Structural modification of bacterial cellulose

The microfibrillar nature of bacterial cellulose produced by Acetobacter was modified by various chemical reagents in a culture medium. The chemical reagents included antibiotics to inhibit cell division or certain protein synthesis, and reducing reagents that induce reductive cleavage of disulfide bonds in proteins. Among the reagents tested, nalidixic acid and chloramphenicol induced elongation of bacteria, resulting in the formation of wider cellulose ribbons or aggregates of ribbons. The Young's modulus of the sheets made from such cellulose increased, while dithiothreitol, which produced ribbons having only 45% of the width of the control, produced sheets with undiminished Young's modulus. Although further study is necessary to clarify the effect of such modifications, nalidixic acid and chloramphenicol produced a bacterial cellulose with superior mechanical properties.     

Surface acetylation of bacterial cellulose

Bacterial cellulose was partially acetylated by the fibrous acetylationmethod to modify its physical properties, while preserving the microfibrillarmorphology. The overall degree of substitution was varied from 0.04 to 2.77 bychanging the amount of acetic anhydride added. X-ray diffraction of thepartially acetylated samples showed the crystalline pattern of unmodified celluloseI up to moderate degrees of acetylation, and the change in peak widthsindicatedthat acetylation proceeded from the surface of microfibrils, leaving the coreportion unreacted. Scanning electron microscopy revealed that even low levelsofacetylation were effective to maintain the original microfibrillar morphologyofbacterial cellulose on direct drying from water.     

Surface modification of cellulose with plant triglycerides for hydrophobicity

Hydrophobic cotton was achieved by surface modification of the cellulose with triglycerides from several plant oils including soybean, rapeseed, olive and coconut oils. These oils were delivered to the cellulose substrates in homogeneous solutions of ethanol or acetone as well as aqueous emulsions. Surface modification was facilitated by solvent evaporation followed by heating between 110 and 120 °C for 60 min. All oils, except for coconut, produced hydrophobic and less water-absorbing cotton, supporting the desirable role of higher unsaturation in the fatty acids to achieve crosslinked network. The most hydrophobic surfaces were obtained by the reaction with 1% soybean oil in acetone. On both bleached and scoured cotton, a water contact angle of 80° and water absorption value of 0.82 μL/mg were achieved. The acquired hydrophobicity was not only retained after water washing but also improved with subsequent exposures to elevated temperatures. The surface tension of scoured cotton cellulose was lowered from 63.81 mJ/m² to 25.74 mJ/m² when modified by soybean oil delivered in acetone, which is lower than that of poly(ethylene terephthalate). An aqueous emulsion of soybean oil also rendered the scoured cotton hydrophobic, which shows promise for a green chemistry and bio-based approach to achieve water repellency on cellulosic materials.     

Characterization of anionic and cationic functionalized bacterial cellulose nanofibres for controlled release applications

Bacterial cellulose (BC) is a biocompatible biopolymer synthesized by Gluconacetobacter xylinus. In this study, BC was oxidized and aminated to produce hydrogels for biomedical applications, and the products were characterized. A carboxyl (pK_a of 3.9 ± 0.1) content of 1.13 ± 0.02 mmol/g was obtained with the TEMPO-catalyzed oxidation. Epichlorohydrin-mediated amination introduced amine groups (pK_a of 11.0 ± 0.1) up to 1.74 ± 0.06 mmol/g. The oxidation of BC caused a decrease in its ζ-potential to ?103 ± 6 mV, and amination increased the ζ-potential to ?4 ± 6 mV. The fibre diameter decreased after both reactions. The high absolute value of the ζ-potential for oxidized BC led to superior colloidal stability in water, and a 390 % increase in water retention. The oxidized BC hydrogel was also found to increase in water retention fivefold from pH 1 to 7, making it a smart hydrogel. The cationic and anionic BC hydrogels described here could be used for several biomedical applications, including self-assembling drug delivery devices.     

Homogeneous and porous modified bacterial cellulose achieved by in situ modification with low amounts of carboxymethyl cellulose

To improve the rehydration ability of bacterial cellulose (BC), many macromolecules have been used as modifiers in previous reports. However, the aggregation of additives in the BC matrix appears to be inevitable. We investigated different parts of a BC pellicle, which was achieved by in situ modification with carboxymethyl cellulose (CMC) in culture with Gluconacetobacter xylinus ATCC53582 or Enterobacter sp. FY-07. We observed a concentration gradient of CMC in the BC pellicle from G. xylinus ATCC53582, but not with Enterobacter sp. FY-07. Low concentrations of CMC (0.01 %, m/v) are sufficient to modify BC in situ in culture with Enterobacter sp. FY-07, in which CMC could sufficiently contact with the newly formed BC. The crystallinity of the modified BC decreased by more than 39.8 %, and its rehydration ability and water holding capacity increased by 43.3 and 31.0 %, respectively. Unlike the pellicle of modified BC achieved from obligate aerobes, such as G. xylinus ATCC53582, that produced by Enterobacter sp. FY-07 exhibited better homogeneity and porosity.     

