Efficient Preparation of Small-Sized Transition Metal Dichalcogenide Nanosheets by Polymer-Assisted Ball Milling

Two-dimensional (2D) transition metal dichalcogenide nanosheets (TMDC NSs) have attracted growing interest due to their unique structure and properties. Although various methods have been developed to prepare TMDC NSs, there is still a great need for a novel strategy combining simplicity, generality, and high efficiency. In this study, we developed a novel polymer-assisted ball milling method for the efficient preparation of TMDC NSs with small sizes. The use of polymers can enhance the interaction of milling balls and TMDC materials, facilitate the exfoliation process, and prevent the exfoliated nanosheets from aggregating. The WSe₂ NSs prepared by carboxymethyl cellulose sodium (CMC)-assisted ball milling have small lateral sizes (8~40 nm) with a high yield (~60%). The influence of the experimental conditions (polymer, milling time, and rotation speed) on the size and yield of the nanosheets was studied. Moreover, the present approach is also effective in producing other TMDC NSs, such as MoS₂, WS₂, and MoSe₂. This study demonstrates that polymer-assisted ball milling is a simple, general, and effective method for the preparation of small-sized TMDC NSs.     

Biodegradation of ldpe/cellulose blends by common fungi

We have developed a cellulose-polyethylene blend polymer film for degradative susceptibility to brown rot or cellulasic fungi. Paxon low-density polyethylene (LDPE) polymer pellets were melt-blended with 8855 cellulose. A pure polyethylene sample was melted, pressed and used as the control. Naturally occurring fungi were harvested from decaying wood and cultured on full nutrient agar until individual phenotypes developed. The discrete fungal colonies were isolated and transferred to bacteriological agar with carboxymethylcellulose as the only carbon source. Surviving fungi were subjected to an indirect cellulase assay to confirm cellulolytic properties. Trichoderma viride showed 100% surface area growth on low-density polyethylene (LDPE) blended with 8% (w/w) cellulose in 90 days. Growth coverage by Gliomastix on LDPE blended with 8% cellulose reached 100 % in 150 days, and up to 72% growth activity on blends with 1.5% cellulose, 1% cellulose, and the control LDPE.     

Aqueous pretreatment for reactive ball milling of cellulose

Aqueous swelling pretreatment of cellulose was found highly effective for reactive ball milling to prepare surface-esterified cellulose nanofibers. Compared with starting from dry cellulose, water- or 2 % NaOH-pre-swollen materials were esterified and dispersed in significantly shorter milling time. Especially commercial kraft pulp was difficult to disperse even with water pretreatment, but 2 % NaOH treatment gave full surface esterification with a bulk degree of substitution of 0.69 by 12-h ball milling, presumably because of removal of non-cellulosic components.     

Fabrication of carbon quantum dots via ball milling and their application to bioimaging

Carbon quantum dots (CQDs) with an average diameter of 3 nm, exhibiting blue photoluminescence, have been obtained from commercial conductive carbon black by a cost-effective and straightforward exfoliation method using dry ball milling in the presence of sodium carbonate. As a secondary abrasive medium, sodium carbonate provides effective exfoliation of carbon black with a high degree of CQD graphitization and plays an essential role in the functionalization of CQDs with oxygen groups. Due to the low toxicity of CQDs against HeLa cancer cells (cell viability above 90% at a CQD concentration of 200 μg cm⁻³) and the ability to penetrate cells and emit blue light, CQDs are possibly suitable for biological imaging of cells.     

Oxidation of Primary Alcohol Groups of Naturally Occurring Polysaccharides with 2,2,6,6-Tetramethyl-1-Piperidine Oxoammonium Ion

ABSTRACT

The primary alcohol groups of ten polysaccharides, with widely different structures and water solubilities, were oxidized to carboxyl groups using 2,2,6,6-tetramethyl-1-piperidine oxoammonium ion (TEMPO) at pH 10.8 and 0°C. The yield and selectivity for the primary alcohol group were high for all ten of the polysaccharides. The oxidation greatly increased the water-solubility of the polysaccharides. Water-insoluble polysaccharides such as amylose, cellulose, and chitin became water-soluble to the extent of approximately 10% (w/v). The water-soluble polysaccharides had their degree of solubility doubled or tripled. The specific optical rotation, viscosity, and gelling properties with calcium ion were determined. The oxidized polysaccharides are new anionic polymers with unique structures that could have application as gums, gels, and films.     

Fabrication of carbon nanofiber by pyrolysis of freeze-dried cellulose nanofiber

The possibility of fabricating carbon nanofibers from cellulose nanofibers was investigated. Cellulose nanofiber of ~50 nm in diameter was produced using ball milling in an eco-friendly manner. The effect of the drying techniques of cellulose nanofibers on the morphology of carbon residue was studied. After pyrolysis of freeze-dried cellulose nanofibers below 600 °C, amorphous carbon fibers of ~20 nm in diameter were obtained. The pyrolysis of oven-dried precursors resulted in the loss of original fibrous structures. The different results arising from the two drying techniques are attributed to the difference in the spatial distance between cellulose nanofiber precursors.     

