The results revealed absorption bands of the HEC backbone and new absorption bands from the grafted copolymer. Furthermore, the FT-IR spectrum was proved that washing with distilled water can alter the chemical functional group of SAPs.
Cho, H S; Moon, H S; Kim, M; Nam, K; Kim, J Y
2011-03-01
The biodegradability and the biodegradation rate of two kinds biodegradable polymers; poly(caprolactone) (PCL)-starch blend and poly(butylene succinate) (PBS), were investigated under both aerobic and anaerobic conditions. PCL-starch blend was easily degraded, with 88% biodegradability in 44 days under aerobic conditions, and showed a biodegradation rate of 0.07 day(-1), whereas the biodegradability of PBS was only 31% in 80 days under the same conditions, with a biodegradation rate of 0.01 day(-1). Anaerobic bacteria degraded well PCL-starch blend (i.e., 83% biodegradability for 139 days); however, its biodegradation rate was relatively slow (6.1 mL CH(4)/g-VS day) compared to that of cellulose (13.5 mL CH(4)/g-VS day), which was used as a reference material. The PBS was barely degraded under anaerobic conditions, with only 2% biodegradability in 100 days. These results were consistent with the visual changes and FE-SEM images of the two biodegradable polymers after the landfill burial test, showing that only PCL-starch blend had various sized pinholes on the surface due to attack by microorganisms. This result may be use in deciding suitable final disposal approaches of different types of biodegradable polymers in the future. Copyright © 2010 Elsevier Ltd. All rights reserved.
Miscible displacement of a non-Newtonian fluid in a capillary tube
NASA Astrophysics Data System (ADS)
Soori, Tejaswi; Ward, Thomas
2017-11-01
This talk focuses on experiments conducted to further our understanding of how to displace an aqueous polymer within a capillary tube (diameter < 1 mm) using a Newtonian fluid. Estimates of the residual film were measured as a function of Reynolds (Re), viscous Atwood (At) and Péclet (Pé) numbers. Aqueous polymers were prepared by mixing ϕ = 0.01-0.1% (wt/wt) Carboxymethyl Cellulose (CMC) in water. We measure the shear viscosity of the aqueous polymer over a broad range of shear rates and fit the data obtained to the Carreau fluid parameters. Separately we measure the average bulk diffusion coefficient of the aqueous polymer and water in water and aqueous polymer phases respectively. Previous studies on the immiscible displacement of polymers have shown residual film thickness to be dependent on the tube diameter. We will investigate if this is true when the two fluids are miscible in nature. American Chemical Society Petroleum Research Fund.
Recent patents on genetic modification of plants and microbes for biomass conversion to biofuels.
Lubieniechi, Simona; Peranantham, Thinesh; Levin, David B
2013-04-01
Development of sustainable energy systems based on renewable biomass feedstocks is now a global effort. Lignocellulosic biomass contains polymers of cellulose, hemicellulose, and lignin, bound together in a complex structure. Liquid biofuels, such as ethanol, can be made from biomass via fermentation of sugars derived from the cellulose and hemicellulose within lignocellulosic materials, but pre-treatment of the biomass to release sugars for microbial conversion is a significant barrier to commercial success of lignocellulosic biofuel production. Strategies to reduce the energy and cost inputs required for biomass pre-treatment include genetic modification of plant materials to reduce lignin content. Significant efforts are also underway to create recombinant microorganisms capable of converting sugars derived from lignocellulosic biomass to a variety of biofuels. An alternative strategy to reduce the costs of cellulosic biofuel production is the use of cellulolytic microorganisms capable of direct microbial conversion of ligno-cellulosic biomass to fuels. This paper reviews recent patents on genetic modification of plants and microbes for biomass conversion to biofuels.
Yan, Hong-Xiang; Zhang, Shuang-Shuang; He, Jian-Hua; Liu, Jian-Ping
2016-09-05
The present study aimed to develop and optimize the wax based floating sustained-release dispersion pellets for a weakly acidic hydrophilic drug protocatechuic acid to achieve prolonged gastric residence time and improved bioavailability. This low-density drug delivery system consisted of octadecanol/microcrystalline cellulose mixture matrix pellet cores prepared by extrusion-spheronization technique, coated with drug/ethyl cellulose 100cp solid dispersion using single-step fluid-bed coating method. The formulation-optimized pellets could maintain excellent floating state without lag time and sustain the drug release efficiently for 12h based on non-Fickian transport mechanism. Observed by SEM, the optimized pellet was the dispersion-layered spherical structure containing a compact inner core. DSC, XRD and FTIR analysis revealed drug was uniformly dispersed in the amorphous molecule form and had no significant physicochemical interactions with the polymer dispersion carrier. The stability study of the resultant pellets further proved the rationality and integrity of the developed formulation. Copyright © 2016 Elsevier Ltd. All rights reserved.
Cationic nanofibrillar cellulose with high antibacterial properties.
Chaker, Achraf; Boufi, Sami
2015-10-20
Cationic nanofibrillar cellulose (C-NFC) has been prepared via a high pressure homogenization using quaternized cellulose fibers with glycidyltrimethylammonium chloride. It has been shown that the quaternization of dried softwood pulp facilitated the defibrillation processes and prevented clogging of the homogenizer. The effects of the trimethylammonium chloride content on the fibrillation yield, the transparency degree of the gel, the rheological behavior of the NFC suspension and their electrokinetic properties were investigated. AFM observation showed that the NFC suspension consisted of individualized cellulose I nanofibrils 4-5nm in width and length in the micronic scale. In addition to their strong reinforcing potential, the inclusion of C-NFC into a polymer matrix was shown to efficiently enhance the antibacterial activity. The reinforcing potential of C-NFC, studied by dynamic mechanical analysis (DMA), was compared to anionic NFC and the difference was explained in terms of the nanofibrils capacities to build up a strong networks held by hydrogen bonding. Copyright © 2015 Elsevier Ltd. All rights reserved.
Noorbakhsh-Soltani, S M; Zerafat, M M; Sabbaghi, S
2018-06-01
Environmental concerns have led to extensive research for replacing polymer-based food packaging with bio-nano-composites. In this study, incorporation of nano-cellulose into gelatin and starch matrices is investigated for this purpose. Chitosan is used to improve mechanical, anti-fungal and waterproof properties. Experiments are designed and analyzed using response surface methodology. Nano-Cellulose is synthesized via acid hydrolysis and incorporated in base matrices through wet processing. Also, tensile strength test, food preservation, transparency in visible and UV and water contact angle are performed on the nano-composite films. DSC/TGA and air permeability tests are also performed on the optimal films. The results show that increasing nano-cellulose composition to 10% leads to increase the tensile strength at break to 8121 MN/m 2 and decrease the elongation at break. Also, increasing chitosan composition from 5% to 30% can enhance food preservation up to 15 days. Copyright © 2018 Elsevier Ltd. All rights reserved.
Inhibition effect of Arabic gum and cellulose acetate coatings on aluminium in acid/base media
NASA Astrophysics Data System (ADS)
Alva, S.; Sundari, R.; Rahmatullah, A.; Wahyudi, H.
2018-03-01
Nowadays aluminium is broadly used for battery purpose due to its conductivity, non toxic and economic reasons. Arabic gum and cellulose acetate are used as potential inhibitors to hinder corrosion effect on aluminium plate immersed in a solution of hydrochloric acid or sodium hydroxide. This investigation has studied the corrosion rate in terms of different concentrations of acid or base media. The average inhibition efficiency in the interested concentration range of both HCl and NaOH (0.1 M – 3.0 M) for 1 × 1 cm2 aluminium (Al) plate coated by 20% Arabic gum (AG) and 5% cellulose acetate (CA) with each thickness of 0.5 mm is found to be higher than 90%. The electrochemical behavior of corrosion effect is examined by cyclic voltammetric performance with respect to HCl or NaOH media. This investigation is useful especially for the study of Arabic gum and cellulose acetate utilized as polymer inhibitor in strong corrosive media.
Secretion of clostridium cellulase by E. coli
Yu, Ida Kuo
1998-01-01
A gene, encoding an endocellulase from a newly isolated mesophilic Clostridium strain IY-2 which can digest bamboo fibers, cellulose, rice straw, and sawdust, was isolated by shotgun cloning in an E. coli expression plasmid pLC2833. E. coli positive clones were selected based on their ability to hydrolyze milled bamboo fibers and cellulose present in agar plates. One clone contained a 2.8 kb DNA fragment that was responsible for cellulase activity. Western blot analyses indicated that the positive clone produced a secreted cellulase with a mass of about 58,000 daltons that was identical in size to the subunit of one of the three major Clostridium cellulases. The products of cellulose digestion by this cloned cellulase were cellotetraose and soluble higher polymers. The cloned DNA contained signal sequences capable of directing the secretion of heterologous proteins from an E. coli host. The invention describes a bioprocess for the treatment of cellulosic plant materials to produce cellular growth substrates and fermentation end products suitable for production of liquid fuels, solvents, and acids.
Cellulose nanofiber extraction from grass by a modified kitchen blender
NASA Astrophysics Data System (ADS)
Nakagaito, Antonio Norio; Ikenaga, Koh; Takagi, Hitoshi
2015-03-01
Cellulose nanofibers have been used to reinforce polymers, delivering composites with strength that in some cases can be superior to that of engineering plastics. The extraction of nanofibers from plant fibers can be achieved through specialized equipment that demands high energy input, despite delivering extremely low yields. The high extraction cost confines the use of cellulose nanofibers to the laboratory and not for industrial applications. This study aims to extract nanofibers from grass by using a kitchen blender. Earlier studies have demonstrated that paper sheets made of blender-extracted nanofibers (after 5 min to 10 min of blending) have strengths on par with paper sheets made from commercially available cellulose nanofibers. By optimizing the design of the blender bottle, nanofibrillation can be achieved in shorter treatment times, reducing the energy consumption (in the present case, to half) and the overall extraction cost. The raw materials used can be extended to the residue straw of agricultural crops, as an alternative to the usual pulp fibers obtained from wood.
Multifunctional PLA-PHB/cellulose nanocrystal films: processing, structural and thermal properties.
Arrieta, M P; Fortunati, E; Dominici, F; Rayón, E; López, J; Kenny, J M
2014-07-17
Cellulose nanocrystals (CNCs) synthesized from microcrystalline cellulose by acid hydrolysis were added into poly(lactic acid)-poly(hydroxybutyrate) (PLA-PHB) blends to improve the final properties of the multifunctional systems. CNC were also modified with a surfactant (CNCs) to increase the interfacial adhesion in the systems maintaining the thermal stability. Firstly, masterbatch pellets were obtained for each formulation to improve the dispersion of the cellulose structures in the PLA-PHB and then nanocomposite films were processed. The thermal stability as well as the morphological and structural properties of nanocomposites was investigated. While PHB increased the PLA crystallinity due to its nucleation effect, well dispersed CNC and CNCs not only increased the crystallinity but also improved the processability, the thermal stability and the interaction between both polymers especially in the case of the modified CNCs based PLA-PHB formulation. Likewise, CNCs were better dispersed in PLA-CNCs and PLA-PHB-CNCs, than CNC. Copyright © 2014 Elsevier Ltd. All rights reserved.
Blackburn, Richard S; Harvey, Anna; Kettle, Lorna L; Payne, John D; Russell, Stephen J
2006-06-20
Antimicrobial agents such as poly(hexamethylene biguanide) (PHMB) find application in medical, apparel, and household textile sectors; although it is understood that certain concentrations need to be applied to achieve suitable performance, there has been very little work published concerning the interactions of the polymer and its adsorption mechanism on cellulose. In this paper, such physical chemistry parameters are examined and related to computational chemistry studies. Adsorption isotherms were constructed: at low concentrations, these were typical Langmuir isotherms; at higher concentrations, they were more indicative of Freundlich isotherms, attributed to a combination of electrostatic and hydrogen-bonding forces, which endorsed computational chemistry proposals. At lower concentrations, electrostatic interactions between PHMB and carboxylic acid groups in the cellulose dominate with a contribution to binding through hydrogen bonding; as the concentration of PHMB increases, hydrogen bonding with cellulose becomes increasingly dominant. At high PHMB concentrations, observations of increasing PHMB adsorption are attributed to monolayer aggregation and multilayer stacking of PHMB through electrostatic interactions with counterions and hydrogen bonding of biguanide groups.
Surface interaction forces of cellulose nanocrystals grafted with thermoresponsive polymer brushes.
Zoppe, Justin O; Osterberg, Monika; Venditti, Richard A; Laine, Janne; Rojas, Orlando J
2011-07-11
The colloidal stability and thermoresponsive behavior of poly(N-isopropylacrylamide) brushes grafted from cellulose nanocrystals (CNCs) of varying graft densities and molecular weights was investigated. Indication of the grafted polymer brushes was obtained after AFM imaging of CNCs adsorbed on silica. Also, aggregation of the nanoparticles carrying grafts of high degree of polymerization was observed. The responsiveness of grafted CNCs in aqueous dispersions and as an ultrathin film was evaluated by using light scattering, viscosimetry, and colloidal probe microscopy (CPM). Light transmittance measurements showed temperature-dependent aggregation originating from the different graft densities and molecular weights. The lower critical solution temperature (LCST) of grafted poly(NiPAAm) brushes was found to decrease with the ionic strength, as is the case for free poly(NiPAAm) in aqueous solution. Thermal responsive behavior of grafted CNCs in aqueous dispersions was observed by a sharp increase in dispersion viscosity as the temperature approached the LCST. CPM in liquid media for asymmetric systems consisting of ultrathin films of CNCs and a colloidal silica probe showed the distinctive effects of the grafted polymer brushes on interaction and adhesive forces. The origin of such forces was found to be mainly electrostatic and steric in the case of bare and grafted CNCs, respectively. A decrease in the onset of attractive and adhesion forces of grafted CNCs films were observed with the ionic strength of the aqueous solution. The decreased mobility of polymer brushes upon partial collapse and decreased availability of hydrogen bonding sites with higher electrolyte concentration were hypothesized as the main reasons for the less prominent polymer bridging between interacting surfaces.
Cellulose Synthesis in Agrobacterium tumefaciens
DOE Office of Scientific and Technical Information (OSTI.GOV)
Alan R. White; Ann G. Matthysse
2004-07-31
We have cloned the celC gene and its homologue from E. coli, yhjM, in an expression vector and expressed the both genes in E. coli; we have determined that the YhjM protein is able to complement in vitro cellulose synthesis by extracts of A. tumefaciens celC mutants, we have purified the YhjM protein product and are currently examining its enzymatic activity; we have examined whole cell extracts of CelC and various other cellulose mutants and wild type bacteria for the presence of cellulose oligomers and cellulose; we have examined the ability of extracts of wild type and cellulose mutants includingmore » CelC to incorporate UDP-14C-glucose into cellulose and into water-soluble, ethanol-insoluble oligosaccharides; we have made mutants which synthesize greater amounts of cellulose than the wild type; and we have examined the role of cellulose in the formation of biofilms by A. tumefaciens. In addition we have examined the ability of a putative cellulose synthase gene from the tunicate Ciona savignyi to complement an A. tumefaciens celA mutant. The greatest difference between our knowledge of bacterial cellulose synthesis when we started this project and current knowledge is that in 1999 when we wrote the original grant very few bacteria were known to synthesize cellulose and genes involved in this synthesis were sequenced only from Acetobacter species, A. tumefaciens and Rhizobium leguminosarum. Currently many bacteria are known to synthesize cellulose and genes that may be involved have been sequenced from more than 10 species of bacteria. This additional information has raised the possibility of attempting to use genes from one bacterium to complement mutants in another bacterium. This will enable us to examine the question of which genes are responsible for the three dimensional structure of cellulose (since this differs among bacterial species) and also to examine the interactions between the various proteins required for cellulose synthesis. We have carried out one preliminary experiment of this type and have successfully complemented an A. tumefaciens CelC mutant with the homologous gene (yhjM) from E. coli.« less
USDA-ARS?s Scientific Manuscript database
The polysaccharides, cellulose, hemicellulose, and other additional carbohydrate polymers of terrestrial biomass, comprise renewable feedstocks for carbon-based chemicals and fuels. Biomass pretreatment is required to overcome its recalcitrance to biochemical deconstruction to monomeric sugars for ...
DYNAPHORE, INC. FORAGER SPONGE TECHNOLOGY - INNOVATIVE TECHNOLOGY EVALUATION REPORT
The Forager Sponge is an open-celled cellulose sponge incorporating an amine-containing chelating polymer that selectively absorbs dissolved heavy metals from aqueous waste streams. The Developer states that the technology can be utilized to remove and concentrate heavy metals f...
Prigent-Combaret, Claire; Zghidi-Abouzid, Ouafa; Effantin, Géraldine; Lejeune, Philippe; Reverchon, Sylvie; Nasser, William
2012-10-01
Bacteria use biofilm structures to colonize surfaces and to survive in hostile conditions, and numerous bacteria produce cellulose as a biofilm matrix polymer. Hence, expression of the bcs operon, responsible for cellulose biosynthesis, must be finely regulated in order to allow bacteria to adopt the proper surface-associated behaviours. Here we show that in the phytopathogenic bacterium, Dickeya dadantii, production of cellulose is required for pellicle-biofilm formation and resistance to chlorine treatments. Expression of the bcs operon is growth phase-regulated and is stimulated in biofilms. Furthermore, we unexpectedly found that the nucleoid-associated protein and global regulator of virulence functions, Fis, directly represses bcs operon expression by interacting with an operator that is absent from the bcs operon of animal pathogenic bacteria and the plant pathogenic bacterium Pectobacterium. Moreover, production of cellulose enhances plant surface colonization by D. dadantii. Overall, these data suggest that cellulose production and biofilm formation may be important factors for surface colonization by D. dadantii and its subsequent survival in hostile environments. This report also presents a new example of how bacteria can modulate the action of a global regulator to co-ordinate basic metabolism, virulence and modifications of lifestyle. © 2012 Blackwell Publishing Ltd.
Electro-mechanical characterization of structural supercapacitors
NASA Astrophysics Data System (ADS)
Gallagher, T.; LaMaster, D.; Ciocanel, C.; Browder, C.
2012-04-01
The paper presents electrical and mechanical properties of structural supercapacitors and discusses limitations associated with the approach taken for the electrical properties evaluation. The structural supercapacitors characterized in this work had the electrodes made of carbon fiber weave, separator made of several cellulose based products, and the solid electrolyte made as PEGDGE based polymer blend. The reported electrical properties include capacitance and leakage resistance; the former was measured using cyclic voltammetry. Mechanical properties have been evaluated thorough tensile and three point bending tests performed on structural supercapacitor coupons. The results indicate that the separator material plays an important role on the electrical as well as mechanical properties of the structural capacitor, and that Celgard 3501 used as separator leads to most benefits for both mechanical and electrical properties. Specific capacitance and leakage resistance as high as 1.4kF/m3 and 380kΩ, respectively, were achieved. Two types of solid polymer electrolytes were used in fabrication, with one leading to higher and more consistent leakage resistance values at the expense of a slight decrease in specific capacitance when compared to the other SPE formulation. The ultimate tensile strength and modulus of elasticity of the developed power storage composite were evaluated at 466MPa and 18.9MPa, respectively. These values are 58% and 69% of the tensile strength and modulus of elasticity values measured for a single layer composite material made with the same type of carbon fiber and with a West System 105 epoxy instead of solid polymer electrolyte.
Active polymer materials for optical fiber CO2 sensors
NASA Astrophysics Data System (ADS)
Wysokiński, Karol; Filipowicz, Marta; Stańczyk, Tomasz; Lipiński, Stanisław; Napierała, Marek; Murawski, Michał; Nasiłowski, Tomasz
2017-04-01
CO2 optical fiber sensors based on polymer active materials are presented in this paper. Ethyl cellulose was proven to be a good candidate for a matrix material of the sensor, since it gives porous, thick and very sensitive layers. Low-cost sensors based on polymer optical fibers have been elaborated. Sensors have been examined for their sensitivity to CO2, temperature and humidity. Response time during cyclic exposures to CO2 have been also determined. Special layers exhibiting irreversible change of color during exposure to carbon dioxide have been developed. They have been verified for a possible use in smart food packaging.