Surface modification of alumina nanofibres for the selective adsorption of alachlor and imazaquin herbicides

The effective removal of pollutants using a thermally and chemically stable substrate that has controllable absorption properties is a goal of water treatment. In this study, the surfaces of thin alumina (γ-Al(2)O(3)) nanofibres were modified by the grafting either of two organosilane agents, 3-chloro-propyl-triethoxysilane (CPTES) and octyl-triethoxysilane (OTES). These modified materials were then trialed as absorbents for the removal of two herbicides, alachlor and imazaquin from water. The formation of organic groups during the functionalisation process established super hydrophobic sites on the surfaces of the nanofibres. This super hydrophobic group is a kind of protruding adsorption site which facilitates the intimate contact with the pollutants. OTES grafted substrate were shown to be more selective for alachlor while imazaquin selectivity is shown by the CPTES grafted substrate. Kinetics studies revealed that imazaquin was rapidly adsorbed on CPTES-modified surfaces. However, the adsorption of alachlor by OTES grafted surface was achieved more slowly.     

Surface modification of cellulose nanocrystal with chitosan oligosaccharide for drug delivery applications

A novel drug delivery system based on two of the most abundant natural biopolymers was developed by modifying the surface of oxidized cellulose nanocrystal (CNC) with chitosan oligosaccharide (CS_OS). First, the primary alcohol moieties of CNC were selectively oxidized to carboxyl groups using the 2,2,6,6-tetramethylpiperidine-1-oxyl radical catalyst. The amino groups of CS_OS were then reacted with carboxylic acid groups on oxidized CNC (CNC-OX) via the carbodiimide reaction using N-hydroxysuccinimide and 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide as coupling agents. Successful grafting of CS_OS to CNC-OX was confirmed by infrared spectroscopy, thermogravimetry, potentiometric titration, and zeta potential measurements. The grafting resulted in a conversion of ~90 % carboxyl groups on CNC-OX and the degree of substitution was 0.26. CNC–CS_OS nanoparticles showed a binding efficiency of 21.5 % and a drug loading of 14 % w/w. A drug selective electrode was used to directly measure the concentration of procaine hydrochloride released from CNC–CS_OS particles. The in vitro drug release was studied at pH 8 and the nanoparticles revealed a fast release of up to 1 h, which can be used as biocompatible and biodegradable drug carriers for transdermal delivery applications.     

Surface oxidation of carbon nanofibres

Carbon nanofibres of the fishbone and parallel types were surface-oxidised by several methods. The untreated and oxidised fibres were studied with infrared spectroscopy, thermogravimetric analysis and X-ray photoelectron spectroscopy (XPS). Oxidation in a mixture of concentrated nitric and sulfuric acids proved to be the most effective method for creating oxygen-containing surface groups. This treatment results not only in the formation of carboxy and carboxyic anhydride groups, but also in the generation of ether-type oxygen groups between graphitic layers that are puckered at their edges. The IR spectroscopic data clearly show that the formation of oxygen-containing surface groups occurs at defect sites on the carbon nanofibres and that oxidation proceeds via carbonyl groups and other oxides to carboxy and carboxyic anhydride groups. Owing to the presence of defects, the two types of fibre have similar surface reactivities. With parallel nanofibres, in contrast to fishbone fibres, the macroscopic structure was severely affected by treatment with HNO(3)/H(2)SO(4). The HNO(3)/H(2)SO(4)-treated fibres are highly wettable by water.     

Susceptibility of never-dried and freeze-dried bacterial cellulose towards esterification with organic acid

The susceptibility of (1) never-dried and (2) freeze-dried bacterial cellulose (BC) towards organic acid esterification is reported in this work. When never-dried BC (BC which was solvent exchanged from water through methanol into pyridine) was modified with hexanoic acid, it was found that the degree of substitution (DS) was significantly lower than that of hexanoic acid modified freeze-dried BC. The crystallinity of freeze-dried BC hexanoate was found to be significantly lower compared to neat BC and never-dried BC hexanoate. This result, along with the high DS indicates that significant bulk modification occurred during the esterification of freeze-dried BC. Such results were not observed for never-dried BC hexanoate. All these evidence point towards to fact that freeze-dried BC was more susceptible to organic acid esterification compared to never-dried BC. A few hypotheses were explored to explain the observed behaviour and further investigated to elucidate our observation; the effect of residual water in cellulose, the accessibility of hydroxyl groups and the crystal structure of never-dried and freeze-dried BC on the susceptibility of cellulose fibrils to esterification, respectively. However, the investigation of these hypotheses raised more questions and we are still left with the main question; why do BC nanofibres behave differently when modifying freeze-dried BC or never-dried BC?     