Comparative evaluation of single and bilayered lamotrigine floating tablets
Lakshmi, PK; Sridhar, M; Shruthi, B
2013-01-01
Aim: The purpose of this study was to prepare lamotrigine (LM) bilayered and single layered floating tablets and to compare their release profiles. Materials and Methods: LM floating tablets were prepared by direct compression method. Drug, hydroxy propyl methyl cellulose K4M, lactose monohydrate and polyvinylpyrrolidone K30 constitute controlled release layer components and floating layer components includes polymers and sodium bicarbonate. The prepared tablets were evaluated for physicochemical parameters such as hardness, friability, weight variation, thickness, floating lag time (FLT), floating time, in vitro buoyancy study, in vitro release studies. The drug-polymer interaction was studied by fourier transform infrared and differential scanning calorimetry. Results and Discussion: The FLT of all the formulations were within the prescribed limits (<3 min). When ethyl cellulose was used as floating layer component, tablets showed good buoyancy effect but eroded within 6-8 h. Hence it was replaced with hydroxypropyl cellulose -M hydrophilic polymer, which showed good FLT and floating duration for 16 h. Formulation LFC4 was found to be optimized with dissolution profile of zero order kinetics showing fickian diffusion. A comparative study of bilayered and single layered tablets of LM showed a highest similarity factor of 83.03, difference factor of 2.74 and t-test (P < 0.05) indicates that there is no significant difference between them. Conclusion: Though bilayered tablet possess many advantages, single layered tablet would be economical, cost-effective and reproducible for large scale production in the industry. However, the results of present study demonstrated that the in vitro development of bilayered gastro retentive floating tablets with controlled drug release profile for LM is feasible. PMID:24167788
NASA Astrophysics Data System (ADS)
Dewantara, Fauzi; Budianto, Emil
2018-04-01
Chitosan-methyl cellulose semi-IPN hydrogel is used as floating drug delivery system, and calcium carbonate also added as pore forming agent. The hydrogel network arranged by not only using biopolymer chitosan and methyl cellulose, but also the crosslink agent that is glutaraldehyde. Amoxicillin trihydrate entrapped into the polymer network with two different method, in situ loading and post loading. Furthermore both method has been tested for drug entrapment efficiency along with drug dissolution test, and the result for drug entrapment efficiency is in situ loading method has highest value of 100%, compared to post loading method which has value only 71%. Moreover, at the final time of drug dissolution test shows in situ loading method has value of 96% for total accumulative of drug dissolution, meanwhile post loading method has 72%. The value of drug dissolution test from both method is used for analyzing drug dissolution mechanism of amoxicillin trihydrate from hydrogel network with four mathematical drug mechanism models as parameter. The polymer network encounter destructive degradation causes by acid solution which used as dissolution medium, and the level of degradation is observed with optical microscope. However the result shows that degradation of the polymer network doesn't affect drug dissolution mechanism directly. Although the pore forming agent causes the pore inside the hydrogel network create interconnection and it was quite influential to drug dissolution mechanism. Interconnected pore is observed with Scanning Electron Microscope (SEM) and shows that the amount and area of interconnected pore inside the hydrogel network is increasing as drug dissolution goes on.
Design, development and evaluation of clopidogrel bisulfate floating tablets.
Rao, K Rama Koteswara; Lakshmi, K Rajya
2014-01-01
The objective of the present work was to formulate and to characterize a floating drug delivery system for clopidogrel bisulphate to improve bioavailability and to minimize the side effects of the drug such as gastric bleeding and drug resistance development. Clopidogrel floating tablets were prepared by direct compression technique by the use of three polymers xanthan gum, hydroxypropyl methylcellulose (HPMC) K15M and HPMC K4M in different concentrations (20%, 25% and 30% w/w). Sodium bicarbonate (15% w/w) and microcrystalline cellulose (30% w/w) were used as gas generating agent and diluent respectively. Studies were carried out on floating behavior and influence of type of polymer on drug release rate. All the formulations were subjected to various quality control and in-vitro dissolution studies in 0.1 N hydrochloric acid (1.2 pH) and corresponding dissolution data were fitted to popular release kinetic equations in order to evaluate release mechanisms and kinetics. All the clopidogrel floating formulations followed first order kinetics, Higuchi drug release kinetics with diffusion as the dominant mechanism of drug release. As per Korsmeyer-Peppas equation, the release exponent "n" ranged 0.452-0.654 indicating that drug release from all the formulations was by non-Fickian diffusion mechanism. The drug release rate of clopidogrel was found to be affected by the type and concentration of the polymer used in the formulation (P < 0.05). As the concentration of the polymer was increased, the drug release was found to be retarded. Based on the results, clopidogrel floating tablets prepared by employing xanthan gum at concentration 25% w/w (formulation F2) was the best formulation with desired in-vitro floating time and drug dissolution.
Knott, Brandon C; Crowley, Michael F; Himmel, Michael E; Zimmer, Jochen; Beckham, Gregg T
2016-05-01
The processive cycle of the bacterial cellulose synthase (Bcs) includes the addition of a single glucose moiety to the end of a growing cellulose chain followed by the translocation of the nascent chain across the plasma membrane. The mechanism of this translocation and its precise location within the processive cycle are not well understood. In particular, the molecular details of how a polymer (cellulose) whose basic structural unit is a dimer (cellobiose) can be constructed by adding one monomer (glucose) at a time are yet to be elucidated. Here, we have utilized molecular dynamics simulations and free energy calculations to the shed light on these questions. We find that translocation forward by one glucose unit is quite favorable energetically, giving a free energy stabilization of greater than 10 kcal/mol. In addition, there is only a small barrier to translocation, implying that translocation is not rate limiting within the Bcs processive cycle (given experimental rates for cellulose synthesis in vitro ). Perhaps most significantly, our results also indicate that steric constraints at the transmembrane tunnel entrance regulate the dimeric structure of cellulose. Namely, when a glucose molecule is added to the cellulose chain in the same orientation as the acceptor glucose, the terminal glucose freely rotates upon forward motion, thus suggesting a regulatory mechanism for the dimeric structure of cellulose. We characterize both the conserved and non-conserved enzyme-polysaccharide interactions that drive translocation, and find that 20 of the 25 residues that strongly interact with the translocating cellulose chain in the simulations are well conserved, mostly with polar or aromatic side chains. Our results also allow for a dynamical analysis of the role of the so-called `finger helix' in cellulose translocation that has been observed structurally. Taken together, these findings aid in the elucidation of the translocation steps of the Bcs processive cycle and may be widely relevant to polysaccharide synthesizing or degrading enzymes that couple catalysis with chain translocation.
Prevalence and trends of cellulosics in pharmaceutical dosage forms.
Mastropietro, David J; Omidian, Hossein
2013-02-01
Many studies have shown that cellulose derivatives (cellulosics) can provide various benefits when used in virtually all types of dosage forms. Nevertheless, the popularity of their use in approved drug products is rather unknown. This research reports the current prevalence and trends of use for 15 common cellulosics in prescription drug products. The cellulosics were powdered and microcrystalline cellulose (MCC), ethyl cellulose, hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), hypromellose (HPMC), HPMC phthalate, HPMC acetate succinate, cellulose acetate (CA), CA phthalate, sodium (Na) and calcium (Ca) carboxymethylcellulose (CMC), croscarmellose sodium (XCMCNa), methyl cellulose, and low substituted HPC. The number of brand drug products utilizing each cellulosics was determined using the online drug index Rxlist. A total of 607 brand products were identified having one or more of the cellulosics as an active or inactive ingredient. An array of various dosage forms was identified and revealed HPMC and MCC to be the most utilized cellulosics in all products followed by XCMCNa and HPC. Many products contained two or more cellulosics in the formulation (42% containing two, 23% containing three, and 4% containing 4-5). The largest combination occurrence was HPMC with MCC. The use of certain cellulosics within different dosage form types was found to contain specific trends. All injectables utilized only CMCNa, and the same with all ophthalmic solutions utilizing HPMC, and otic suspensions utilizing HEC. Popularity and trends regarding cellulosics use may occur based on many factors including functionality, safety, availability, stability, and ease of manufacturing.
Polylactic acid composites incorporating casein functionalized cellulose nanowhiskers
2013-01-01
Background Polylactic acid (PLA) is considered to be a sustainable alternative to petroleum-based polymers for many applications. Using cellulose fiber to reinforce PLA is of great interest recently due to its complete biodegradability and potential improvement of the mechanical performance. However, the dispersion of hydrophilic cellulose fibers in the hydrophobic polymer matrix is usually poor without using hazardous surfactants. The goal of this study was to develop homogenously dispersed cellulose nanowhisker (CNW) reinforced PLA composites using whole milk casein protein, which is an environmentally compatible dispersant. Results In this study, whole milk casein was chosen as a dispersant in the PLA-CNW system because of its potential to interact with the PLA matrix and cellulose. The affinity of casein to PLA was studied by surface plasmon resonance (SPR) imaging. CNWs were functionalized with casein and used as reinforcements to make PLA composites. Fluorescent staining of CNWs in the PLA matrix was implemented as a novel and simple way to analyze the dispersion of the reinforcements. The dispersion of CNWs in PLA was improved when casein was present. The mechanical properties of the composites were studied experimentally. Compared to pure PLA, the PLA composites had higher Young’s modulus. Casein (CS) functionalized CNW reinforced PLA (PLA-CS-CNW) at 2 wt% filler content maintained higher strain at break compared to normal CNW reinforced PLA (PLA-CNW). The Young’s modulus of PLA-CS-CNW composites was also higher than that of PLA-CNW composites at higher filler content. However, all composites exhibited lower strain at break and tensile strength at high filler content. Conclusions The presence of whole milk casein improved the dispersion of CNWs in the PLA matrix. The improved dispersion of CNWs provided higher modulus of the PLA composites at higher reinforcement loading and maintained the strain and stress at break of the composites at relatively low reinforcement loading. The affinity of the dispersant to PLA is important for the ultimate strength and stiffness of the composites. PMID:24341897
Endoglucanases: insights into thermostability for biofuel applications
2013-01-01
Obtaining bioethanol from cellulosic biomass involves numerous steps, among which the enzymatic conversion of the polymer to individual sugar units has been a main focus of the biotechnology industry. Among the cellulases that break down the polymeric cellulose are endoglucanases that act synergistically for subsequent hydrolytic reactions. The endoglucanases that have garnered relatively more attention are those that can withstand high temperatures, i.e., are thermostable. Although our understanding of thermostability in endoglucanases is incomplete, some molecular features that are responsible for increased thermostability have been recently identified. This review focuses on the investigations of endoglucanases and their implications for biofuel applications. PMID:24070146
Usov, Ivan; Nyström, Gustav; Adamcik, Jozef; Handschin, Stephan; Schütz, Christina; Fall, Andreas; Bergström, Lennart; Mezzenga, Raffaele
2015-01-01
Nanocellulose fibrils are ubiquitous in nature and nanotechnologies but their mesoscopic structural assembly is not yet fully understood. Here we study the structural features of rod-like cellulose nanoparticles on a single particle level, by applying statistical polymer physics concepts on electron and atomic force microscopy images, and we assess their physical properties via quantitative nanomechanical mapping. We show evidence of right-handed chirality, observed on both bundles and on single fibrils. Statistical analysis of contours from microscopy images shows a non-Gaussian kink angle distribution. This is inconsistent with a structure consisting of alternating amorphous and crystalline domains along the contour and supports process-induced kink formation. The intrinsic mechanical properties of nanocellulose are extracted from nanoindentation and persistence length method for transversal and longitudinal directions, respectively. The structural analysis is pushed to the level of single cellulose polymer chains, and their smallest associated unit with a proposed 2 × 2 chain-packing arrangement. PMID:26108282
McKee, Jason R; Huokuna, Johannes; Martikainen, Lahja; Karesoja, Mikko; Nykänen, Antti; Kontturi, Eero; Tenhu, Heikki; Ruokolainen, Janne; Ikkala, Olli
2014-05-12
Even though nanocomposites have provided a plethora of routes to increase stiffness and strength, achieving increased toughness with suppressed catastrophic crack growth has remained more challenging. Inspired by the concepts of mechanically excellent natural nanomaterials, one-component nanocomposites were fabricated involving reinforcing colloidal nanorod cores with polymeric grafts containing supramolecular binding units. The concept is based on mechanically strong native cellulose nanocrystals (CNC) grafted with glassy polymethacrylate polymers, with side chains that contain 2-ureido-4[1H]-pyrimidone (UPy) pendant groups. The interdigitation of the grafts and the ensuing UPy hydrogen bonds bind the nanocomposite network together. Under stress, UPy groups act as sacrificial bonds: simultaneously providing adhesion between the CNCs while allowing them to first orient and then gradually slide past each other, thus dissipating fracture energy. We propose that this architecture involving supramolecular binding units within side chains of polymer grafts attached to colloidal reinforcements opens generic approaches for tough nanocomposites. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Mechanical and thermal properties of promising polymer composites for food packaging applications
NASA Astrophysics Data System (ADS)
Abdellah Ali, S. F.
2016-07-01
Blending starches with biodegradable polycaprolactone (PCL) was used as a route to make processable thermoplastics. When developing biodegradable polymer composites it is important to use high concentrations of starch for legislative and cost reasons. The addition of starch has a significant effect on all physical properties including toughness, elongation at break and the rheological behaviour of the melt. To enhance the physical properties, we used cellulose acetate propionate (CAP) as a cellulose derivative with high amylase starch and PCL blends. It is suggested that the PCL/starch/CAP blends are partially miscible. It was found that the yield tensile strengths of most PCL/Starch/CAP blends were higher than that of pure PCL itself. There was a big difference between glass transition temperature values of PCL/Starch/CAP blends and the pure PCL glass transition temperature which indicates that no phase separation occurs. Addition of CAP to starch and PCL blends improved the mechanical and thermal properties even at high content of starch.
Zhuang, Chen; Shi, Chengmei; Tao, Furong; Cui, Yuezhi
2017-12-01
The functionalized cellulose ester MCN was firstly synthesized and used to cross-link gelatin by amidation between -NH 2 in gelatin and active ester groups in MCN to form a composite polymer network Gel-MCN, which was confirmed by Van Slyke method, FTIR, XRD and TGA-DTG spectra. The model drug omeprazole was loaded in Gel-MCN composites mainly by electrostatic interaction and hydrogen bonds, which were certified by FTIR, XRD and TGA-DSC. Thermal stability, anti-biodegradability, mechanical property and surface hydrophobicity of the composites with different cross-linking extents and drug loading were systematically investigated. SEM images demonstrated the honeycomb structural cells of cross-linked gelatin networks and this ensured drug entrapment. The drug release mechanism was dominated by a combined effect of diffusion and degradation, and the release rate decreased with cross-linking degree increased. The developed drug delivery system had profound significance in improving pesticide effect and bioavailability of drugs. Copyright © 2017. Published by Elsevier B.V.
Fabrication of high exposure nuclear fuel pellets
Frederickson, James R.
1987-01-01
A method is disclosed for making a fuel pellet for a nuclear reactor. A mixture is prepared of PuO.sub.2 and UO.sub.2 powders, where the mixture contains at least about 30% PuO.sub.2, and where at least about 12% of the Pu is the Pu.sup.240 isotope. To this mixture is added about 0.3 to about 5% of a binder having a melting point of at least about 250.degree. F. The mixture is pressed to form a slug and the slug is granulated. Up to about 4.7% of a lubricant having a melting point of at least about 330.degree. F. is added to the granulated slug. Both the binder and the lubricant are selected from a group consisting of polyvinyl carboxylate, polyvinyl alcohol, naturally occurring high molecular weight cellulosic polymers, chemically modified high molecular weight cellulosic polymers, and mixtures thereof. The mixture is pressed to form a pellet and the pellet is sintered.
Rooijakkers, Bart J. M.
2018-01-01
Six fungal-type cellulose binding domains were found in the genome of the coccolithophore Emiliania huxleyi and cloned and expressed in Escherichia coli. Sequence comparison indicate high similarity to fungal cellulose binding domains, raising the question of why these domains exist in coccolithophores. The proteins were tested for binding with cellulose and chitin as ligands, which resulted in the identification of two functional carbohydrate binding modules: EHUX2 and EHUX4. Compared to benchmark fungal cellulose binding domain Cel7A-CBM1 from Trichoderma reesei, these proteins showed slightly lower binding to birch and bacterial cellulose, but were more efficient chitin binders. Finally, a set of cellulose binding domains was created based on the shuffling of one well-functioning and one non-functional domain. These were characterized in order to get more information of the binding domain’s sequence–function relationship, indicating characteristic differences between the molecular basis of cellulose versus chitin recognition. As previous reports have showed the presence of cellulose in coccoliths and here we find functional cellulose binding modules, a possible connection is discussed. PMID:29782536
Rooijakkers, Bart J M; Ikonen, Martina S; Linder, Markus B
2018-01-01
Six fungal-type cellulose binding domains were found in the genome of the coccolithophore Emiliania huxleyi and cloned and expressed in Escherichia coli. Sequence comparison indicate high similarity to fungal cellulose binding domains, raising the question of why these domains exist in coccolithophores. The proteins were tested for binding with cellulose and chitin as ligands, which resulted in the identification of two functional carbohydrate binding modules: EHUX2 and EHUX4. Compared to benchmark fungal cellulose binding domain Cel7A-CBM1 from Trichoderma reesei, these proteins showed slightly lower binding to birch and bacterial cellulose, but were more efficient chitin binders. Finally, a set of cellulose binding domains was created based on the shuffling of one well-functioning and one non-functional domain. These were characterized in order to get more information of the binding domain's sequence-function relationship, indicating characteristic differences between the molecular basis of cellulose versus chitin recognition. As previous reports have showed the presence of cellulose in coccoliths and here we find functional cellulose binding modules, a possible connection is discussed.
How cellulose stretches: synergism between covalent and hydrogen bonding.
Altaner, Clemens M; Thomas, Lynne H; Fernandes, Anwesha N; Jarvis, Michael C
2014-03-10
Cellulose is the most familiar and most abundant strong biopolymer, but the reasons for its outstanding mechanical performance are not well understood. Each glucose unit in a cellulose chain is joined to the next by a covalent C-O-C linkage flanked by two hydrogen bonds. This geometry suggests some form of cooperativity between covalent and hydrogen bonding. Using infrared spectroscopy and X-ray diffraction, we show that mechanical tension straightens out the zigzag conformation of the cellulose chain, with each glucose unit pivoting around a fulcrum at either end. Straightening the chain leads to a small increase in its length and is resisted by one of the flanking hydrogen bonds. This constitutes a simple form of molecular leverage with the covalent structure providing the fulcrum and gives the hydrogen bond an unexpectedly amplified effect on the tensile stiffness of the chain. The principle of molecular leverage can be directly applied to certain other carbohydrate polymers, including the animal polysaccharide chitin. Related but more complex effects are possible in some proteins and nucleic acids. The stiffening of cellulose by this mechanism is, however, in complete contrast to the way in which hydrogen bonding provides toughness combined with extensibility in protein materials like spider silk.
Morouço, Pedro; Biscaia, Sara; Viana, Tânia; Franco, Margarida; Malça, Cândida; Mateus, Artur; Moura, Carla; Ferreira, Frederico C; Mitchell, Geoffrey; Alves, Nuno M
2016-01-01
Biomaterial properties and controlled architecture of scaffolds are essential features to provide an adequate biological and mechanical support for tissue regeneration, mimicking the ingrowth tissues. In this study, a bioextrusion system was used to produce 3D biodegradable scaffolds with controlled architecture, comprising three types of constructs: (i) poly( ε -caprolactone) (PCL) matrix as reference; (ii) PCL-based matrix reinforced with cellulose nanofibers (CNF); and (iii) PCL-based matrix reinforced with CNF and hydroxyapatite nanoparticles (HANP). The effect of the addition and/or combination of CNF and HANP into the polymeric matrix of PCL was investigated, with the effects of the biomaterial composition on the constructs (morphological, thermal, and mechanical performances) being analysed. Scaffolds were produced using a single lay-down pattern of 0/90°, with the same processing parameters among all constructs being assured. The performed morphological analyses showed a satisfactory distribution of CNF within the polymer matrix and high reliability was obtained among the produced scaffolds. Significant effects on surface wettability and thermal properties were observed, among scaffolds. Regarding the mechanical properties, higher scaffold stiffness in the reinforced scaffolds was obtained. Results from the cytotoxicity assay suggest that all the composite scaffolds presented good biocompatibility. The results of this first study on cellulose and hydroxyapatite reinforced constructs with controlled architecture clearly demonstrate the potential of these 3D composite constructs for cell cultivation with enhanced mechanical properties.
The past, present and future of the dialyzer.
Mineshima, Michio
2015-01-01
Several types of dialysis membranes have been developed in the history of hemodialysis therapy. Regenerated cellulose had been widely used for a long time, since the beginning of dialysis therapy. Regenerated cellulose is strongly hydrophilic, which enables lower membrane thickness and miniaturization of the dialyzer. The cellulose triacetate membrane has greater performance because of the lower thickness of the membrane and its lack of swelling due to high hydrophobicity. Many types of synthetic membranes, such as polysulfone, polyethersulfone and polyester polymer alloy membranes, have asymmetrical structures. Dialyzers with these membranes show higher capacities for water and solute transport because the actual membrane thickness, which is related to the water and solute transfer resistance, is quite small compared to that in membranes with homogeneous structures. The development of highly biocompatible membranes will be required in the future so as to prevent the development of adverse reactions and related complications. The performance of a dialyzer depends not only on the membrane permeability but also on the flow conditions of the blood and dialysate. Many types of dialyzers with high-performance membranes have been developed as a result of advances in membrane and device technologies. Recently, many types of high-flux dialyzers with high-performance membranes with a high internal filtration (IF)/backfiltration (BF) flow rate have been introduced. IF-enhanced hemodialysis using an enhanced IF dialyzer seems to be more convenient than hemodiafiltration therapy because it requires no additional equipment, such as a roller pump. In the near future, dialyzers should be developed with high capacities for the removal of low-molecular-weight proteins (LMWPs) related to complications and with low capacities for the loss of albumin and amino acid. Dialyzers with a sharp cut-off membrane between LMWPs and albumin and dialyzers with a special function, i.e., an adsorptive property for some LMWPs, are required. In addition, dialyzers with biocompatible membranes are necessary to prevent severe adverse reactions, although the causal relationship between these reactions and some complications are yet to be clarified. © 2015 S. Karger AG, Basel.
Ionic liquid processing of cellulose.
Wang, Hui; Gurau, Gabriela; Rogers, Robin D
2012-02-21
Utilization of natural polymers has attracted increasing attention because of the consumption and over-exploitation of non-renewable resources, such as coal and oil. The development of green processing of cellulose, the most abundant biorenewable material on Earth, is urgent from the viewpoints of both sustainability and environmental protection. The discovery of the dissolution of cellulose in ionic liquids (ILs, salts which melt below 100 °C) provides new opportunities for the processing of this biopolymer, however, many fundamental and practical questions need to be answered in order to determine if this will ultimately be a green or sustainable strategy. In this critical review, the open fundamental questions regarding the interactions of cellulose with both the IL cations and anions in the dissolution process are discussed. Investigations have shown that the interactions between the anion and cellulose play an important role in the solvation of cellulose, however, opinions on the role of the cation are conflicting. Some researchers have concluded that the cations are hydrogen bonding to this biopolymer, while others suggest they are not. Our review of the available data has led us to urge the use of more chemical units of solubility, such as 'g cellulose per mole of IL' or 'mol IL per mol hydroxyl in cellulose' to provide more consistency in data reporting and more insight into the dissolution mechanism. This review will also assess the greenness and sustainability of IL processing of biomass, where it would seem that the choices of cation and anion are critical not only to the science of the dissolution, but to the ultimate 'greenness' of any process (142 references).
Optimal Substitution of Cotton Burr and Linters in Thermoplastic Composites
USDA-ARS?s Scientific Manuscript database
A study was conducted to evaluate various substitutions of cotton burr and linters fractions of cotton gin waste (CGW) as a natural fiber source in ligno-cellulosic polymer composites (LCPC.) Samples were fabricated with approximately 50% natural fiber, 40% of high-density polyethylene (HDPE) powder...
2008-04-15
cellulose acetate polymers, and diols. Common sol- uble metal/metal oxide-bearing materials are metal alkoxides, metal diketonates, and metal ... carboxylates . Metal-organic compounds are usually subjected to hydrolysis and condensa- tion reactions to produce polymeric or colloidal metal-oxide
Facile Fabrication of 100% Bio-Based and Degradable Ternary Cellulose/PHBV/PLA Composites
Wang, Jinwu
2018-01-01
Modifying bio-based degradable polymers such as polylactide (PLA) and poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) with non-degradable agents will compromise the 100% degradability of their resultant composites. This work developed a facile and solvent-free route in order to fabricate 100% bio-based and degradable ternary cellulose/PHBV/PLA composite materials. The effects of ball milling on the physicochemical properties of pulp cellulose fibers, and the ball-milled cellulose particles on the morphology and mechanical properties of PHBV/PLA blends, were investigated experimentally and statistically. The results showed that more ball-milling time resulted in a smaller particle size and lower crystallinity by way of mechanical disintegration. Filling PHBV/PLA blends with the ball-milled celluloses dramatically increased the stiffness at all of the levels of particle size and filling content, and improved their elongation at the break and fracture work at certain levels of particle size and filling content. It was also found that the high filling content of the ball-milled cellulose particles was detrimental to the mechanical properties for the resultant composite materials. The ternary cellulose/PHBV/PLA composite materials have some potential applications, such as in packaging materials and automobile inner decoration parts. Furthermore, filling content contributes more to the variations of their mechanical properties than particle size does. Statistical analysis combined with experimental tests provide a new pathway to quantitatively evaluate the effects of multiple variables on a specific property, and figure out the dominant one for the resultant composite materials. PMID:29495315
A cellulose fiber-based diet for screwworm (Diptera: Calliphoridae) larvae.
Chaudhury, M F; Skoda, S R
2007-02-01
A highly absorbent cellulose fiber from recycled paper was tested and compared with a polyacrylate gelling agent, Aquatain, normally used for bulking and solidifying larval rearing medium of screwworm, Cochliomyia hominivorax (Coquerel) (Diptera: Calliphoridae). The absorbent fiber, when mixed with water and dietary ingredients, produced a diet medium of homogeneous texture that supported larval growth and development comparable with the standard gelled diet. Larval and pupal weights from two concentrations of cellulose fiber-based diet were significantly higher than those obtained using gelled diet. The number of pupae per tray, percentage of adult emergence, oviposition, percentage of egg hatch, and adult longevity obtained from the insects reared in the cellulose fiber-based diet were comparable or slightly better than the biological parameters recorded from flies reared in the gelled diet. Moreover, results indicate that a lesser amount of the cellulose fiber-based diet than the normal amount of gelled diet per tray would support normal larval growth. Physical properties and texture of the new diet seem to allow the larvae to move and feed more freely than they do on the semisolid gelled diet, resulting in less wasted diet. The cellulose fiber is biodegradable and inexpensive, whereas the polyacrylate gel polymer is not biodegradable and is relatively expensive. Replacing gel with cellulose fiber in the screwworm larval diet for mass rearing should result in substantial cost savings in material and labor as well as eliminating concern of environmental pollution due to diet waste disposal.
Majoinen, Johanna; Walther, Andreas; McKee, Jason R; Kontturi, Eero; Aseyev, Vladimir; Malho, Jani Markus; Ruokolainen, Janne; Ikkala, Olli
2011-08-08
Herein we report the synthesis of cellulose nanocrystals (CNCs) grafted with poly(acrylic acid) (PAA) chains of different lengths using Cu-mediated surface initiated-controlled radical polymerization (SI-CRP). First, poly(tert-butylacrylate) (PtBA) brushes were synthesized; then, subsequent acid hydrolysis was used to furnish PAA brushes tethered onto the CNC surfaces. The CNCs were chemically modified to create initiator moieties on the CNC surfaces using chemical vapor deposition (CVD) and continued in solvent phase in DMF. A density of initiator groups of 4.6 bromine ester groups/nm(2) on the CNC surface was reached, suggesting a dense functionalization and a promising starting point for the controlled/living radical polymerization. The SI-CRP of tert-butylacrylate proceeded in a well-controlled manner with the aid of added sacrificial initiator, yielding polymer brushes with polydispersity values typically well below 1.12. We calculated the polymer brush grafting density to almost 0.3 chains/nm(2), corresponding to high grafting densities and dense polymer brush formation on the nanocrystals. Successful rapid acid hydrolysis to remove the tert-butyl groups yielded pH-responsive PAA-polyelectrolyte brushes bound to the CNC surface. Individually dispersed rod-like nanoparticles with brushes of PtBA or PAA were clearly visualized by AFM and TEM imaging.
Khan, Zulfequar Ahamad; Tripathi, Rahul; Mishra, Brahmeshwar
2011-12-01
The present work investigates the feasibility of the design of a novel floating elementary osmotic pump tablet (FEOPT) to prolong the gastric residence of a highly water-soluble drug. Diethylcarbamazine citrate (DEC) was chosen as a model drug. The FEOPT consisted of an osmotic core (DEC, mannitol, and hydrophilic polymers) coated with a semipermeable layer (cellulose acetate) and a gas-generating gelling layer (sodium bicarbonate, hydrophilic polymers) followed by a polymeric film (Eudragit RL 30D). The effect of formulation variables such as concentration of polymers, types of diluent, and coat thickness of semipermeable membrane was evaluated in terms of physical parameters, floating lag time, duration of floatation, and in vitro drug release. The Fourier transform infrared and X-ray diffraction analysis were carried out to study the physicochemical changes in the drug excipients powder blend. The integrity of the orifice and polymeric film layer was confirmed from scanning electron microscopy image. All the developed FEOPT showed floating lag time of less than 8 min and floating duration of 24 h. A zero-order drug release could be attained for DEC. The formulations were found to be stable up to 3 months of stability testing at 40°C/75% relative humidity.
El Achaby, Mounir; Kassab, Zineb; Aboulkas, Adil; Gaillard, Cédric; Barakat, Abdellatif
2018-01-01
Red algae is widely available around the world and its exploitation for the production of agar products has become an important industry in recent years. The industrial processing of red algae generates a large quantity of solid fibrous wastes, which constitutes a source of serious environmental problems. In the present work, the utilization of red algae waste as raw material to produce high-quality cellulose nanocrystals (CNC) has been investigated, and the ability of the as-isolated CNC to reinforce polymer has been studied. Red algae waste was chemically treated via alkali, bleaching and acid hydrolysis treatments, in order to obtain pure cellulose microfibers and CNC. The raw waste and the as-extracted cellulosic materials were successively characterized at different stages of treatments using serval analysis techniques. It was found that needle-like shaped CNC were successfully isolated at nanometric scale with diameters and lengths ranged from 5.2±2.9 to 9.1±3.1nm, and from 285.4±36.5 to 315.7±30.3nm, respectively, and the crystallinity index ranged from 81 to 87%, depending on the hydrolysis time (30, 40 and 80min). The as-extracted CNC were used as nanofillers for the production of polyvinyl alcohol (PVA)-based nanocomposite films with improved thermal and tensile properties, as well as optical transparency. It is shown that the addition of 8wt% CNC into the PVA matrix increased the Young's modulus by 215%, the tensile strength by 150%, and the toughness by 45%. Additionally, the nanocomposite films maintained the same transparency level of the neat PVA film (transmittance of ∼90% in the visible region), suggesting that the CNC were dispersed at the nanoscale. Copyright © 2017 Elsevier B.V. All rights reserved.
Thermodynamics of Interaction between Some Cellulose Ethers and SDS by Titration Microcalorimetry.
Singh; Nilsson
1999-05-01
The interaction between certain nonionic cellulose ethers (ethyl hydroxyethyl cellulose and hydroxypropyl methyl cellulose) and sodium dodecyl sulphate (SDS) has been investigated using isothermal titration microcalorimetry at temperatures between 25-50 degrees C. The observed heat flow curves have been interpreted in terms of a plausible mechanism of the interaction of the substituent groups with SDS monomers and clusters. The data have been related to changes occuring in the system at the macro- and microscopic levels with the addition of surfactants and with temperature. The process consists predominantly of polymer-surfactant interactions initially and surfactant-surfactant interactions at the later stages. A phenomenological model of the cooperative interaction (adsorption) process has been derived, and earlier published equilibrium binding data have been used to recover binding constants and Gibbs energy changes for this process. The adsorption enthalpies and entropies have been recovered along with the heat capacity change. The enthalpic cost of confining the nonpolar regions of the polymers in surfactant clusters is high, but the entropy gain from release of hydration shell water molecules as well as increased freedom of movement of these nonpolar regions in the clusters gives the process a strong entropic driving force. The process is entropy-driven initially and converts to being both enthalpy and entropy-driven at high SDS concentrations. An enthalpy-entropy compensation behavior is seen. Strongly negative heat capacity changes have been obtained resulting from the transfer of nonpolar groups from aqueous into nonpolar environments, as well as a reduction of conformational domains that the chains can populate. Changes in these two components cause the heat capacity change to become less negative at the higher binding levels. The system can be classified as exhibiting nonclassical hydrophobic binding at the later stages of binding. Copyright 1999 Academic Press.
Class III peroxidases in cellulose deficient cultured maize cells during cell wall remodelling.
Martínez-Rubio, Romina; Acebes, José Luis; Encina, Antonio; Kärkönen, Anna
2018-02-21
Maize (Zea mays L.) suspension-cultured cells habituated to a cellulose biosynthesis inhibitor 2,6-dichlorobenzonitrile (DCB) have a modified cell wall, in which the reduction in the cellulose content is compensated by a network of highly cross-linked feruloylated arabinoxylans and the deposition of lignin-like polymers. For both arabinoxylan cross-linking and lignin polymerization, class III peroxidases (POXs) have been demonstrated to have a prominent role. For the first time, a comparative study of POX activity and isoforms in control and cellulose-impaired cells has been addressed, also taking into account their cellular distribution in different compartments. Proteins from the spent medium (SM), soluble cellular (SC), ionically (ICW) and covalently bound cell wall protein fractions were assayed for total and specific peroxidase activity by using coniferyl and sinapyl alcohol and ferulic acid as substrates. The isoPOX profile was obtained by isoelectric focusing. POX activity was higher in DCB-habituated than in non-habituated cells in all protein fractions at all cell culture stages. For all substrates assayed, SC and ICW fractions showed higher activity at the early-log growth phase than at the late-log phase. However, the highest POX activity in the spent medium was found at the late-log phase. According to the isoPOX profiles, the highest diversity of isoPOXs was detected in the ICW and SM protein fractions. The latter fraction contained isoPOXs with higher activity in DCB-habituated cells. Some of the isoPOXs detected could be involved in cross-linking of arabinoxylans and in the lignin-like polymer formation in DCB-habituated cells. This article is protected by copyright. All rights reserved.
Engineering Cellulase Enzymes for Bioenergy
NASA Astrophysics Data System (ADS)
Atreya, Meera Elizabeth
Sustainable energy sources, such as biofuels, offer increasingly important alternatives to fossil fuels that contribute less to global climate change. The energy contained within cellulosic biofuels derives from sunlight energy stored in the form of carbon-carbon bonds comprising sugars such as glucose. Second-generation biofuels are produced from lignocellulosic biomass feedstocks, including agricultural waste products and non-food crops like Miscanthus, that contain lignin and the polysaccharides hemicellulose and cellulose. Cellulose is the most abundant biological material on Earth; it is a polymer of glucose and a structural component of plant cell walls. Accessing the sugar is challenging, as the crystalline structure of cellulose resists degradation; biochemical and thermochemical means can be used to depolymerize cellulose. Cellulase enzymes catalyze the biochemical depolymerization of cellulose into glucose. Glucose can be used as a carbon source for growth of a biofuel-producing microorganism. When it converts glucose to a hydrocarbon fuel, this microbe completes the biofuels process of transforming sunlight energy into accessible, chemical energy capable of replacing non-renewable transportation fuels. Due to strong intermolecular interactions between polymer chains, cellulose is significantly more challenging to depolymerize than starch, a more accessible polymer of glucose utilized in first-generation biofuels processes (often derived from corn). While most mammals cannot digest cellulose (dietary fiber), certain fungi and bacteria produce cellulase enzymes capable of hydrolyzing it. These organisms secrete a wide variety of glycoside hydrolase and other classes of enzymes that work in concert. Because cellulase enzymes are slow-acting and expensive to produce, my aim has been to improve the properties of these enzymes as a means to make a cellulosic biofuels process possible that is more efficient and, consequently, more economical than current methods. Protein engineering targets to improve cellulases include reducing enzyme inhibition, improving inter-enzyme synergy, and increasing enzyme thermotolerance. Ameliorating enzyme inhibition could improve catalytic activity and thus the speed of conversion from biomass to fermentable sugars. Improved enzyme synergy could reduce the enzyme loading required to achieve equivalent biomass conversion. Finally, thermostable enzymes could enable more biomass to be processed at a time, due to high temperatures decreasing the viscosity of biomass slurries. A high-temperature enzyme saccharification reaction could also decrease the risk of contamination in the resulting concentrated sugar solution. Throughout my PhD, I have explored research projects broadly across all of these topics, with the most success in addressing the issue of enzyme inhibition. Cellulase enzyme Cel7A is the most abundant cellulase employed by natural systems for cellulose hydrolysis. Cellobiohydrolase enzymes like Cel7A break down cellulose into cellobiose (two glucose molecules). Unfortunately, upon cleavage, this product molecule interferes with continued hydrolysis activity of Cel7A; the strong binding of cellobiose in the active site can obstruct the enzyme from processing down the cellulase chain. This phenomenon, known as product inhibition, is a bottleneck to efficient biomass breakdown. Using insights from computational protein modeling studies, I experimentally generated and tested mutant Cel7A enzymes for improved tolerance to cellobiose. Indeed, this strategy yielded Cel7A enzymes exhibiting reduced product inhibition, including some mutants completely impervious to cellobiose. The improvements in tolerance to cellobiose, however, resulted in an overall reduction of enzyme activity for the mutants tested. Nevertheless, my findings substantiated computational reports with experimental evidence and pinpointed an amino acid residue in the Cel7A product binding site that is of interest for follow-up mutational studies. My goal was to improve the effective catalytic activity of cellulase enzymes in industrially-relevant conditions (such as in the presence of high concentrations of cellobiose or at elevated temperatures). The insights gained from my work on enzyme inhibition may inform future efforts to address this important issue. More efficient enzymes should reduce the amount of these proteins needed to break down cellulose to glucose. This, in turn, should decrease the price of the resulting biofuel making it more cost-competitive with fossil fuels and thus encouraging adoption of renewable transportation fuels that reduce our greenhouse gas emissions.