Surface characterization of TEMPO‐oxidized bacterial cellulose

In this study, we focused on the surface character of bacterial cellulose (BC) before and after oxidation mediated by 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO).Solid‐state ¹³C NMR, XPS, SEM, contact angle and surface free energy analyses were performed to investigate the effects of various parameters (reaction time and oxidant and catalyst concentrations) on the surface composition, morphology and polarity of the BC. The results provided by the combined use of these techniques showed that hydrogen bonds were disrupted on the BC surface after carboxylation occurred; therefore, the surface of oxidized BC was rougher than that of the original BC, and the surface free energy, especially the polar components, increased after oxidation. Copyright © 2013 John Wiley & Sons, Ltd.     

Surface modification of hydroxyapatite to avoid bacterial adhesion

Hydroxyapatite was surface-modified by adsorption of nonionic polymers carrying phosphate groups as anchoring groups. A combination of alcohol ethoxylate and alkyl phosphate was also used. The possibility of interfering with early microbial colonization on apatite, mimicking the tooth surface, was investigated using radiolabelledStreptococcus mutans as model bacteria. The polymers, a nonionic cellulose ether and an EO/PO block copolymer based on polyglycerol as starting alcohol, were effective in buffer but gave only limited reduction of bacterial adhesion when the apatite had been pretreated with saliva. A 11 molar mixture of alcohol ethoxylate and alkyl phosphate was effective both with and without saliva, however. Studies with¹⁴C-labeled compounds, as well as microelectrophoresis experiments, indicate that an unsymmetrical double layer is formed on the apatite surface with predominantly alkyl phosphate in the inner layer and with alcohol ethoxylate pointing towards the water phase.     

Surface modification of oxidized cellulose haemostat by argon plasma treatment

In this paper we focused on cold plasma treatment of oxidized cellulose haemostat. Oxidized cellulose was modified in inert argon plasma. The changes of surface composition were examined by XPS and FTIR. Surface morphology of fibres was studied by SEM. Gravimetry was used to study ablation and water absorption. Antibacterial effect of pristine and plasma treated samples was examined by growth of Escherichia coli and Staphylococcus epidermidis. Behaviour of pristine and plasma treated samples in water, physiological saline solution and phosphate buffered saline was observed by changes in the pH of their solutions. Modification of oxidized cellulose by inert argon plasma caused significant changes in the chemical composition of its surface layers as well as changes in morphology of those layers while maintaining or improving the antibacterial properties. We found out that modification by inert argon plasma improves the properties necessary for haemostatic function of oxidized cellulose.     

Surface modification of cellulose nanowhiskers for application in thermosetting epoxy polymers

Cellulose nanowhiskers (CNWs) were chemically modified with dodecenyl succinic anhydride to obtain hydrophobic CNWs called DCNWs. Surface modification was confirmed by infrared spectroscopy, transmission electron microscopy, and X-ray diffraction. The surface substitution degree determined by X-ray photoelectron spectroscopy was 0.30. Nanocomposites were prepared by incorporating different amounts of DCNWs pre-dispersed in a small amount of acetone into an epoxy matrix. Scanning electron microscope demonstrated that DCNWs dispersed well in the epoxy matrix. A strong interaction was proved between the DCNWs and epoxy matrix, as results of which the nanocomposites exhibited an obvious increase in T _g by about 30 °C, simultaneous increases in tensile strength, Young’s modulus, and strain at break; and an improvement in the hydrothermal properties. Compared with the neat epoxy, the nanocomposite containing 3.5 wt% of DCNWs exhibited an increase in tensile strength by 82 %, Young’s modulus by 21 %, and a strain at break by 198 %.     

Surface modification of materials: Electrografting of organic films

The modification of surfaces is possible through a number of reagents (silanes, thiols, phosphonic acids, amines, and so on) among which diazonium salts have gained an increasing importance; this short review highlights the new achievements in this field.     

Thermal degradation behavior of cellulose fibers partially esterified with some long chain organic acids

The thermal degradation behavior of cellulose fibers and some fibrous cellulose esters with partial degree of substitution has been studied by thermogravimetry analysis (TG) and differential scanning calorimetry (DSC). Cellulose esters were prepared by heterogeneous esterification in Py/TsCl with unsaturated or saturated long chain organic acids [undecylenic (C₁₁), undecanoic (C₁₁), oleic (C₁₈) and stearic (C₁₈)]. The thermal degradation of cellulose fibers follows a one-step process. The thermal stability of cellulose esters is inferior to that of unmodified cellulose fibers and the thermograms show a two-step degradation process, probably controlled by crosslinking reactions, which occur during thermal decomposition. Exothermic peaks in the DSC thermograms are also an indication of such reactions. Kinetic parameters such as the activation energy E, order of decomposition n, and frequency factor Z were obtained following the Friedman method. The cellulose sample followed first order of decomposition, however for cellulose esters higher orders were observed.     