NASA Astrophysics Data System (ADS)
Prakash, Sai Sivasankaran
2001-11-01
Time-sectioning cryogenic scanning electron microscopy (cryo-SEM) is a unique method of visualizing how the microstructure of liquid coatings evolves during processing. Time-sectioning means rapidly freezing (nearly) identical specimens at successively later stages of the process; doing this requires that coating and drying be well controlled in the dry phase inversion process, and solvents exchange likewise in the wet phase inversion process. With control, frozen specimens are fractured, etched by limited sublimation, sputter-coated, and imaged at temperatures of ca -175°C. The coatings examined were of cellulose acetate, of high and low molecular weights, and polysulfone in mixed solvents and nonsolvents: acetone and water with cellulose acetate undergoing dry phase inversion; and tetrahydrofuran, dimethylacetamide, ethanol with polysulfone undergoing dry-wet phase inversion. All coatings, cast on silicon substrates, were initially homogeneous. The initial compositions of the high and low molecular weight cellulose acetate ternary solutions were "off-critical" and "near-critical", respectively, connoting their proximities to the critical or plait point of the phase diagram. The initial composition of the polysulfone quaternary solution was located near the binodal of the pseudo-ternary phase diagram. It appeared that as the higher molecular weight cellulose acetate coating dries, it nucleates and grows polymer-poor droplets that coalesce into a bicontinuous structure underlying a thin, dense skin. Bicontinuity of structure was verified by stereomicroscopy of the dry sample. The lower molecular weight cellulose acetate coating phase-separates, seemingly spinodally, directly into a bicontinuous structure whose polymer-rich network, stressed by frustrated in-plane shrinkage, ruptures far beneath the skin in some locales to form macrovoids. When, after partial drying, the polysulfone coating was immersed in a bath of water, a nonsolvent, it appeared to swell in thickness as it phase-separates. A dense skin, thinner than a micron, appeared to overlie a two-phase substructure that is punctuated with pear-shaped macrovoids. At early immersion times, this substructure is visibly bicontinuous or open-celled near the bath-side, and dispersion-like (droplets dispersed in a polymeric matrix) or closed-celled near the substrate-side. Moreover, in the bicontinuous regions, length-scales of the individual phases seem to increase across the coating thickness from the bath-side to the substrate-side. After prolonged immersion, the substructure, excluding the macrovoids, is entirely bicontinuous. The bicontinuity presumably results from a combination of spinodal decomposition and nucleation and growth plus coalescence. Quite strikingly, macrovoids are present exclusively in regions where phases are bicontinuous, and are absent where droplets are dispersed in the polymeric matrix. Evidence suggests that macrovoids result from an instability caused by a progressive rupture of polymer-rich links deeper and deeper beneath the skin, aggravated by stress localization in the rupturing network and a buildup of pressure in the polymer-poor phase (the pore space), as suspected by Grobe and Meyer in 1959.
Zhang, Mingliang; Wei, Feng; Guo, Kai; Hu, Zhen; Li, Yuyang; Xie, Guosheng; Wang, Yanting; Cai, Xiwen; Peng, Liangcai; Wang, Lingqiang
2016-01-01
We report isolation and characterization of a fragile culm mutant fc116 that displays reduced mechanical strength caused by decreased cellulose content and altered cell wall structure in rice. Map-based cloning revealed that fc116 was a base substitution mutant (G to A) in a putative beta-1,6-N-acetylglucosaminyltransferase (C2GnT) gene (LOC_Os05g07790, allelic to BC10). This mutation resulted in one amino acid missing within a newly-identified protein motif “R, RXG, RA.” The FC116/BC10 gene was lowly but ubiquitously expressed in the all tissues examined across the whole life cycle of rice, and slightly down-regulated during secondary growth. This mutant also exhibited a significant increase in the content of hemicelluloses and lignins, as well as the content of pentoses (xylose and arabinose). But the content of hexoses (glucose, mannose, and galactose) was decreased in both cellulosic and non-cellulosic (pectins and hemicelluloses) fractions of the mutant. Transcriptomic analysis indicated that the typical genes in the fc116 mutant were up-regulated corresponding to xylan biosynthesis, as well as lignin biosynthesis including p-hydroxyphenyl (H), syringyl (S), and guaiacyl (G). Our results indicate that FC116 has universal function in regulation of the cell wall polymers in rice. PMID:27708650
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tsuzuki, M.; Hagiwara, I.; Shiraishi, N.
1980-12-01
Graft copolymerization of styrene onto cellulose was studied in a homogeneous system (SO/sub 2/(liquid)- diethylamine (DEA)-dimethyl sulfoxide (DMSO) medium)) by ..gamma..-ray mutual irradiation technique. At the same time, homopolymerization of styrene was also examined separately in DMSO, SO/sub 2/-DMSO, DEA-DMSO, and SO/sub 2/-DEA-DMSO media by the same technique. Polymerization of styrene hardly occurs on concentrations above 10 mole SO/sub 2/-DEA complex per mole glucose unit. Maximum percent grafting was obtained in concentrations of 4 mole, after which it decreased rapidly. Total conversion and percent grafting increased with the irradiation time. The value (=0.55) of the slope of the total conversionmore » rate plotted against the dose was only a little higher than the 1/2 which was expected from normal kinetics. No retardation in homopolymerization of styrene in DMSO, SO/sub 2/-DMSO, and DEA-DMSO was evident, while the retardation of homopolymerization in the SO/sub 2/-DEA-DMSO medium was measurable. Sulfur atoms were detected in the polymers obtained in both of SO/sub 2/-DMSO and SO/sub 2/-DEA-DMSO solutions. All of the molecular weights of polymers obtained in the present experiment were very low (3.9 x 10/sup 3/-1.75 x 10/sup 4/).« less
Gierlinger, Notburga; Luss, Saskia; König, Christian; Konnerth, Johannes; Eder, Michaela; Fratzl, Peter
2010-01-01
The functional characteristics of plant cell walls depend on the composition of the cell wall polymers, as well as on their highly ordered architecture at scales from a few nanometres to several microns. Raman spectra of wood acquired with linear polarized laser light include information about polymer composition as well as the alignment of cellulose microfibrils with respect to the fibre axis (microfibril angle). By changing the laser polarization direction in 3° steps, the dependency between cellulose and laser orientation direction was investigated. Orientation-dependent changes of band height ratios and spectra were described by quadratic linear regression and partial least square regressions, respectively. Using the models and regressions with high coefficients of determination (R2 > 0.99) microfibril orientation was predicted in the S1 and S2 layers distinguished by the Raman imaging approach in cross-sections of spruce normal, opposite, and compression wood. The determined microfibril angle (MFA) in the different S2 layers ranged from 0° to 49.9° and was in coincidence with X-ray diffraction determination. With the prerequisite of geometric sample and laser alignment, exact MFA prediction can complete the picture of the chemical cell wall design gained by the Raman imaging approach at the micron level in all plant tissues. PMID:20007198
Cazón, Patricia; Vázquez, Manuel; Velazquez, Gonzalo
2018-09-01
Nowadays consumers are aware of environmental problems. As an alternative to petrochemical polymers for food packaging, researchers have been focused on biopolymeric materials as raw material. The aim of this study was to evaluate mechanical properties (toughness, burst strength and distance to burst), water adsorption, light-barrier properties and transparency of composite films based on cellulose, glycerol and polyvinyl alcohol. Scanning electron microscopy, spectral analysis (FT-IR and UV-VIS-NIR) and differential scanning calorimetry were performed to explain the morphology, structural and thermal properties of the films. Results showed that polyvinyl alcohol enhances the toughness of films up to 44.30 MJ/m 3 . However, toughness decreases when glycerol concentration is increased (from 23.41 to 10.55 MJ/m 3 ). Water adsorption increased with increasing polyvinyl alcohol concentration up to 222%. Polyvinyl alcohol increased the film thickness. The films showed higher burst strength (up to 12014 g) than other biodegradable films. The films obtained have optimal values of transparency like those values of synthetic polymers. Glycerol produced a UV protective effect in the films, an important effect for food packaging to prevent lipid oxidative deterioration. Results showed that it is feasible to obtain cellulose-glycerol-polyvinyl alcohol composite films with improved properties. Copyright © 2018 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Abiddin, Jamal Farghali Bin Zainal; Ahmad, Azizah Hanom; Institute of Science, Universiti Teknologi MARA, 40450 Shah Alam, Selangor D.E.
2015-08-28
Sodium ion (Na{sup +}) based solid polymer electrolyte (SPE) has been prepared using solution cast technique with distilled water as solvent and Methylcellulose (MC) as a polymer host. Methylcellulose polymer was chosen as the polymer host due to the abundance of lone pair electrons in the carbonyl and C-O-C constituents, which in turn provide multiple hopping sites for the Na{sup +} conducting ions. Variable compositions of sodium iodide (NaI) salt were prepared to investigate the optimum MC-NaI weight ratio. Results from Electrical Impedance Spectroscopy (EIS) technique show that pure methylcellulose has a low conductivity of 3.61 × 10{sup −11} S/cm.Themore » conductivity increases as NaI content increases up to optimum NaIcomposition of 40 wt%, which yields an average conductivity of 2.70 × 10{sup −5} S/cm.« less
NASA Astrophysics Data System (ADS)
Abiddin, Jamal Farghali Bin Zainal; Ahmad, Azizah Hanom
2015-08-01
Sodium ion (Na+) based solid polymer electrolyte (SPE) has been prepared using solution cast technique with distilled water as solvent and Methylcellulose (MC) as a polymer host. Methylcellulose polymer was chosen as the polymer host due to the abundance of lone pair electrons in the carbonyl and C-O-C constituents, which in turn provide multiple hopping sites for the Na+ conducting ions. Variable compositions of sodium iodide (NaI) salt were prepared to investigate the optimum MC-NaI weight ratio. Results from Electrical Impedance Spectroscopy (EIS) technique show that pure methylcellulose has a low conductivity of 3.61 × 10-11 S/cm.The conductivity increases as NaI content increases up to optimum NaIcomposition of 40 wt%, which yields an average conductivity of 2.70 × 10-5 S/cm.
Zhu, Baolei; Merindol, Remi; Benitez, Alejandro J; Wang, Baochun; Walther, Andreas
2016-05-04
Natural composites are hierarchically structured by combination of ordered colloidal and molecular length scales. They inspire future, biomimetic, and lightweight nanocomposites, in which extraordinary mechanical properties are in reach by understanding and mastering hierarchical structure formation as tools to engineer multiscale deformation mechanisms. Here we describe a hierarchically self-assembled, cholesteric nanocomposite with well-defined colloid-based helical structure and supramolecular hydrogen bonds engineered on the molecular level in the polymer matrix. We use reversible addition-fragmentation transfer polymerization to synthesize well-defined hydrophilic, nonionic polymers with a varying functionalization density of 4-fold hydrogen-bonding ureidopyrimidinone (UPy) motifs. We show that these copolymers can be coassembled with cellulose nanocrystals (CNC), a sustainable, stiff, rod-like reinforcement, to give ordered cholesteric phases with characteristic photonic stop bands. The dimensions of the helical pitch are controlled by the ratio of polymer/CNC, confirming a smooth integration into the colloidal structure. With respect to the effect of the supramolecular motifs, we demonstrate that those regulate the swelling when exposing the biomimetic hybrids to water, and they allow engineering the photonic response. Moreover, the amount of hydrogen bonds and the polymer fraction are decisive in defining the mechanical properties. An Ashby plot comparing previous ordered CNC-based nanocomposites with our new hierarchical ones reveals that molecular engineering allows us to span an unprecedented mechanical property range from highest inelastic deformation (strain up to ∼13%) to highest stiffness (E ∼ 15 GPa) and combinations of both. We envisage that further rational design of the molecular interactions will provide efficient tools for enhancing the multifunctional property profiles of such bioinspired nanocomposites.
NASA Astrophysics Data System (ADS)
Hidema, R.
2014-08-01
In order to study the effects of extensional viscosities on turbulent drag reduction, experimental studies using two-dimensional turbulence have been made. Anisotropic structures and variations of energy transfer induced by polymers are considered. Polyethyleneoxide and hydroxypropyl cellulose having different flexibility, which is due to different characteristics of extensional viscosity, are added to 2D turbulence. Variations of the turbulence were visualized by interference patterns of 2D flow, and were analysed by an image processing. The effects of polymers on turbulence in the streamwise and normal directions were also analysed by 2D Fourier transform. In addition, characteristic scales in 2D turbulence were analysed by wavelet transform.
Kinetics of shear-induced gel deswelling/solvent release.
Zeo, Undina; Tarabukina, Elena; Budtova, Tatiana
2005-11-02
The kinetics of shear-induced deswelling of gel particles based on synthetic (sodium polyacrylate) and natural (alginate) polymers was studied by rheo-optical technique. A swollen spherical gel particle of 100+/-50 microm diameter was placed in silicone oil and the evolution of the gel size as a function of time and shear rate was monitored. Different aqueous polymer solutions were used as synthetic gel solvent: polyvinylpyrrolidone, hydroxypropyl cellulose and glucose-based polymer. The interfacial tension (gel solvent)/(silicone oil), gel degree of swelling, solvent quality and viscosity are the main parameters influencing the kinetics of shear-induced gel deswelling. The kinetics of gel volume loss was approximated by a modified Weibull equation.
Solution-Based 3D Printing of Polymers of Intrinsic Microporosity.
Zhang, Fengyi; Ma, Yao; Liao, Jianshan; Breedveld, Victor; Lively, Ryan P
2018-05-28
Current additive manufacturing methods have significant limitations in the classes of compatible polymers. Many polymers of significant technological interest cannot currently be 3D printed. Here, a generalizable method for 3D printing of viscous tenary polymer solutions (polymer/solvent/nonsolvent) is applied to both "intrinsically porous" (a polymer of intrinsic microporosity, PIM-1) and "intrinsically nonporous" (cellulose acetate) polymers. Successful ternary ink formulations require balancing of solution thermodynamics (phase separation), mass transfer (solvent evaporation), and rheology. As a demonstration, a microporous polymer (PIM-1) incompatible with current additive manufacturing technologies is 3D printed into a high-efficiency mass transfer contactor exhibiting hierarchical porosity ranging from sub-nanometer to millimeter pores. Short contactors (1.27 cm) can fully purify (<1 ppm) toluene vapor (1000 ppm) in N 2 gas for 1.7 h, which is six times longer than PIM-1 in traditional structures, and more than 4000 times the residence time of gas in the contactor. This solution-based additive manufacturing approach greatly extends the range of 3D-printable materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Matthysse, Ann G; Marry, Mazz; Krall, Leonard; Kaye, Mitchell; Ramey, Bronwyn E; Fuqua, Clay; White, Alan R
2005-09-01
Agrobacterium tumefaciens growing in liquid attaches to the surface of tomato and Arabidopsis thaliana roots, forming a biofilm. The bacteria also colonize roots grown in sterile quartz sand. Attachment, root colonization, and biofilm formation all were markedly reduced in celA and chvB mutants, deficient in production of cellulose and cyclic beta-(1,2)-D-glucans, respectively. We have identified two genes (celG and cell) in which mutations result in the overproduction of cellulose as judged by chemical fractionation and methylation analysis. Wild-type and chvB mutant strains carrying a cDNA clone of a cellulose synthase gene from the marine urochordate Ciona savignyi also overproduced cellulose. The overproduction in a wild-type strain resulted in increased biofilm formation on roots, as evaluated by light microscopy, and levels of root colonization intermediate between those of cellulose-minus mutants and the wild type. Overproduction of cellulose by a nonattaching chvB mutant restored biofilm formation and bacterial attachment in microscopic and viable cell count assays and partially restored root colonization. Although attachment to plant surfaces was restored, overproduction of cellulose did not restore virulence in the chvB mutant strain, suggesting that simple bacterial binding to plant surfaces is not sufficient for pathogenesis.
Effect of coupling agents on the weathering characteristics of bio-fiber composites
USDA-ARS?s Scientific Manuscript database
Bio-fiber polymer composites (BFPC) are composite materials made from a thermoplastic or thermoset resin (substrate) with cellulosic fibers as fillers or reinforcement. BFPC have shown a significant growth in the last decade as a building product, automotive parts, and landscaping products. BFPC com...
NASA Technical Reports Server (NTRS)
Senturia, S. D.
1977-01-01
Polymer responses to a variety of smouldering sources, including cellulose, acrylic, urethane, polyvinyl chloride, and wool were investigated. A suitable trapping system for combustion products was developed and a charge flow transistor was fabricated to monitor the transverse or sheet resistance of a thin film.
Roger M. Rowell; Roger Pettersen; James S. Han; Jeffrey S. Rowell; Mandla A. Tshabalala
2005-01-01
In chemical terms, wood is best defined as a three-dimensional biopolymer composite composed of an interconnected network of cellulose, hemicelluloses, and lignin with minor amounts of extractives and inorganics. The major chemical component of a living tree is water, but on a dryweight basis, all wood cell walls consist mainly of sugar-based polymers (carbohydrates,...
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
Preliminary Modulus and Breakage Calculations on Cellulose Models
USDA-ARS?s Scientific Manuscript database
The Young’s modulus of polymers can be calculated by stretching molecular models with the computer. The molecule is stretched and the derivative of the changes in stored potential energy for several displacements, divided by the molecular cross-section area, is the stress. The modulus is the slope o...
Relating nanoindentation to macroindentation of wood
Robert J. Moon; Joseph E. Jakes; Jim F. Beecher; Charles R. Frihart; Donald S. Stone
2009-01-01
Wood has several levels of hierarchical structure, spanning from the configuration of growth-rings down to the configuration of the base polymers (cellulose, hemicellulose, and lignin). The bulk properties of wood result from the culmination of interactions over all length scales. Gaps presently exist in the fundamental knowledge relating the contribution of wood...
Hydrogenation of biomass extracts for production of chemicals concurrently from sugars and lignin
USDA-ARS?s Scientific Manuscript database
The efficient conversion of biomass to commodity or specialty chemicals is critical to the success of the biorefinery concept. Biomass consists largely of the three interwoven polymers cellulose, hemicellulose, and lignin [1]. A key step toward utilization is the pretreatment of biomass which includ...
NASA Astrophysics Data System (ADS)
Jha, Praveen Kumar; Mahto, Vikas; Saxena, Vinod Kumar
2018-05-01
A new type of oil-in-water (O/W) Pickering emulsion systems, which were prepared by polymers such as xanthan gum, carboxymethyl cellulose (CMC), and sodium lignosulfonate have been investigated for their properties as multifunctional emulsion muds with respect to rheological control and filtration control properties. Diesel oil was used as dispersed phase and KCl-brine as continuous phase in the developed emulsions. Initially, rheological parameters like apparent viscosity, plastic viscosity, gel strength, and filtration control properties were measured using recommended practices. Emulsion stability was analyzed using steady state shear stress-shear rate and oscillatory (dynamic) rheological measurement techniques. The emulsions were found to exhibit shear-thinning (pseudoplastic) behavior. Experiments conducted for oscillatory rheological measurements have shown that emulsions are stable as per the stability criteria G' (elastic modulus) > G'' (loss modulus) and both are independent of changing ω (Frequency). These fluids have shown stable properties upto 70°C which shows that they can be used as drilling muds for drilling oil and gas wells.
Recent advances in green hydrogels from lignin: a review.
Thakur, Vijay Kumar; Thakur, Manju Kumari
2015-01-01
Recently, biorenewable polymers from different natural resources have attracted a greater attention of the research community for different applications starting from biomedical to automotive. Lignin is the second most abundant non-food biomass next to cellulose in the category of biorenewable polymers and is abundantly available as byproduct of several industries involved in paper making, ethanol production, etc. The development of various green materials from lignin, which is most often considered as waste, is therefore of prime interest from environmental and economic points of view. Over the last few years, little studies have been made into the use of lignin as an indispensable component in the hydrogels. This article provides an overview of the research work carried out in the last few years on lignin based hydrogels. This article comprehensively reviews the potential efficacy of lignin in biopolymer based green hydrogels with particular emphasis on synthesis, characterization and applications. In this article, several examples of hydrogels synthesized using different types of lignin are discussed to illustrate the state of the art in the use of lignin.
Schell, William J.
1979-01-01
A dry, fabric supported, polymeric gas separation membrane, such as cellulose acetate, is prepared by casting a solution of the polymer onto a shrinkable fabric preferably formed of synthetic polymers such as polyester or polyamide filaments before washing, stretching or calendering (so called griege goods). The supported membrane is then subjected to gelling, annealing, and drying by solvent exchange. During the processing steps, both the fabric support and the membrane shrink a preselected, controlled amount which prevents curling, wrinkling or cracking of the membrane in flat form or when spirally wound into a gas separation element.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
1983-01-01
Descriptions are given of 42 processes which use biomass to produce chemical products. Marketing and economic background, process description, flow sheets, costs, major equipment, and availability of technology are given for each of the 42 processes. Some of the chemicals discussed are: ethanol, ethylene, acetaldehyde, butanol, butadiene, acetone, citric acid, gluconates, itaconic acid, lactic acid, xanthan gum, sorbitol, starch polymers, fatty acids, fatty alcohols, glycerol, soap, azelaic acid, perlargonic acid, nylon-11, jojoba oil, furfural, furfural alcohol, tetrahydrofuran, cellulose polymers, products from pulping wastes, and methane. Processes include acid hydrolysis, enzymatic hydrolysis, fermentation, distillation, Purox process, and anaerobic digestion.
Sharma, Rita; Cao, Peijian; Jung, Ki-Hong; Sharma, Manoj K.; Ronald, Pamela C.
2013-01-01
Glycoside hydrolases (GH) catalyze the hydrolysis of glycosidic bonds in cell wall polymers and can have major effects on cell wall architecture. Taking advantage of the massive datasets available in public databases, we have constructed a rice phylogenomic database of GHs (http://ricephylogenomics.ucdavis.edu/cellwalls/gh/). This database integrates multiple data types including the structural features, orthologous relationships, mutant availability, and gene expression patterns for each GH family in a phylogenomic context. The rice genome encodes 437 GH genes classified into 34 families. Based on pairwise comparison with eight dicot and four monocot genomes, we identified 138 GH genes that are highly diverged between monocots and dicots, 57 of which have diverged further in rice as compared with four monocot genomes scanned in this study. Chromosomal localization and expression analysis suggest a role for both whole-genome and localized gene duplications in expansion and diversification of GH families in rice. We examined the meta-profiles of expression patterns of GH genes in twenty different anatomical tissues of rice. Transcripts of 51 genes exhibit tissue or developmental stage-preferential expression, whereas, seventeen other genes preferentially accumulate in actively growing tissues. When queried in RiceNet, a probabilistic functional gene network that facilitates functional gene predictions, nine out of seventeen genes form a regulatory network with the well-characterized genes involved in biosynthesis of cell wall polymers including cellulose synthase and cellulose synthase-like genes of rice. Two-thirds of the GH genes in rice are up regulated in response to biotic and abiotic stress treatments indicating a role in stress adaptation. Our analyses identify potential GH targets for cell wall modification. PMID:23986771
Li, Meng; Wang, Jun; Yang, Yuezhou; Xie, Guanghui
2016-05-01
Jerusalem artichoke (JA) has been known as a potential nonfood feedstock for biofuels. Based on systems analysis of total 59 accessions, both soluble sugar and ash could positively affect biomass digestibility after dilute sodium hydroxide pretreatment (A). In this study, one representative accession (HEN-3) was used to illustrate its enzymatic digestibility with pretreatments of ultrasonic-assisted dilute sodium hydroxide (B), alkaline peroxide (C), and ultrasonic-assisted alkaline peroxide (D). Pretreatment D exhibited the highest hexose release rate (79.4%) and total sugar yield (10.4 g/L), which were 2.4 and 2.6 times higher, respectively, than those of the control. The analysis of cellulose crystalline index (CrI), cellulose degree of polymerization (DP), thermal behavior and SEM suggested that alkali-based pretreatments could distinctively extract lignin and pectin polymers, leading to significant alterations of cellulose CrI and DP for high biomass saccharification. Additionally, hydrogen peroxide (H2O2) could significant reduce the generation of fermentation inhibitors during alkali-based pretreatments. Copyright © 2016 Elsevier Ltd. All rights reserved.
Statistical thermodynamics unveils the dissolution mechanism of cellobiose.
Nicol, Thomas W J; Isobe, Noriyuki; Clark, James H; Shimizu, Seishi
2017-08-30
In the study of the cellulose dissolution mechanism opinion is still divided. Here, the solution interaction components of the most prominent hypotheses for the driving force of cellulose dissolution were evaluated quantitatively. Combining a rigorous statistical thermodynamic theory and cellobiose solubility data in the presence of chloride salts, whose cations progress in the Hofmeister series (KCl, NaCl, LiCl and ZnCl 2 ), we have shown that cellobiose solubilization is driven by the preferential accumulation of salts around the solutes which is stronger than cellobiose hydration. Yet contrary to the classical chaotropy hypothesis, increasing salt concentration leads to cellobiose dehydration in the presence of the strongest solubilizer ZnCl 2 . However, thanks to cellobiose dehydration, cellobiose-salt interaction still remains preferential despite weakening salt accumulation. Based on such insights, the previous hypotheses based on hydrophobicity and polymer charging have also been evaluated quantitatively. Thus, our present study successfully paved a way towards identifying the basic driving forces for cellulose solubilization in a quantitative manner for the first time. When combined with unit additivity methods this quantitative information could lead to a full understanding of cellulose solubility.
Hambardzumyan, Arayik; Foulon, Laurence; Chabbert, Brigitte; Aguié-Béghin, Véronique
2012-12-10
Novel nanocomposite coatings composed of cellulose nanocrystals (CNCs) and lignin (either synthetic or fractionated from spruce and corn stalks) were prepared without chemical modification or functionalization (via covalent attachment) of one of the two biopolymers. The spectroscopic properties of these coatings were investigated by UV-visible spectrophotometry and spectroscopic ellipsometry. When using the appropriate weight ratio of CNC/lignin (R), these nanocomposite systems exhibited high-performance optical properties, high transmittance in the visible spectrum, and high blocking in the UV spectrum. Atomic force microscopy analysis demonstrated that these coatings were smooth and homogeneous, with visible dispersed lignin nodules in a cellulosic matrix. It was also demonstrated that the introduction of nanoparticles into the medium increases the weight ratio and the CNC-specific surface area, which allows better dispersion of the lignin molecules throughout the solid film. Consequently, the larger molecular expansion of these aromatic polymers on the surface of the cellulosic nanoparticles dislocates the π-π aromatic aggregates, which increases the extinction coefficient and decreases the transmittance in the UV region. These nanocomposite coatings were optically transparent at visible wavelengths.
Modification of nanofibrillated cellulose using amphiphilic block-structured galactoglucomannans.
Lozhechnikova, Alina; Dax, Daniel; Vartiainen, Jari; Willför, Stefan; Xu, Chunlin; Österberg, Monika
2014-09-22
Nanofibrillated cellulose (NFC) and hemicelluloses have shown to be highly promising renewable components both as barrier materials and in novel biocomposites. However, the hydrophilic nature of these materials restricts their use in some applications. In this work, the usability of modified O-acetyl galactoglucomannan (GGM) for modification of NFC surface properties was studied. Four GGM-block-structured, amphiphilic derivatives were synthesized using either fatty acids or polydimethylsiloxane as hydrophobic tails. The adsorption of these GGM derivatives was consecutively examined in aqueous solution using a quartz crystal microbalance with dissipation monitoring (QCM-D). It was found that the hydrophobic tails did not hinder adsorption of the GGM derivatives to cellulose, which was concluded to be due to the presence of the native GGM-block with high affinity to cellulose. The layer properties of the adsorbed block-co-polymers were discussed and evaluated. Self-standing NFC films were further prepared and coated with the GGM derivatives and the effect of the surface modification on wetting properties and oxygen permeability (OP) of the modified films was assessed. Copyright © 2014 Elsevier Ltd. All rights reserved.
Choong, Ferdinand X; Bäck, Marcus; Fahlén, Sara; Johansson, Leif Bg; Melican, Keira; Rhen, Mikael; Nilsson, K Peter R; Richter-Dahlfors, Agneta
2016-01-01
Extracellular matrix (ECM) is the protein- and polysaccharide-rich backbone of bacterial biofilms that provides a defensive barrier in clinical, environmental and industrial settings. Understanding the dynamics of biofilm formation in native environments has been hindered by a lack of research tools. Here we report a method for simultaneous, real-time, in situ detection and differentiation of the Salmonella ECM components curli and cellulose, using non-toxic, luminescent conjugated oligothiophenes (LCOs). These flexible conjugated polymers emit a conformation-dependent fluorescence spectrum, which we use to kinetically define extracellular appearance of curli fibres and cellulose polysaccharides during bacterial growth. The scope of this technique is demonstrated by defining biofilm morphotypes of Salmonella enterica serovars Enteritidis and Typhimurium, and their isogenic mutants in liquid culture and on solid media, and by visualising the ECM components in native biofilms. Our reported use of LCOs across a number of platforms, including intracellular cellulose production in eukaryotic cells and in infected tissues, demonstrates the versatility of this optotracing technology, and its ability to redefine biofilm research.
Choong, Ferdinand X; Bäck, Marcus; Fahlén, Sara; Johansson, Leif BG; Melican, Keira; Rhen, Mikael; Nilsson, K Peter R; Richter-Dahlfors, Agneta
2016-01-01
Extracellular matrix (ECM) is the protein- and polysaccharide-rich backbone of bacterial biofilms that provides a defensive barrier in clinical, environmental and industrial settings. Understanding the dynamics of biofilm formation in native environments has been hindered by a lack of research tools. Here we report a method for simultaneous, real-time, in situ detection and differentiation of the Salmonella ECM components curli and cellulose, using non-toxic, luminescent conjugated oligothiophenes (LCOs). These flexible conjugated polymers emit a conformation-dependent fluorescence spectrum, which we use to kinetically define extracellular appearance of curli fibres and cellulose polysaccharides during bacterial growth. The scope of this technique is demonstrated by defining biofilm morphotypes of Salmonella enterica serovars Enteritidis and Typhimurium, and their isogenic mutants in liquid culture and on solid media, and by visualising the ECM components in native biofilms. Our reported use of LCOs across a number of platforms, including intracellular cellulose production in eukaryotic cells and in infected tissues, demonstrates the versatility of this optotracing technology, and its ability to redefine biofilm research. PMID:28721253
Membrane materials for storing biological samples intended for comparative nanotoxicological testing
NASA Astrophysics Data System (ADS)
Metelkin, A.; Kuznetsov, D.; Kolesnikov, E.; Chuprunov, K.; Kondakov, S.; Osipov, A.; Samsonova, J.
2015-11-01
The study is aimed at identifying the samples of most promising membrane materials for storing dry specimens of biological fluids (Dried Blood Spots, DBS technology). Existing sampling systems using cellulose fiber filter paper have a number of drawbacks such as uneven distribution of the sample spot, dependence of the spot spreading area on the individual biosample properties, incomplete washing-off of the sample due to partially inconvertible sorption of blood components on cellulose fibers, etc. Samples of membrane materials based on cellulose, polymers and glass fiber with applied biosamples were studied using methods of scanning electron microscopy, FT-IR spectroscopy and surface-wetting measurement. It was discovered that cellulose-based membrane materials sorb components of biological fluids inside their structure, while membranes based on glass fiber display almost no interaction with the samples and biological fluid components dry to films in the membrane pores between the structural fibers. This characteristic, together with the fact that membrane materials based on glass fiber possess sufficient strength, high wetting properties and good storage capacity, attests them as promising material for dry samples of biological fluids storage systems.
Shape and size engineered cellulosic nanomaterials as broad spectrum anti-microbial compounds.
Sharma, Priyanka R; Kamble, Sunil; Sarkar, Dhiman; Anand, Amitesh; Varma, Anjani J
2016-06-01
Oxidized celluloses have been used for decades as antimicrobial wound gauzes and surgical cotton. We now report the successful synthesis of a next generation narrow size range (25-35nm) spherical shaped nanoparticles of 2,3,6-tricarboxycellulose based on cellulose I structural features, for applications as new antimicrobial materials. This study adds to our previous study of 6-carboxycellulose. A wide range of bacteria such as Escherichia coli, Staphloccocus aureus, Bacillus subtilis and Mycobacterium tuberculosis (non-pathogenic as well as pathogenic strains) were affected by these polymers in in vitro studies. Activity against Mycobacteria were noted at high concentrations (MIC99 values 250-1000μg/ml, as compared to anti-TB drug Isoniazid 0.3μg/ml). However, the broad spectrum activity of oxidized celluloses and their nanoparticles against a wide range of bacteria, including Mycobacteria, show that these materials are promising new biocompatible and biodegradable drug delivery vehicles wherein they can play the dual role of being a drug encapsulant as well as a broad spectrum anti-microbial and anti-TB drug. Copyright © 2016. Published by Elsevier B.V.
Glucose biosensors with enzyme entrapped in polymer coating.
Yang, S; Atanasov, P; Wilkins, E
1995-01-01
The pursuit of reliable biosensors for measuring glucose levels has been ongoing for decades. Their importance lies partly in the development of the implantable artificial pancrease, which can be used to deliver insulin to diabetics without the need to test glucose levels externally, with automatic delivery based on physiologic demand. Glucose sensors can also be used in short-term monitoring of glucose levels in hospitals and clinical laboratories. Three types of glucose biosensors were studied. All were based on a two-electrode system: an insulated platinum wire as a hydrogen peroxide electrode, and a silver wire twisted around the platinum wire as both a reference and a counter electrode. Each was coated with the enzyme glucose oxidase entrapped in a polymer matrix of cellulose acetate (CA) or poly 2-hydroxyethyl methacrylate (HEMA), then dip-coated by an additional polymer coating of polyvinylchloride (PVC), polyurethane (PU), or HEMA. The experiments were designed mainly to study the effectiveness of polymer coatings as diffusion-limiting membranes. The effect of each coating on the linear response to glucose concentration was examined. It was shown that additional (multiple) coatings can increase the linearity of the sensor response. The best results were obtained when the sensor was PVC-dip-coated three times. This preparation had a linear response up to 600 mg/DL glucose concentration. The sensors coated with PU and HEMA have linearity up to 280 and 240 mg/DL glucose concentrations, respectively. It was also shown that the coatings reduce interference from certain body chemicals.
Recyclable organic solar cells on cellulose nanocrystal substrates
Zhou, Yinhua; Fuentes-Hernandez, Canek; Khan, Talha M.; Liu, Jen-Chieh; Hsu, James; Shim, Jae Won; Dindar, Amir; Youngblood, Jeffrey P.; Moon, Robert J.; Kippelen, Bernard
2013-01-01
Solar energy is potentially the largest source of renewable energy at our disposal, but significant advances are required to make photovoltaic technologies economically viable and, from a life-cycle perspective, environmentally friendly, and consequently scalable. Cellulose nanomaterials are emerging high-value nanoparticles extracted from plants that are abundant, renewable, and sustainable. Here, we report on the first demonstration of efficient polymer solar cells fabricated on optically transparent cellulose nanocrystal (CNC) substrates. The solar cells fabricated on the CNC substrates display good rectification in the dark and reach a power conversion efficiency of 2.7%. In addition, we demonstrate that these solar cells can be easily separated and recycled into their major components using low-energy processes at room temperature, opening the door for a truly recyclable solar cell technology. Efficient and easily recyclable organic solar cells on CNC substrates are expected to be an attractive technology for sustainable, scalable, and environmentally-friendly energy production. PMID:23524333
Pretreatment methods for bioethanol production.
Xu, Zhaoyang; Huang, Fang
2014-09-01
Lignocellulosic biomass, such as wood, grass, agricultural, and forest residues, are potential resources for the production of bioethanol. The current biochemical process of converting biomass to bioethanol typically consists of three main steps: pretreatment, enzymatic hydrolysis, and fermentation. For this process, pretreatment is probably the most crucial step since it has a large impact on the efficiency of the overall bioconversion. The aim of pretreatment is to disrupt recalcitrant structures of cellulosic biomass to make cellulose more accessible to the enzymes that convert carbohydrate polymers into fermentable sugars. This paper reviews several leading acidic, neutral, and alkaline pretreatments technologies. Different pretreatment methods, including dilute acid pretreatment (DAP), steam explosion pretreatment (SEP), organosolv, liquid hot water (LHW), ammonia fiber expansion (AFEX), soaking in aqueous ammonia (SAA), sodium hydroxide/lime pretreatments, and ozonolysis are intensively introduced and discussed. In this minireview, the key points are focused on the structural changes primarily in cellulose, hemicellulose, and lignin during the above leading pretreatment technologies.
Liu, Wei; Mu, Wei; Liu, Mengjie; Zhang, Xiaodan; Cai, Hongli; Deng, Yulin
2014-01-01
The current polymer-exchange membrane fuel cell technology cannot directly use biomass as fuel. Here we present a solar-induced hybrid fuel cell that is directly powered with natural polymeric biomasses, such as starch, cellulose, lignin, and even switchgrass and wood powders. The fuel cell uses polyoxometalates as the photocatalyst and charge carrier to generate electricity at low temperature. This solar-induced hybrid fuel cell combines some features of solar cells, fuel cells and redox flow batteries. The power density of the solar-induced hybrid fuel cell powered by cellulose reaches 0.72 mW cm(-2), which is almost 100 times higher than cellulose-based microbial fuel cells and is close to that of the best microbial fuel cells reported in literature. Unlike most cell technologies that are sensitive to impurities, the cell reported in this study is inert to most organic and inorganic contaminants present in the fuels.
Recyclable organic solar cells on cellulose nanocrystal substrates.
Zhou, Yinhua; Fuentes-Hernandez, Canek; Khan, Talha M; Liu, Jen-Chieh; Hsu, James; Shim, Jae Won; Dindar, Amir; Youngblood, Jeffrey P; Moon, Robert J; Kippelen, Bernard
2013-01-01
Solar energy is potentially the largest source of renewable energy at our disposal, but significant advances are required to make photovoltaic technologies economically viable and, from a life-cycle perspective, environmentally friendly, and consequently scalable. Cellulose nanomaterials are emerging high-value nanoparticles extracted from plants that are abundant, renewable, and sustainable. Here, we report on the first demonstration of efficient polymer solar cells fabricated on optically transparent cellulose nanocrystal (CNC) substrates. The solar cells fabricated on the CNC substrates display good rectification in the dark and reach a power conversion efficiency of 2.7%. In addition, we demonstrate that these solar cells can be easily separated and recycled into their major components using low-energy processes at room temperature, opening the door for a truly recyclable solar cell technology. Efficient and easily recyclable organic solar cells on CNC substrates are expected to be an attractive technology for sustainable, scalable, and environmentally-friendly energy production.
Bioinspired Bouligand cellulose nanocrystal composites: a review of mechanical properties
NASA Astrophysics Data System (ADS)
Natarajan, Bharath; Gilman, Jeffrey W.
2017-12-01
The twisted plywood, or Bouligand, structure is the most commonly observed microstructural motif in natural materials that possess high mechanical strength and toughness, such as that found in bone and the mantis shrimp dactyl club. These materials are isotropically toughened by a low volume fraction of soft, energy-dissipating polymer and by the Bouligand structure itself, through shear wave filtering and crack twisting, deflection and arrest. Cellulose nanocrystals (CNCs) are excellent candidates for the bottom-up fabrication of these structures, as they naturally self-assemble into `chiral nematic' films when cast from solutions and possess outstanding mechanical properties. In this article, we present a review of the fabrication techniques and the corresponding mechanical properties of Bouligand biomimetic CNC nanocomposites, while drawing comparison to the performance standards set by tough natural composite materials. This article is part of a discussion meeting issue `New horizons for cellulose nanotechnology'.
NASA Astrophysics Data System (ADS)
Liu, Wei; Mu, Wei; Liu, Mengjie; Zhang, Xiaodan; Cai, Hongli; Deng, Yulin
2014-02-01
The current polymer-exchange membrane fuel cell technology cannot directly use biomass as fuel. Here we present a solar-induced hybrid fuel cell that is directly powered with natural polymeric biomasses, such as starch, cellulose, lignin, and even switchgrass and wood powders. The fuel cell uses polyoxometalates as the photocatalyst and charge carrier to generate electricity at low temperature. This solar-induced hybrid fuel cell combines some features of solar cells, fuel cells and redox flow batteries. The power density of the solar-induced hybrid fuel cell powered by cellulose reaches 0.72 mW cm-2, which is almost 100 times higher than cellulose-based microbial fuel cells and is close to that of the best microbial fuel cells reported in literature. Unlike most cell technologies that are sensitive to impurities, the cell reported in this study is inert to most organic and inorganic contaminants present in the fuels.