Surface modification of natural cellulose substances:toward functional materials and applications

Combining various synthetic chemical processes and biological assemblies provides a promising strategy for the design and fabrication of functional materials with tailored structures and properties.The unique multilevel structures and morphologies of natural cellulose substances such as ordinary commercial laboratory filter paper make them ideal platforms for the self-assemblies of various functional guest molecules that are to be deposited on the surfaces of their fine structures,and the resulting composite matters show significant potentials for various applications.The surface sol-gel process was employed to deposit ultrathin metal-oxide(e.g.,titania and zirconia)gel films to coat the cellulose nanofibers in bulk filter papers;thereafter,monolayers of specific guest substrates were immobilized onto the surfaces of the metal-oxide gel films.Highly selective,sensitive,and reversible chemosensors based on the surface modification of filter paper were obtained toward the fluorescence and colorimetric detection of various analytes such as heavy-metal ions,inorganic anions,amino acids,and gases.Cellulosebased composite materials with superhydrophobic,antibacterial,or luminescent properties were fabricated by self-assembly approaches toward practical applications.     

Surface modification of inorganic oxide particles with silane coupling agent and organic dyes

The silane coupling agent 3‐glycidoxypropyl trimethoxylsilane (GPS) was grafted onto the surface of silica gel, P ₂ glass beads and TiO ₂ oxide particles. FT‐IR, thermogravimetric and elemental analysis were used to characterize the modified particles. The effects of various factors on the GPS grafting efficiency such as catalyst, GPS concentration, reaction temperature and time were studied. After modification with GPS, the xanthene dye rhodamine B and azo dyes 4‐phenylazophenol and 4‐phenylazoaniline, respectively, were grafted on to the particles, which were then used as pigment fillers. The colors of the pigments were adjusted by changing the kind of dyes, the concentration, the pH and the reaction solvents. Copyright © 2001 John Wiley & Sons, Ltd.     

Topochemical modification of cotton fibres with carboxymethyl cellulose

Adsorption of carboxymethyl cellulose (CMC) as a method to introduce charged (ionizable) groups onto cellulose cotton fibre surfaces was investigated. The method was based on application of a previously published method used for wood fibres. The amount of adsorbed ionizable groups was determined indirectly by analysis of CMC in solution by the phenol–sulphuric acid method and directly by conductometric titration of the fibres. Results from the two methods correlated well. The molecular weight and purity of the CMC had an influence on its adsorption onto cotton; high molecular weight CMC was preferentially adsorbed. The adsorbed charge correlated linearly with the amount of CMC adsorbed. The total charge of the cotton fibres could be increased by more than 50% by adsorption of CMC. It is expected that this modification procedure can be used in a wide spectrum of practical applications. Lidija Fras Zemljič and Karin Stana-Kleinschek are the members of the European Polysaccharide Network of Excellence (EPNOE).     

Homogeneous modification of carbon nanotubes with cellulose acetate

An efficient strategy that comprised shorten,chain extension,active groups introducing and homogeneous reaction tactics,was adopted to modify multiwalled carbon nanotubes(MWNTs) with cellulose acetate(CA).Specially,by utilizing 2,4,6-trichloro- 1,3,5-triazine,a reactive intermediate of the MWNTs(MWNT-triazine) was obtained.Suitable solubility of the MWNT-triazine helps make the homogeneous modification become reality.Detailed characterizations further verified that reaction between chloride atoms in the ...     

Surface modification and characterization of indium-tin oxide for organic light-emitting devices

In this work, we used different treatment methods (ultrasonic degreasing, hydrochloric acid treatment, and oxygen plasma) to modify the surfaces of indium-tin oxide (ITO) substrates for organic light-emitting devices. The surface properties of treated ITO substrates were studied by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), sheet resistance, contact angle, and surface energy measurements. Experimental results show that the ITO surface properties are closely related to the treatment methods, and the oxygen plasma is more efficient than the other treatments since it brings about smoother surfaces, lower sheet resistance, higher work function, and higher surface energy and polarity of the ITO substrate. Moreover, polymer light-emitting electrochemical cells (PLECs) with differently treated ITO substrates as device electrodes were fabricated and characterized. It is found that surface treatments of ITO substrates have a certain degree of influence upon the injection current, brightness, and efficiency, but hardly upon the turn-on voltages of current injection and light emission, which are in agreement with the measured optical energy gap of the electroluminescent polymer. The oxygen plasma treatment on the ITO substrate yields the best performance of PLECs, due to the improvement of interface formation and electrical contact of the ITO substrate with the polymer blend in the PLECs.