Nanotechnology : emerging applications of cellulose-based green magnetic nanocomposites
Tao Wang; Zhiyong Cai; Lei Liu; Ilker S. Bayer; Abhijit Biswas
2010-01-01
In recent years, a new type of nanocomposite â cellulose based hybrid nanocomposites, which adopts cellulose nanofibers as matrices, has been intensively developed. Among these materials, hybrid nanocomposites consisting of cellulosic fibers and magnetic nanoparticles have recently attracted much attention due to their potential novel applications in biomedicine,...
Cellulose microfibril structure: inspirations from plant diversity
NASA Astrophysics Data System (ADS)
Roberts, A. W.
2018-03-01
Cellulose microfibrils are synthesized at the plasma membrane by cellulose synthase catalytic subunits that associate to form cellulose synthesis complexes. Variation in the organization of these complexes underlies the variation in cellulose microfibril structure among diverse organisms. However, little is known about how the catalytic subunits interact to form complexes with different morphologies. We are using an evolutionary approach to investigate the roles of different catalytic subunit isoforms in organisms that have rosette-type cellulose synthesis complexes.
Deng, Ying; Nagachar, Nivedita; Fang, Lin; ...
2015-03-19
Gluconacetobacter hansenii, a Gram-negative bacterium, produces and secrets highly crystalline cellulose into growth medium, and has long been used as a model system for studying cellulose synthesis in higher plants. Cellulose synthesis involves the formation of β-1,4 glucan chains via the polymerization of glucose units by a multi-enzyme cellulose synthase complex (CSC). These glucan chains assemble into ordered structures including crystalline microfibrils. AcsA is the catalytic subunit of the cellulose synthase enzymes in the CSC, and AcsC is required for the secretion of cellulose. However, little is known about other proteins required for the assembly of crystalline cellulose. To addressmore » this question, we visually examined cellulose pellicles formed in growth media of 763 individual colonies of G. hansenii generated via Tn5 transposon insertion mutagenesis, and identified 85 that produced cellulose with altered morphologies. X-ray diffraction analysis of these 85 mutants identified two that produced cellulose with significantly lower crystallinity than wild type. The gene disrupted in one of these two mutants encoded a lysine decarboxylase and that in the other encoded an alanine racemase. Solid-state NMR analysis revealed that cellulose produced by these two mutants contained increased amounts of non-crystalline cellulose and monosaccharides associated with non-cellulosic polysaccharides as compared to the wild type. Monosaccharide analysis detected higher percentages of galactose and mannose in cellulose produced by both mutants. Field emission scanning electron microscopy showed that cellulose produced by the mutants was unevenly distributed, with some regions appearing to contain deposition of non-cellulosic polysaccharides; however, the width of the ribbon was comparable to that of normal cellulose. As both lysine decarboxylase and alanine racemase are required for the integrity of peptidoglycan, we propose a model for the role of peptidoglycan in the assembly of crystalline cellulose.« less
Deng, Ying; Nagachar, Nivedita; Fang, Lin; Luan, Xin; Catchmark, Jeffrey M; Tien, Ming; Kao, Teh-hui
2015-01-01
Gluconacetobacter hansenii, a Gram-negative bacterium, produces and secrets highly crystalline cellulose into growth medium, and has long been used as a model system for studying cellulose synthesis in higher plants. Cellulose synthesis involves the formation of β-1,4 glucan chains via the polymerization of glucose units by a multi-enzyme cellulose synthase complex (CSC). These glucan chains assemble into ordered structures including crystalline microfibrils. AcsA is the catalytic subunit of the cellulose synthase enzymes in the CSC, and AcsC is required for the secretion of cellulose. However, little is known about other proteins required for the assembly of crystalline cellulose. To address this question, we visually examined cellulose pellicles formed in growth media of 763 individual colonies of G. hansenii generated via Tn5 transposon insertion mutagenesis, and identified 85 that produced cellulose with altered morphologies. X-ray diffraction analysis of these 85 mutants identified two that produced cellulose with significantly lower crystallinity than wild type. The gene disrupted in one of these two mutants encoded a lysine decarboxylase and that in the other encoded an alanine racemase. Solid-state NMR analysis revealed that cellulose produced by these two mutants contained increased amounts of non-crystalline cellulose and monosaccharides associated with non-cellulosic polysaccharides as compared to the wild type. Monosaccharide analysis detected higher percentages of galactose and mannose in cellulose produced by both mutants. Field emission scanning electron microscopy showed that cellulose produced by the mutants was unevenly distributed, with some regions appearing to contain deposition of non-cellulosic polysaccharides; however, the width of the ribbon was comparable to that of normal cellulose. As both lysine decarboxylase and alanine racemase are required for the integrity of peptidoglycan, we propose a model for the role of peptidoglycan in the assembly of crystalline cellulose.
Deng, Ying; Nagachar, Nivedita; Fang, Lin; Luan, Xin; Catchmark, Jeffrey M.; Tien, Ming; Kao, Teh-hui
2015-01-01
Gluconacetobacter hansenii, a Gram-negative bacterium, produces and secrets highly crystalline cellulose into growth medium, and has long been used as a model system for studying cellulose synthesis in higher plants. Cellulose synthesis involves the formation of β-1,4 glucan chains via the polymerization of glucose units by a multi-enzyme cellulose synthase complex (CSC). These glucan chains assemble into ordered structures including crystalline microfibrils. AcsA is the catalytic subunit of the cellulose synthase enzymes in the CSC, and AcsC is required for the secretion of cellulose. However, little is known about other proteins required for the assembly of crystalline cellulose. To address this question, we visually examined cellulose pellicles formed in growth media of 763 individual colonies of G. hansenii generated via Tn5 transposon insertion mutagenesis, and identified 85 that produced cellulose with altered morphologies. X-ray diffraction analysis of these 85 mutants identified two that produced cellulose with significantly lower crystallinity than wild type. The gene disrupted in one of these two mutants encoded a lysine decarboxylase and that in the other encoded an alanine racemase. Solid-state NMR analysis revealed that cellulose produced by these two mutants contained increased amounts of non-crystalline cellulose and monosaccharides associated with non-cellulosic polysaccharides as compared to the wild type. Monosaccharide analysis detected higher percentages of galactose and mannose in cellulose produced by both mutants. Field emission scanning electron microscopy showed that cellulose produced by the mutants was unevenly distributed, with some regions appearing to contain deposition of non-cellulosic polysaccharides; however, the width of the ribbon was comparable to that of normal cellulose. As both lysine decarboxylase and alanine racemase are required for the integrity of peptidoglycan, we propose a model for the role of peptidoglycan in the assembly of crystalline cellulose. PMID:25790428
Fujita, Miki; Wasteneys, Geoffrey O
2014-05-01
Cellulose microfibrils are critical for plant cell specialization and function. Recent advances in live cell imaging of fluorescently tagged cellulose synthases to track cellulose synthesis have greatly advanced our understanding of cellulose biosynthesis. Nevertheless, cellulose deposition patterns remain poorly described in many cell types, including those in the process of division or differentiation. In this study, we used field emission scanning electron microscopy analysis of cryo-planed tissues to determine the arrangement of cellulose microfibrils in various faces of cells undergoing cytokinesis or specialized development, including cell types in which cellulose cannot be imaged by conventional approaches. In dividing cells, we detected microfibrillar meshworks in the cell plates, consistent with the concentration at the cell plate of cellulose synthase complexes, as detected by fluorescently tagged CesA6. We also observed a loss of parallel cellulose microfibril orientation in walls of the mother cell during cytokinesis, which corresponded with the loss of fluorescently tagged cellulose synthase complexes from these surfaces. In recently formed guard cells, microfibrils were randomly organized and only formed a highly ordered circumferential pattern after pore formation. In pit fields, cellulose microfibrils were arranged in circular patterns around plasmodesmata. Microfibrils were random in most cotyledon cells except the epidermis and were parallel to the growth axis in trichomes. Deposition of cellulose microfibrils was spatially delineated in metaxylem and protoxylem cells of the inflorescence stem, supporting recent studies on microtubule exclusion mechanisms.
Conte, Pellegrino; Maccotta, Antonella; De Pasquale, Claudio; Bubici, Salvatore; Alonzo, Giuseppe
2009-10-14
Many processes have been proposed to produce glucose as a substrate for bacterial fermentation to obtain bioethanol. Among others, cellulose degradation appears as the most convenient way to achieve reliable amounts of glucose units. In fact, cellulose is the most widespread biopolymer, and it is considered also as a renewable resource. Due to extended intra- and interchain hydrogen bonds that provide a very efficient packing structure, however, cellulose is also a very stable polymer, the degradation of which is not easily achievable. In the past decade, researchers enhanced cellulose reactivity by increasing its solubility in many solvents, among which concentrated phosphoric acid (H(3)PO(4)) played the major role because of its low volatility and nontoxicity. In the present study, the solubilization mechanism of crystalline cellulose in H(3)PO(4) has been elucidated by using high- and low-field NMR spectroscopy. In particular, high-field NMR spectra showed formation of direct bonding between phosphoric acid and dissolved cellulose. On the other hand, molecular dynamics studies by low-field NMR with a fast field cycling (FFC) setup revealed two different H(3)PO(4) relaxing components. The first component, described by the fastest longitudinal relaxation rate (R(1)), was assigned to the H(3)PO(4) molecules bound to the biopolymer. Conversely, the second component, characterized by the slowest R(1), was attributed to the bulk solvent. The understanding of cellulose dissolution in H(3)PO(4) represents a very important issue because comprehension of chemical mechanisms is fundamental for process ameliorations to produce bioenergy from biomasses.
Thermophilic, anaerobic co-digestion of microalgal biomass and cellulose for H2 production.
Carver, Sarah M; Hulatt, Chris J; Thomas, David N; Tuovinen, Olli H
2011-07-01
Microalgal biomass has been a focus in the sustainable energy field, especially biodiesel production. The purpose of this study was to assess the feasibility of treating microalgal biomass and cellulose by anaerobic digestion for H2 production. A microbial consortium, TC60, known to degrade cellulose and other plant polymers, was enriched on a mixture of cellulose and green microalgal biomass of Dunaliella tertiolecta, a marine species, or Chlorella vulgaris, a freshwater species. After five enrichment steps at 60°C, hydrogen yields increased at least 10% under all conditions. Anaerobic digestion of D. tertiolecta and cellulose by TC60 produced 7.7 mmol H2/g volatile solids (VS) which were higher than the levels (2.9-4.2 mmol/g VS) obtained with cellulose and C. vulgaris biomass. Both microalgal slurries contained satellite prokaryotes. The C. vulgaris slurry, without TC60 inoculation, generated H2 levels on par with that of TC60 on cellulose alone. The biomass-fed anaerobic digestion resulted in large shifts in short chain fatty acid concentrations and increased ammonium levels. Growth and H2 production increased when TC60 was grown on a combination of D. tertiolecta and cellulose due to nutrients released from algal cells via lysis. The results indicated that satellite heterotrophs from C. vulgaris produced H2 but the Chlorella biomass was not substantially degraded by TC60. To date, this is the first study to examine H2 production by anaerobic digestion of microalgal biomass. The results indicate that H2 production is feasible but higher yields could be achieved by optimization of the bioprocess conditions including biomass pretreatment.
McDonald, James E; Houghton, James N I; Rooks, David J; Allison, Heather E; McCarthy, Alan J
2012-04-01
Cellulose is reputedly the most abundant organic polymer in the biosphere, yet despite the fundamental role of cellulolytic microorganisms in global carbon cycling and as potential sources of novel enzymes for biotechnology, their identity and ecology is not well established. Cellulose is a major component of landfill waste and its degradation is therefore a key feature of the anaerobic microbial decomposition process. Here, we targeted a number of taxa containing known cellulolytic anaerobes (members of the bacterial genus Fibrobacter, lineages of Clostridium clusters I, III, IV and XIV, and anaerobic fungi of the Neocallimastigales) in landfill leachate and colonized cellulose 'baits' via PCR and quantitative PCR (qPCR). Fibrobacter spp. and Clostridium clusters III, IV and XIV were detected in almost all leachate samples and cluster III and XIV clostridia were the most abundant (1-6% and 1-17% of total bacterial 16S rRNA gene copies respectively). Two landfill leachate microcosms were constructed to specifically assess those microbial communities that colonize and degrade cellulose substrates in situ. Scanning electron microscopy (SEM) of colonized cotton revealed extensive cellulose degradation in one microcosm, and Fibrobacter spp. and Clostridium cluster III represented 29% and 17%, respectively, of total bacterial 16S rRNA gene copies in the biofilm. Visible cellulose degradation was not observed in the second microcosm, and this correlated with negligible relative abundances of Clostridium cluster III and Fibrobacter spp. (≤ 0.1%), providing the first evidence that the novel fibrobacters recently detected in landfill sites and other non-gut environments colonize and degrade cellulose substrates in situ. © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.
Wang, Tuo; Park, Yong Bum; Hong, Mei
2015-01-01
The structural role of pectins in plant primary cell walls is not yet well understood because of the complex and disordered nature of the cell wall polymers. We recently introduced multidimensional solid-state nuclear magnetic resonance spectroscopy to characterize the spatial proximities of wall polysaccharides. The data showed extensive cross peaks between pectins and cellulose in the primary wall of Arabidopsis (Arabidopsis thaliana), indicating subnanometer contacts between the two polysaccharides. This result was unexpected because stable pectin-cellulose interactions are not predicted by in vitro binding assays and prevailing cell wall models. To investigate whether the spatial contacts that give rise to the cross peaks are artifacts of sample preparation, we now compare never-dried Arabidopsis primary walls with dehydrated and rehydrated samples. One-dimensional 13C spectra, two-dimensional 13C-13C correlation spectra, water-polysaccharide correlation spectra, and dynamics data all indicate that the structure, mobility, and intermolecular contacts of the polysaccharides are indistinguishable between never-dried and rehydrated walls. Moreover, a partially depectinated cell wall in which 40% of homogalacturonan is extracted retains cellulose-pectin cross peaks, indicating that the cellulose-pectin contacts are not due to molecular crowding. The cross peaks are observed both at −20°C and at ambient temperature, thus ruling out freezing as a cause of spatial contacts. These results indicate that rhamnogalacturonan I and a portion of homogalacturonan have significant interactions with cellulose microfibrils in the native primary wall. This pectin-cellulose association may be formed during wall biosynthesis and may involve pectin entrapment in or between cellulose microfibrils, which cannot be mimicked by in vitro binding assays. PMID:26036615
Podolich, O; Zaets, I; Kukharenko, O; Orlovska, I; Reva, O; Khirunenko, L; Sosnin, M; Haidak, A; Shpylova, S; Rohutskyy, I; Kharina, A; Skoryk, М; Kremenskoy, M; Klymchuk, D; Demets, R; de Vera, J-P; Kozyrovska, N
2017-06-01
Biofilm-forming microbial communities are known as the most robust assemblages that can survive in harsh environments. Biofilm-associated microorganisms display greatly increased resistance to physical and chemical adverse conditions, and they are expected to be the first form of life on Earth or anywhere else. Biological molecules synthesized by biofilm -protected microbiomes may serve as markers of the nucleoprotein life. We offer a new experimental model, a kombucha multimicrobial culture (KMC), to assess a structural integrity of a widespread microbial polymer - cellulose - as a biosignature of bacteria-producers for the multipurpose international project "BIOlogical and Mars Experiment (BIOMEX)", which aims to study the vitality of pro- and eukaryotic organisms and the stability of organic biomolecules in contact with minerals to analyze the detectability of life markers in the context of a planetary background. In this study, we aimed to substantiate the detectability of mineralized cellulose with spectroscopy and to study the KMC macrocolony phenotype stability under adverse conditions (UV, excess of inorganics etc.). Cellulose matrix of the KMC macrocolony has been mineralized in the mineral-water interface under assistance of KMC-members. Effect of bioleached ions on the cellulose matrix has been visible, and the FT-IR spectrum proved changes in cellulose structure. However, the specific cellulose band vibration, confirming the presence of β(1,4)-linkages between monomers, has not been quenched by secondary minerals formed on the surface of pellicle. The cellulose-based KMC macrocolony phenotype was in a dependence on extracellular matrix components (ionome, viriome, extracellular membrane vesicles), which provided its integrity and rigidness in a certain extent under impact of stressful factors.
NASA Astrophysics Data System (ADS)
Podolich, O.; Zaets, I.; Kukharenko, O.; Orlovska, I.; Reva, O.; Khirunenko, L.; Sosnin, M.; Haidak, A.; Shpylova, S.; Rohutskyy, I.; Kharina, A.; Skoryk, M.; Kremenskoy, M.; Klymchuk, D.; Demets, R.; de Vera, J.-P.; Kozyrovska, N.
2017-06-01
Biofilm-forming microbial communities are known as the most robust assemblages that can survive in harsh environments. Biofilm-associated microorganisms display greatly increased resistance to physical and chemical adverse conditions, and they are expected to be the first form of life on Earth or anywhere else. Biological molecules synthesized by biofilm -protected microbiomes may serve as markers of the nucleoprotein life. We offer a new experimental model, a kombucha multimicrobial culture (KMC), to assess a structural integrity of a widespread microbial polymer - cellulose - as a biosignature of bacteria-producers for the multipurpose international project "BIOlogical and Mars Experiment (BIOMEX)", which aims to study the vitality of pro- and eukaryotic organisms and the stability of organic biomolecules in contact with minerals to analyze the detectability of life markers in the context of a planetary background. In this study, we aimed to substantiate the detectability of mineralized cellulose with spectroscopy and to study the KMC macrocolony phenotype stability under adverse conditions (UV, excess of inorganics etc.). Cellulose matrix of the KMC macrocolony has been mineralized in the mineral-water interface under assistance of KMC-members. Effect of bioleached ions on the cellulose matrix has been visible, and the FT-IR spectrum proved changes in cellulose structure. However, the specific cellulose band vibration, confirming the presence of β(1,4)-linkages between monomers, has not been quenched by secondary minerals formed on the surface of pellicle. The cellulose-based KMC macrocolony phenotype was in a dependence on extracellular matrix components (ionome, viriome, extracellular membrane vesicles), which provided its integrity and rigidness in a certain extent under impact of stressful factors.
Li, Ying; Chen, Hongmei; Liu, Dian; Wang, Wenxi; Liu, Ye; Zhou, Shaobing
2015-06-17
In this study, we developed a pH-responsive shape-memory polymer nanocomposite by blending poly(ethylene glycol)-poly(ε-caprolactone)-based polyurethane (PECU) with functionalized cellulose nanocrystals (CNCs). CNCs were functionalized with pyridine moieties (CNC-C6H4NO2) through hydroxyl substitution of CNCs with pyridine-4-carbonyl chloride and with carboxyl groups (CNC-CO2H) via 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) mediated surface oxidation, respectively. At a high pH value, the CNC-C6H4NO2 had attractive interactions from the hydrogen bonding between pyridine groups and hydroxyl moieties; at a low pH value, the interactions reduced or disappeared due to the protonation of pyridine groups, which are a Lewis base. The CNC-CO2H responded to pH variation in an opposite manner. The hydrogen bonding interactions of both CNC-C6H4NO2 and CNC-CO2H can be readily disassociated by altering pH values, endowing the pH-responsiveness of CNCs. When these functionalized CNCs were added in PECU polymer matrix to form nanocomposite network which was confirmed with rheological measurements, the mechanical properties of PECU were not only obviously improved but also the pH-responsiveness of CNCs could be transferred to the nanocomposite network. The pH-sensitive CNC percolation network in polymer matrix served as the switch units of shape-memory polymers (SMPs). Furthermore, the modified CNC percolation network and polymer molecular chains also had strong hydrogen bonding interactions among hydroxyl, carboxyl, pyridine moieties, and isocyanate groups, which could be formed or destroyed through changing pH value. The shape memory function of the nanocomposite network was only dependent on the pH variation of the environment. Therefore, this pH-responsive shape-memory nancomposite could be potentially developed into a new smart polymer material.
Knott, Brandon C.; Crowley, Michael F.; Himmel, Michael E.; ...
2016-01-29
The processive cycle of the bacterial cellulose synthase (Bcs) includes the addition of a single glucose moiety to the end of a growing cellulose chain followed by the translocation of the nascent chain across the plasma membrane. The mechanism of this translocation and its precise location within the processive cycle are not well understood. In particular, the molecular details of how a polymer (cellulose) whose basic structural unit is a dimer (cellobiose) can be constructed by adding one monomer (glucose) at a time are yet to be elucidated. Here, we have utilized molecular dynamics simulations and free energy calculations tomore » the shed light on these questions. We find that translocation forward by one glucose unit is quite favorable energetically, giving a free energy stabilization of greater than 10 kcal mol-1. In addition, there is only a small barrier to translocation, implying that translocation is not rate limiting within the Bcs processive cycle (given experimental rates for cellulose synthesis in vitro). Perhaps most significantly, our results also indicate that steric constraints at the transmembrane tunnel entrance regulate the dimeric structure of cellulose. Namely, when a glucose molecule is added to the cellulose chain in the same orientation as the acceptor glucose, the terminal glucose freely rotates upon forward motion, thus suggesting a regulatory mechanism for the dimeric structure of cellulose. We characterize both the conserved and non-conserved enzyme-polysaccharide interactions that drive translocation, and find that 20 of the 25 residues that strongly interact with the translocating cellulose chain in the simulations are well conserved, mostly with polar or aromatic side chains. Our results also allow for a dynamical analysis of the role of the so-called 'finger helix' in cellulose translocation that has been observed structurally. Taken together, these findings aid in the elucidation of the translocation steps of the Bcs processive cycle and may be widely relevant to polysaccharide synthesizing or degrading enzymes that couple catalysis with chain translocation.« less
Bamboo reinforced polymer composite - A comprehensive review
NASA Astrophysics Data System (ADS)
Roslan, S. A. H.; Rasid, Z. A.; Hassan, M. Z.
2018-04-01
Bamboo has greatly attention of researchers due to their advantages over synthetic polymers. It is entirely renewable, environmentally-friendly, non-toxic, cheap, non-abrasive and fully biodegradable. This review paper summarized an oveview of the bamboo, fiber extraction and mechanical behavior of bamboo reinforced composites. A number of studies proved that mechanical properties of bamboo fibers reinforced reinforced polymer composites are excellent and competent to be utilized in high-tech applications. The properties of the laminate are influenced by the fiber loading, fibre orientation, physical and interlaminar adhesion between fibre and matrix. In contrast, the presence of chemical constituents such as cellulose, lignin, hemicellulose and wax substances in natural fibres preventing them from firmly binding with polymer resin. Thus, led to poor mechanical properties for composites. Many attempt has been made in order to overcome this issue by using the chemical treatment.
Shelate, Pragna; Dave, Divyang
2016-01-01
The objective of this work was design, characterization, and optimization of controlled drug delivery system containing antibiotic drug/s. Osmotic drug delivery system was chosen as controlled drug delivery system. The porous osmotic pump tablets were designed using Plackett-Burman and Box-Behnken factorial design to find out the best formulation. For screening of three categories of polymers, six independent variables were chosen for Plackett-Burman design. Osmotic agent sodium chloride and microcrystalline cellulose, pore forming agent sodium lauryl sulphate and sucrose, and coating agent ethyl cellulose and cellulose acetate were chosen as independent variables. Optimization of osmotic tablets was done by Box-Behnken design by selecting three independent variables. Osmotic agent sodium chloride, pore forming agent sodium lauryl sulphate, and coating agent cellulose acetate were chosen as independent variables. The result of Plackett-Burman and Box-Behnken design and ANOVA studies revealed that osmotic agent and pore former had significant effect on the drug release up to 12 hr. The observed independent variables were found to be very close to predicted values of most satisfactory formulation which demonstrates the feasibility of the optimization procedure in successful development of porous osmotic pump tablets containing antibiotic drug/s by using sodium chloride, sodium lauryl sulphate, and cellulose acetate as key excipients. PMID:27610247
Pan-In, Porntip; Wanichwecharungruang, Supason; Hanes, Justin; Kim, Anthony J
2014-01-01
Garcinia mangostana Linn extract (GME) is a natural product that has received considerable attention in cancer therapy, and has the potential to reduce side effects of chemotherapeutics and improve efficacy. We formulated GME-encapsulated ethyl cellulose (GME-EC) and a polymer blend of ethyl cellulose and methyl cellulose (GME-EC/MC) nanoparticles. We achieved high drug-loading and encapsulation efficiency using a solvent-displacement method with particle sizes around 250 nm. Cellular uptake and accumulation of GME was higher for GME-encapsulated nanoparticles compared to free GME. In vitro cytotoxicity analysis showed effective anticancer activity of GME-EC and GME-EC/MC nanoparticles in HeLa cells in a dose-dependent manner. GME-EC/MC nanoparticles showed approximately twofold-higher anticancer activity compared to GME-EC nanoparticles, likely due to their enhanced bioavailability. GME-encapsulated nanoparticles primarily entered HeLa cells by clathrin-mediated endocytosis and trafficked through the endolysosomal pathway. As far as we know, this is the first report on the cellular uptake and intracellular trafficking mechanism of drug-loaded cellulose-based nanoparticles. In summary, encapsulation of GME using cellulose-derivative nanoparticles – GME-EC and GME-EC/MC nanoparticles – successfully improved the bioavailability of GME in aqueous solution, enhanced cellular uptake, and displayed effective anticancer activity. PMID:25125977
2010-01-01
Background The assembly and spatial organization of enzymes in naturally occurring multi-protein complexes is of paramount importance for the efficient degradation of complex polymers and biosynthesis of valuable products. The degradation of cellulose into fermentable sugars by Clostridium thermocellum is achieved by means of a multi-protein "cellulosome" complex. Assembled via dockerin-cohesin interactions, the cellulosome is associated with the cell surface during cellulose hydrolysis, forming ternary cellulose-enzyme-microbe complexes for enhanced activity and synergy. The assembly of recombinant cell surface displayed cellulosome-inspired complexes in surrogate microbes is highly desirable. The model organism Lactococcus lactis is of particular interest as it has been metabolically engineered to produce a variety of commodity chemicals including lactic acid and bioactive compounds, and can efficiently secrete an array of recombinant proteins and enzymes of varying sizes. Results Fragments of the scaffoldin protein CipA were functionally displayed on the cell surface of Lactococcus lactis. Scaffolds were engineered to contain a single cohesin module, two cohesin modules, one cohesin and a cellulose-binding module, or only a cellulose-binding module. Cell toxicity from over-expression of the proteins was circumvented by use of the nisA inducible promoter, and incorporation of the C-terminal anchor motif of the streptococcal M6 protein resulted in the successful surface-display of the scaffolds. The facilitated detection of successfully secreted scaffolds was achieved by fusion with the export-specific reporter staphylococcal nuclease (NucA). Scaffolds retained their ability to associate in vivo with an engineered hybrid reporter enzyme, E. coli β-glucuronidase fused to the type 1 dockerin motif of the cellulosomal enzyme CelS. Surface-anchored complexes exhibited dual enzyme activities (nuclease and β-glucuronidase), and were displayed with efficiencies approaching 104 complexes/cell. Conclusions We report the successful display of cellulosome-inspired recombinant complexes on the surface of Lactococcus lactis. Significant differences in display efficiency among constructs were observed and attributed to their structural characteristics including protein conformation and solubility, scaffold size, and the inclusion and exclusion of non-cohesin modules. The surface-display of functional scaffold proteins described here represents a key step in the development of recombinant microorganisms capable of carrying out a variety of metabolic processes including the direct conversion of cellulosic substrates into fuels and chemicals. PMID:20840763
Tian, Donglin; Li, Tao; Zhang, Rongchun; Wu, Qiang; Chen, Tiehong; Sun, Pingchuan; Ramamoorthy, Ayyalusamy
2017-06-29
Fabricating materials with excellent mechanical performance from the natural renewable and degradable biopolymers has drawn significant attention in recent decades due to the environmental concerns and energy crisis. As two of the most promising substitutes of synthetic polymers, silk fibroin (SF), and cellulose, have been widely used in the field of textile, biomedicine, biotechnology, etc. Particularly, the cellulose/SF blend film exhibits better strength and toughness than that of regenerated cellulose film. Herein, this study is aimed to understand the molecular origin of the enhanced mechanical properties for the cellulose/SF blend film, using solid-state NMR as a main tool to investigate the conformational changes, intermolecular interactions between cellulose and SF and the water organization. It is found that the content of the β-sheet structure is increased in the cellulose/SF blend film with respect to the regenerated SF film, accompanied by the reduction of the content of random coil structures. In addition, the strong hydrogen bonding interaction between the SF and cellulose is clearly elucidated by the two-dimensional (2D) 1 H- 13 C heteronuclear correlation (HETCOR) NMR experiments, demonstrating that the SF and cellulose are miscible at the molecular level. Moreover, it is also found that the -NH groups of SF prefer to form hydrogen bonds with the hydroxyl groups bonded to carbons C2 and C3 of cellulose, while the hydroxyl groups bonded to carbon C6 and the ether oxygen are less favorable for hydrogen bonding interactions with the -NH groups of SF. Interestingly, bound water is found to be present in the air-dried cellulose/SF blend film, which is predominantly associated with the cellulose backbones as determined by 2D 1 H- 13 C wide-line-separation (WISE) experiments with spin diffusion. This clearly reveals the presence of nanoheterogeneity in the cellulose/SF blend film, although cellulose and SF are miscible at a molecular level. Without doubt, these in-depth atomic-level structural information could help reveal the molecular origin of the enhanced mechanical properties of the blend film, and thus to establish the structure-property relationship, which could further provide guidance for the fabrication of high performance biopolymer-based materials.
Crystalline and amorphous cellulose in the secondary walls of Arabidopsis.
Ruel, Katia; Nishiyama, Yoshiharu; Joseleau, Jean-Paul
2012-09-01
In the cell walls of higher plants, cellulose chains are present in crystalline microfibril, with an amorphous part at the surface, or present as amorphous material. To assess the distribution and relative occurrence of the two forms of cellulose in the inflorescence stem of Arabidopsis, we used two carbohydrate-binding modules, CBM3a and CBM28, specific for crystalline and amorphous cellulose, respectively, with immunogold detection in TEM. The binding of the two CBMs displayed specific patterns suggesting that the synthesis of cellulose leads to variable nanodomains of cellulose structures according to cell type. In developing cell walls, only CBM3a bound significantly to the incipient primary walls, indicating that at the onset of its deposition cellulose is in a crystalline structure. As the secondary wall develops, the labeling with both CBMs becomes more intense. The variation of the labeling pattern by CBM3a between transverse and longitudinal sections appeared related to microfibril orientation and differed between fibers and vessels. Although the two CBMs do not allow the description of the complete status of cellulose microstructures, they revealed the dynamics of the deposition of crystalline and amorphous forms of cellulose during wall formation and between cell types adapting cellulose microstructures to the cell function. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.
de Oliveira Faria, Miriam; Cipriano, Tayssa Martins; da Cruz, Adriano Gomes; Santos, Bibiana Alves Dos; Pollonio, Marise Aparecida Rodrigues; Campagnol, Paulo Cezar Bastianello
2015-06-01
Bologna-type sausages were produced with 50% of their pork back-fat content replaced with gels elaborated with different ratios of pork skin, water, and amorphous cellulose (1:1:0, 1:1:0.1, 1:1:0.2, 1:1:0.3, and 1:1:0.4). The impact of such replacement on the physico-chemical characteristics and the consumer sensory profiling was evaluated. The modified treatments had 42% less fat, 18% more protein, and 8% more moisture than the control group. Treatments with amorphous cellulose had a lower cooking loss and higher emulsion stability. High amorphous cellulose content (1:1:0.3 and 1:1:0.4) increased hardness, gumminess, and chewiness. The gel formulated with the ratio of 1:1:0.2 (pork skin: water: amorphous cellulose gel) provided a sensory sensation similar to that provided by fat and allowed products of good acceptance to be obtained. Therefore, a combination of pork skin and amorphous cellulose is useful in improving technological quality and producing healthier and sensory acceptable bologna-type sausages. Copyright © 2015 Elsevier Ltd. All rights reserved.
Cellulose in Cyanobacteria. Origin of Vascular Plant Cellulose Synthase?
Nobles, David R.; Romanovicz, Dwight K.; Brown, R. Malcolm
2001-01-01
Although cellulose biosynthesis among the cyanobacteria has been suggested previously, we present the first conclusive evidence, to our knowledge, of the presence of cellulose in these organisms. Based on the results of x-ray diffraction, electron microscopy of microfibrils, and cellobiohydrolase I-gold labeling, we report the occurrence of cellulose biosynthesis in nine species representing three of the five sections of cyanobacteria. Sequence analysis of the genomes of four cyanobacteria revealed the presence of multiple amino acid sequences bearing the DDD35QXXRW motif conserved in all cellulose synthases. Pairwise alignments demonstrated that CesAs from plants were more similar to putative cellulose synthases from Anabaena sp. Pasteur Culture Collection 7120 and Nostoc punctiforme American Type Culture Collection 29133 than any other cellulose synthases in the database. Multiple alignments of putative cellulose synthases from Anabaena sp. Pasteur Culture Collection 7120 and N. punctiforme American Type Culture Collection 29133 with the cellulose synthases of other prokaryotes, Arabidopsis, Gossypium hirsutum, Populus alba × Populus tremula, corn (Zea mays), and Dictyostelium discoideum showed that cyanobacteria share an insertion between conserved regions U1 and U2 found previously only in eukaryotic sequences. Furthermore, phylogenetic analysis indicates that the cyanobacterial cellulose synthases share a common branch with CesAs of vascular plants in a manner similar to the relationship observed with cyanobacterial and chloroplast 16s rRNAs, implying endosymbiotic transfer of CesA from cyanobacteria to plants and an ancient origin for cellulose synthase in eukaryotes. PMID:11598227
Morphology Evolution of Polypropylene in Immiscible Polymer Blends for Fabrication of Nanofibers
USDA-ARS?s Scientific Manuscript database
Immiscible blends of cellulose acetate butyrate (CAB) and isotactic polypropylenes (iPPs) with different melting index were extruded through a two-strand rod die. The extrudates were hot-drawn at the die exit at different draw ratios by controlling the drawing speed. The morphologies of iPP fibers e...
Roger M. Rowell; Roger Pettersen; Mandla A. Tshabalala
2012-01-01
Wood is best defined as a three-dimensional biopolymer composite composed of an interconnected network of cellulose, hemicelluloses and lignin with minor amounts of extractives, and inorganics. The major chemical component of a living tree is water, but on a dry weight basis, all wood cell walls consist mainly of sugar-based polymers (carbohydrates, 65-75%) that are...
Opportunities for cellulose nanomaterials in packaging films: a review and future trends
Nicole M. Stark
2016-01-01
Performance requirements for packaging films may include barrier properties, transparency, flexibility, and tensile strength. Conventional packaging materials such as plastic films and laminates, are typically made from petroleum-based polymers. Currently, there is a drive to develop sustainable packaging materials. These alternative materials must be able to be...
Liqing Wei; Shupin Luo; Armando G. McDonald; Umesh P. Agarwal; Kolby C. Hirth; Laurent M. Matuana; Ronald C. Sabo; Nicole M. Stark
2017-01-01
Cellulose nanocrystals (CNCs) are renewable and sustainable filler for polymeric nanocomposites. However, their high hydrophilicity limits their use with hydrophobic polymer for composite materials. In this study, freeze-dried CNCs were modified by transesterification with canola oil fatty acid methyl ester to reduce the hydrophilicity. The transesterified CNCs (CNCFE...
Application and Testing of Transparent Plastics Used in Airplane Construction
NASA Technical Reports Server (NTRS)
Riechers, K; Olms, J
1938-01-01
This report concerns the efforts being made to remove the source of danger to passengers arising from the fracturing of silicate glass. Some of the alternatives presented include: single-layer safety glass, multi-layer safety glass, transparent plastic resins. Some of the resins considered are celluloid, cellulose acetates, and mixtures of polymers.
ERIC Educational Resources Information Center
Kaiser, Adrian; Stark, Wendelin J.; Grass, Robert N.
2017-01-01
A chemistry laboratory experiment using everyday items and readily available chemicals is described to introduce advanced high school students and undergraduate college students to porous polymer membranes. In a three-step manufacturing process, a membrane is produced at room temperature. The filtration principle of the membrane is then…
Profit opportunities for the chemical process industries
NASA Technical Reports Server (NTRS)
1971-01-01
Papers given at a seminar designed to assist industry in the utilization of NASA-developed technology are presented. The topics include the following: the Technology Utilization program, NASA patent policy changes, transfer of Hysttl resin technology, nonflammable cellulosic materials development, nonflammable paper technology, circuit board laminates and construction, polymide resins and other polymers, and intumescent coatings.
Bose, Anirbandeep; Wong, Tin Wui; Singh, Navjot
2012-01-01
The objective of this present investigation was to develop and formulate sustained release (SR) matrix tablets of Itopride HCl, by using different polymer combinations and fillers, to optimize by Central Composite Design response surface methodology for different drug release variables and to evaluate drug release pattern of the optimized product. Sustained release matrix tablets of various combinations were prepared with cellulose-based polymers: hydroxy propyl methyl cellulose (HPMC) and polyvinyl pyrolidine (pvp) and lactose as fillers. Study of pre-compression and post-compression parameters facilitated the screening of a formulation with best characteristics that underwent here optimization study by response surface methodology (Central Composite Design). The optimized tablet was further subjected to scanning electron microscopy to reveal its release pattern. The in vitro study revealed that combining of HPMC K100M (24.65 MG) with pvp(20 mg)and use of LACTOSE as filler sustained the action more than 12 h. The developed sustained release matrix tablet of improved efficacy can perform therapeutically better than a conventional tablet. PMID:23960836
Lu, Peng; Xiao, Huining; Zhang, Weiwei; Gong, Glen
2014-10-13
Nanofibrillated cellulose (NFC) easily forms a high strength film but is unable to withstand the influence of water vapor when used in high moisture situations. The water vapor transmission rate (WVTR) of a NFC film was as high as 5088 g/m(2)24h (38 °C, 90% RH). The addition of beeswax latex in a NFC casting film (NFX) lowered the WVTR to 3918 g/m(2)24h. To further reduce the WVTR, a coating agent comprised of acrylated epoxidized soybean oil (AESO) and 3-aminopropyltriethoxysilane (APTS) was applied onto the NFX film using a rod coater. A combination of the suitable AESO/APTS ratio, initiator dosing, curing time and temperature could reduce the WVTR to 188 g/m(2) 24h when the coat weight was 5 g/m(2). Moreover, the coated NFX film was highly hydrophobic along with the improved transparency and thermal stability. This biodegradable polymer-coated NFC film can be used as potential packaging barrier in certain areas. Copyright © 2014 Elsevier Ltd. All rights reserved.
Assembly and enlargement of the primary cell wall in plants
NASA Technical Reports Server (NTRS)
Cosgrove, D. J.
1997-01-01
Growing plant cells are shaped by an extensible wall that is a complex amalgam of cellulose microfibrils bonded noncovalently to a matrix of hemicelluloses, pectins, and structural proteins. Cellulose is synthesized by complexes in the plasma membrane and is extruded as a self-assembling microfibril, whereas the matrix polymers are secreted by the Golgi apparatus and become integrated into the wall network by poorly understood mechanisms. The growing wall is under high tensile stress from cell turgor and is able to enlarge by a combination of stress relaxation and polymer creep. A pH-dependent mechanism of wall loosening, known as acid growth, is characteristic of growing walls and is mediated by a group of unusual wall proteins called expansins. Expansins appear to disrupt the noncovalent bonding of matrix hemicelluloses to the microfibril, thereby allowing the wall to yield to the mechanical forces generated by cell turgor. Other wall enzymes, such as (1-->4) beta-glucanases and pectinases, may make the wall more responsive to expansin-mediated wall creep whereas pectin methylesterases and peroxidases may alter the wall so as to make it resistant to expansin-mediated creep.
Assembly and enlargement of the primary cell wall in plants.
Cosgrove, D J
1997-01-01
Growing plant cells are shaped by an extensible wall that is a complex amalgam of cellulose microfibrils bonded noncovalently to a matrix of hemicelluloses, pectins, and structural proteins. Cellulose is synthesized by complexes in the plasma membrane and is extruded as a self-assembling microfibril, whereas the matrix polymers are secreted by the Golgi apparatus and become integrated into the wall network by poorly understood mechanisms. The growing wall is under high tensile stress from cell turgor and is able to enlarge by a combination of stress relaxation and polymer creep. A pH-dependent mechanism of wall loosening, known as acid growth, is characteristic of growing walls and is mediated by a group of unusual wall proteins called expansins. Expansins appear to disrupt the noncovalent bonding of matrix hemicelluloses to the microfibril, thereby allowing the wall to yield to the mechanical forces generated by cell turgor. Other wall enzymes, such as (1-->4) beta-glucanases and pectinases, may make the wall more responsive to expansin-mediated wall creep whereas pectin methylesterases and peroxidases may alter the wall so as to make it resistant to expansin-mediated creep.
Huang, Chao; Guo, Hai-Jun; Xiong, Lian; Wang, Bo; Shi, Si-Lan; Chen, Xue-Fang; Lin, Xiao-Qing; Wang, Can; Luo, Jun; Chen, Xin-De
2016-01-20
In this study, lipid fermentation wastewater (fermentation broth after separation with yeast biomass) with high Chemical Oxygen Demand (COD) value of 25,591 mg/L was used as substrate for bacterial cellulose (BC) production by Gluconacetobacter xylinus for the first time. After 5 days of fermentation, the highest BC yield (0.659 g/L) was obtained. Both monosaccharide and polysaccharides present in lipid fermentation wastewater could be utilized by G. xylinus simultaneously during fermentation. By this bioconversion, 30.0% of COD could be removed after 10 days of fermentation and the remaining wastewater could be used for further BC fermentation. The crystallinity of BC samples in lipid fermentation wastewater increased gradually during fermentation but overall the environment of lipid fermentation wastewater showed small influence on BC structure by comparison with that in traditional HS medium by using FE-SEM, FTIR, and XRD. By this work, the possibility of using lipid fermentation wastewater containing low value carbohydrate polymer (extracellular polysaccharides) for high value carbohydrate polymer (BC) production was proven. Copyright © 2015 Elsevier Ltd. All rights reserved.
Kaur, Harjot; Bulasara, Vijaya Kumar; Gupta, Raj Kumar
2018-09-01
Polymer-ceramic composite membranes were prepared by dip coating technique using 5 wt.% cellulose acetate (CA) solution at different temperatures (15 °C, 25 °C and 40 °C). The effect of pH (2-12) of the polymeric solution on the properties of the membranes was studied using SEM, EDAX, FTIR, gas and liquid permeation. The thickness of the polymeric layer depended on the interaction of CA solution with the surface of ceramic support. Membrane permeability decreased with increase in pH because of decrease in pore size and porosity resulting from strong interaction of the polymer layer with the ceramic support. The porosity and mean pore size of the prepared membranes were found to be 28-60% and 30-47 nm (ultrafiltration range), respectively. The optimized membrane (pH 7) was used for ultrafiltration of oil in water emulsions (100 and 200 mg/L). Oil rejection of 99.61% was obtained for 100 mg/L of oil concentration in water. Copyright © 2018 Elsevier Ltd. All rights reserved.
Ford, J L
1999-03-15
This review focuses on the thermal analysis of hydroxypropylmethylcellulose (HPMC) and methylcellulose. Differential scanning calorimetry (DSC) of their powders is used to determine temperatures of moisture loss (in conjunction with thermogravimetric analysis) and glass transition temperatures. However, sample preparation and encapsulation affect the values obtained. The interaction of these cellulose ethers with water is evaluated by DSC. Water is added to the powder directly in DSC pans or preformed gels can be evaluated. Data quality depends on previous thermal history but estimates of the quantity of water bound to the polymers may be made. Water uptake by cellulose ethers may be evaluated by the use of polymeric wafers and by following loss of free water, over a series of timed curves, into wafers in contact with water. Cloud points, which assess the reduction of polymer solubility with increase of temperature, may be assessed spectrophotometrically. DSC and rheometric studies are used to follow thermogelation, a process involving hydrophobic interaction between partly hydrated polymeric chains. The advantages and disadvantages of the various methodologies are highlighted. Copyright.
Bose, Anirbandeep; Wong, Tin Wui; Singh, Navjot
2013-04-01
The objective of this present investigation was to develop and formulate sustained release (SR) matrix tablets of Itopride HCl, by using different polymer combinations and fillers, to optimize by Central Composite Design response surface methodology for different drug release variables and to evaluate drug release pattern of the optimized product. Sustained release matrix tablets of various combinations were prepared with cellulose-based polymers: hydroxy propyl methyl cellulose (HPMC) and polyvinyl pyrolidine (pvp) and lactose as fillers. Study of pre-compression and post-compression parameters facilitated the screening of a formulation with best characteristics that underwent here optimization study by response surface methodology (Central Composite Design). The optimized tablet was further subjected to scanning electron microscopy to reveal its release pattern. The in vitro study revealed that combining of HPMC K100M (24.65 MG) with pvp(20 mg)and use of LACTOSE as filler sustained the action more than 12 h. The developed sustained release matrix tablet of improved efficacy can perform therapeutically better than a conventional tablet.
Mohamed, Magdy F; Essawy, Hisham A; Ammar, Nabila S; Ibrahim, Hanan S
2017-01-01
Acrylic acid (AA) was graft copolymerized from cellulose (Cell) in presence of potassium fulvate (KF) in order to enhance the chemical activity of the resulting chelating polymer and the handling as well. Fourier transform infrared (FTIR) proved that KF was efficiently inserted and became a permanent part of the network structure of the sorbent in parallel during the grafting copolymerization. Scanning electron microscopy (SEM) revealed intact homogeneous structure with uniform surface. This indicates improvement of the handling, however, it was not the case for the graft copolymer of acrylic acid onto cellulose in absence of KF, which is known to be brittle and lacks mechanical integrity. Effective insertion of this co-interpenetrating agent provided more functional groups, such as OH and COOH, which improved the chelating power of the produced sorbent as found for the removal of Cu 2+ ions from its aqueous solutions (the removal efficiency reached ∼98.9%). Different models were used to express the experimental data. The results corroborated conformity of the pseudo-second order kinetic model and Langmuir isotherm model to the sorption process, which translates into dominance of the chemisorption. Regeneration of the chelating polymers under harsh conditions did not affect the efficiency of copper ions uptake up to three successive cycles. A thermodynamic investigation ensured exothermic nature of the adsorption process that became less favourable at higher temperatures. Copyright © 2016 Elsevier B.V. All rights reserved.
Essawy, Hisham A; Ghazy, Mohamed B M; El-Hai, Farag Abd; Mohamed, Magdy F
2016-08-01
Superabsorbent polymers fabricated via grafting polymerization of acrylic acid from chitosan (CTS) yields materials that suffer from poor mechanical strength. Hybridization of chitosan with cellulose (Cell) via chemical bonding using thiourea formaldehyde resin increases the flexibility of the produced hybrid (CTS/Cell). The hybridization process and post graft polymerization of acrylic acid was followed using Fourier transform infrared (FTIR). Also, the obtained structures were homogeneous and exhibited uniform surface as could be shown from imaging with scanning electron microscopy (SEM). Thus, the polymers derived from the grafting of polyacrylic acid from (CTS/Cell) gave rise to much more mechanically robust structures ((CTS/Cell)-g-PAA) that bear wide range of pH response due to presence of chitosan and polyacrylic acid in one homogeneous entity. Additionally, the obtained structures possessed greater water absorbency 390, 39.5g/g in distilled water and saline (0.9wt.% NaCl solution), respectively, and enhanced retention potential even at elevated temperatures as revealed by thermogravimetric analysis (TGA). This could be explained by the high grafting efficiency (GE%), 86.4%, and grafting yield (GY%), 750%. The new superabsorbent polymers proved to be very efficient devices for controlled release of fertilizers into the soil which expands their use in agriculture and horticultural applications. Copyright © 2016 Elsevier B.V. All rights reserved.
Domingues, Rui M A; Chiera, Silvia; Gershovich, Pavel; Motta, Antonella; Reis, Rui L; Gomes, Manuela E
2016-06-01
Anisotropically aligned electrospun nanofibrous scaffolds based on natural/synthetic polymer blends have been established as a reasonable compromise between biological and biomechanical performance for tendon tissue engineering (TE) strategies. However, the limited tensile properties of these biomaterials restrict their application in this field due to the load-bearing nature of tendon/ligament tissues. Herein, the use of cellulose nanocrystals (CNCs) as reinforcing nanofillers in aligned electrospun scaffolds based on a natural/synthetic polymer blend matrix, poly-ε-caprolactone/chitosan (PCL/CHT) is reported. The incorporation of small amounts of CNCs (up to 3 wt%) into tendon mimetic nanofiber bundles has a remarkable biomaterial-toughing effect (85% ± 5%, p < 0.0002) and raises the scaffolds mechanical properties to tendon/ligament relevant range (σ = 39.3 ± 1.9 MPa and E = 540.5 ± 83.7 MPa, p < 0.0001). Aligned PCL/CHT/CNC nanocomposite fibrous scaffolds meet not only the mechanical requirements for tendon TE applications but also provide tendon mimetic extracellular matrix (ECM) topographic cues, a key feature for maintaining tendon cell's morphology and behavior. The strategy proposed here may be extended to other anisotropic aligned nanofibrous scaffolds based on natural/synthetic polymer blends and enable the full exploitation of the advantages provided by their tendon mimetic fibrous structures in tendon TE. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
NASA Astrophysics Data System (ADS)
Dagousset, Laure; Pognon, Grégory; Nguyen, Giao T. M.; Vidal, Frédéric; Jus, Sébastien; Aubert, Pierre-Henri
2018-07-01
Electrochemical energy storage is a very active research topic. However, the use of liquid electrolyte in such systems as supercacitors presents several drawbacks on security and packaging. One way to overcome these issues is to design supercapacitors using solid-state electrolytes. We report here the one-pot synthesis and the characterization of self-standing gel polymer electrolyte (SGPE) composed of semi-Interpenetrating Polymer Networks (semi-IPN) based on poly(ethylene oxide) (PEO) network and non cross-linked nitrile butadiene rubber (NBR), self-containing EMITFSI/γ-Butyrolactone (50/50 wt%/wt%) binary mixtures. The SGPE under the form of a thin film are then used as solid electrolyte and also as separator in supercapacitors with Single Wall Carbon Nanotubes (SWCNTs) bucky paper as electrodes. Thermal characterization revealed the suitability of all synthesized membrane in wide range of operating temperature. Electrochemical stabilities of SGPE were close to that of a cellulose separator system (ESW∼3.2-3.6 V) at 20 °C, and were relatively higher than a cellulose system at 100 °C: 2.1-2.5 V and 1.8 V respectively. Furthermore, floating experiments at 100 °C (holding voltage at 2 V) revealed the exceptionally high stability of SGPE, with a residual capacitance of 93% after 500 h. This high electrochemical performance demonstrated the potential of semi-IPN SGPE as separator/electrolyte for high performance supercapacitors.
Gebäck, Tobias; Marucci, Mariagrazia; Boissier, Catherine; Arnehed, Johan; Heintz, Alexei
2015-04-23
Understanding how the pore structure influences the mass transport through a porous material is important in several applications, not the least in the design of polymer film coatings intended to control drug release. In this study, a polymer film made of ethyl cellulose and hydroxypropyl cellulose was investigated. The 3D structure of the films was first experimentally characterized using confocal laser scanning microscopy data and then mathematically reconstructed for the whole film thickness. Lattice Boltzmann simulations were performed to compute the effective diffusion coefficient of water in the film and the results were compared to experimental data. The local porosities and pore sizes were also analyzed to determine how the properties of the internal film structure affect the water effective diffusion coefficient. The results show that the top part of the film has lower porosity, lower pore size, and lower connectivity, which results in a much lower effective diffusion coefficient in this part, largely determining the diffusion rate through the entire film. Furthermore, the local effective diffusion coefficients were not proportional to the local film porosity, indicating that the results cannot be explained by a single tortuosity factor. In summary, the proposed methodology of combining microscopy data, mass transport simulations, and pore space analysis can give valuable insights on how the film structure affects the mass transport through the film.
Hiremath, Praveen S; Saha, Ranendra N
2008-10-01
The aim of the present investigation was to develop controlled release (C.R.) matrix tablet formulations of rifampicin and isoniazid combination, to study the design parameters and to evaluate in vitro release characteristics. In the present study, a series of formulations were developed with different release rates and duration using hydrophilic polymers hydroxypropyl methylcellulose (HPMC) and hydroxypropyl cellulose (HPC). The duration of rifampicin and isoniazid release could be tailored by varying the polymer type, polymer ratio and processing techniques. Further, Eudragit L100-55 was incorporated in the matrix tablets to compensate for the pH-dependent release of rifampicin. Rifampicin was found to follow linear release profile with time from HPMC formulations. In case of formulations with HPC, there was an initial higher release in simulated gastric fluid (SGF) followed by zero order release profiles in simulated intestinal fluid (SIFsp) for rifampicin. The release of isoniazid was found to be predominantly by diffusion mechanism in case of HPMC formulations, and with HPC formulations release was due to combination of diffusion and erosion. The initial release was sufficiently higher for rifampicin from HPC thus ruling out the need to incorporate a separate loading dose. The initial release was sufficiently higher for isoniazid in all formulations. Thus, with the use of suitable polymer or polymer combinations and with the proper optimization of the processing techniques it was possible to design the C.R. formulations of rifampicin and isoniazid combination that could provide the sufficient initial release and release extension up to 24h for both the drugs despite of the wide variations in their physicochemical properties.
Solid state NMR and LVSEM studies on the hardening of latex modified tile mortar systems
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rottstegge, J.; Arnold, M.; Herschke, L.
Construction mortars contain a broad variety of both inorganic and organic additives beside the cement powder. Here we present a study of tile mortar systems based on portland cement, quartz, methyl cellulose and different latex additives. As known, the methyl cellulose stabilizes the freshly prepared cement paste, the latex additive enhances final hydrophobicity, flexibility and adhesion. Measurements were performed by solid state nuclear magnetic resonance (NMR) and low voltage scanning electron microscopy (LVSEM) to probe the influence of the latex additives on the hydration, hardening and the final tile mortar properties. While solid state NMR enables monitoring of the bulkmore » composition, scanning electron microscopy affords visualization of particles and textures with respect to their shape and the distribution of the different phases. Within the alkaline cement paste, the poly(vinyl acetate) (VAc)-based latex dispersions stabilized by poly(vinyl alcohol) (PVA) were found to be relatively stable against hydrolysis. The influence of the combined organic additives methyl cellulose, poly(vinyl alcohol) and latexes stabilized by poly(vinyl alcohol) on the final silicate structure of the cement hydration products is small. But even small amounts of additives result in an increased ratio of ettringite to monosulfate within the final hydrated tile mortar as monitored by {sup 27}Al NMR. The latex was found to be adsorbed to the inorganic surfaces, acting as glue to the inorganic components. For similar latex water interfaces built up by poly(vinyl alcohol), a variation in the latex polymer composition results in modified organic textures. In addition to the networks of the inorganic cement and of the latex, there is a weak network build up by thin polymer fibers, most probably originating from poly(vinyl alcohol). Besides the weak network, polymer fibers form well-ordered textures covering inorganic crystals such as portlandite.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Knott, Brandon C.; Crowley, Michael F.; Himmel, Michael E.
The processive cycle of the bacterial cellulose synthase (Bcs) includes the addition of a single glucose moiety to the end of a growing cellulose chain followed by the translocation of the nascent chain across the plasma membrane. The mechanism of this translocation and its precise location within the processive cycle are not well understood. In particular, the molecular details of how a polymer (cellulose) whose basic structural unit is a dimer (cellobiose) can be constructed by adding one monomer (glucose) at a time are yet to be elucidated. Here, we have utilized molecular dynamics simulations and free energy calculations tomore » the shed light on these questions. We find that translocation forward by one glucose unit is quite favorable energetically, giving a free energy stabilization of greater than 10 kcal mol-1. In addition, there is only a small barrier to translocation, implying that translocation is not rate limiting within the Bcs processive cycle (given experimental rates for cellulose synthesis in vitro). Perhaps most significantly, our results also indicate that steric constraints at the transmembrane tunnel entrance regulate the dimeric structure of cellulose. Namely, when a glucose molecule is added to the cellulose chain in the same orientation as the acceptor glucose, the terminal glucose freely rotates upon forward motion, thus suggesting a regulatory mechanism for the dimeric structure of cellulose. We characterize both the conserved and non-conserved enzyme-polysaccharide interactions that drive translocation, and find that 20 of the 25 residues that strongly interact with the translocating cellulose chain in the simulations are well conserved, mostly with polar or aromatic side chains. Our results also allow for a dynamical analysis of the role of the so-called 'finger helix' in cellulose translocation that has been observed structurally. Taken together, these findings aid in the elucidation of the translocation steps of the Bcs processive cycle and may be widely relevant to polysaccharide synthesizing or degrading enzymes that couple catalysis with chain translocation.« less
Peciulyte, Ausra; Anasontzis, George E; Karlström, Katarina; Larsson, Per Tomas; Olsson, Lisbeth
2014-11-01
The industrial production of cellulolytic enzymes is dominated by the filamentous fungus Trichoderma reesei (anamorph of Hypocrea jecorina). In order to develop optimal enzymatic cocktail, it is of importance to understand the natural regulation of the enzyme profile as response to the growth substrate. The influence of the complexity of cellulose on enzyme production by the microorganisms is not understood. In the present study we attempted to understand how different physical and structural properties of cellulose-rich substrates affected the levels and profiles of extracellular enzymes produced by T. reesei. Enzyme production by T. reesei Rut C-30 was studied in submerged cultures on five different cellulose-rich substrates, namely, commercial cellulose Avicel® and industrial-like cellulosic pulp substrates which consist mainly of cellulose, but also contain residual hemicellulose and lignin. In order to evaluate the hydrolysis of the substrates by the fungal enzymes, the spatial polymer distributions were characterised by cross-polarisation magic angle spinning carbon-13 nuclear magnetic resonance (CP/MAS (13)C-NMR) in combination with spectral fitting. Proteins in culture supernatants at early and late stages of enzyme production were labeled by Tandem Mass Tags (TMT) and protein profiles were analysed by liquid chromatography-tandem mass spectrometry. The data have been deposited to the ProteomeXchange with identifier PXD001304. In total 124 proteins were identified and quantified in the culture supernatants, including cellulases, hemicellulases, other glycoside hydrolases, lignin-degrading enzymes, auxiliary activity 9 (AA9) family (formerly GH61), supporting activities of proteins and enzymes acting on cellulose, proteases, intracellular proteins and several hypothetical proteins. Surprisingly, substantial differences in the enzyme profiles were found even though there were minor differences in the chemical composition between the cellulose-rich substrates. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.