Calorimetric investigation of some polysaccharides subjected to high-pressure plastic deformation

Differential scanning calorimetry is used to establish that, at 20–200°C, an endothermic process proceeds in polysaccharides (cellulose, methyl cellulose, cellulose di- and triacetate, chitin, chitosan, starch, etc.) whose enthalpy is noticeably enhanced after plastic deformation of the polymers at 0.5–2.0 GPa. By the example of cellulose, it is shown that the process is associated with water present in the polymers. An increase in the enthalpy as a result of pressure treatment is due to both structural transformation of cellulose I into cellulose II and the intensification of intermolecular interactions in the polymers that is due to formation of a system of electric charges in the samples.     

Improved anti-inflammatory properties for naproxen with cyclodextrin-grafted polysaccharides

Mannan and carboxymethylcellulose, previously activated by periodate oxidation, were grafted with mono-6-butylenediamino-6-deoxy-beta-cyclodextrin derivatives by reductive alkylation in the presence of sodium borohydride. The formation of supramolecular complexes between these polymers and Naproxen was confirmed by fluorescence spectroscopy. The solubility of the drug was 3.8-4.6 fold increased in the presence of the cyclodextrin-grafted polysaccharides. The in vivo anti-inflammatory property of Naproxen was 1.7 times higher after supramolecular association with beta-cyclodextrin-branched mannan.     

Nonlinear optical absorption of nanocomposite films made from polymers and single-walled carbon nanotubes: The effect of nanotube type and polymer matrix

Nonlinear optical absorption at a wavelength of 1080 nm for nanocomposite thin films made from polymers and single-walled carbon nanotubes (SWNTs) was studied by the longitudinal scanning (z-scan) technique. Two SWNT types differing in the synthesis procedure (HipCO and arc evaporation techniques) were used for the preparation of nanocomposites based on the polymers carboxymethylcellulose (CMC) and poly(vinyl alcohol) (PVAL). The nonlinear absorption coefficients were measured to be ?5.0 × 10^?7 and ?3.9 × 10^?7 cm/W for the CMC-SWNT/HipCO and CMC-SWNT/Arc composite films and ?1.7 × 10^?7 and ?0.9 × 10^?7 cm/W for the PVAL-SWNT/HipCO and PVAL-SWNT/Arc films, respectively. It was found that the film nanocomposites based on carboxymethylcellulose had a higher absolute value of the nonlinear absorption coefficient than the films in which PVAL was used as the polymer matrix.     

A facile one-step way for extraction of nanocellulose with high yield by ball milling with ionic liquid

93.1% yield of nanocellulose was successfully extracted from cellulose powder (CP) by planetary ball milling in the presence of ionic liquid (IL) of 1-butyl-3-methylimidazolium chloride (BMIMCl). The morphology of nanofibrillated cellulose present in fibrous network with 10–25 nm in diameter and micrometer scale in length and the chemical composition and crystal structure were maintained as cellulose type I. At 600 °C degradation temperature, the residue amount of the obtained nanocellulose was about 55% more that of CP, implying it had higher thermal stability. The used BMIMCl was recovered and reused at least 4 times. The nanocellulose obtained by using the recovered IL also demonstrated the same properties as those from the fresh one. For comparison, another kind of IL of 1-ethyl-3-methylimidazolium acetate (EMIMOAc) was also used in this study. It is found that the ball milling of cellulose in the presence of IL is an effective and environmental friendly way for the production of nanocellulose with high yield.     

A novel approach for the homogenization of cellulose to use micro‐amounts for stable isotope analyses

Climate reconstructions using stable isotopes from tree‐rings are steadily increasing. The investigations concentrate mostly on cellulose due to its high stability. In recent years the available amount of cellulose has steadily decreased, mainly because micro‐structures of plant material have had to be analyzed. Today, the amounts of cellulose being studied are frequently in the milligram and often in the microgram range. Consequently, homogeneity problems with regard to the stable isotopes of carbon and oxygen from cellulose have occurred and these have called for new methods in the preparation of cellulose for reliable isotope analyses. Three different methods were tested for preparing isotopically homogenous cellulose, namely mechanical grinding, freezing by liquid nitrogen with subsequent milling and ultrasonic breaking of cellulose fibres. The best precision of isotope data was achieved by freeze‐milling and ultrasonic breaking. However, equipment for freeze‐milling is expensive and the procedure is labour‐intensive. Mechanical grinding resulted in a rather high loss of material and it is also labour‐intensive. The use of ultrasound for breaking cellulose fibres proved to be the best method in terms of rapidity of sample throughput, avoidance of sample loss, precision of isotope results, ease of handling, and cost. Copyright © 2009 John Wiley & Sons, Ltd.     

Inhibitive properties of amphoteric, water-soluble cellulosic polymers on bentonite swelling

Amphoteric, water-soluble cellulose derivatives were prepared by the quaternization of anionic carboxymethylcellulose (CMC) with 3-chloro-2-hydroxypropyltrimethyl-ammonium chloride. These polymers suppress the swelling of bentonite more effectively than CMC and their inhibitive effect depends on the degree of quaternization, the molecular conformation and the type of counterions. Received: 13 October 1998 Accepted in revised form: 24 November 1998     

Preparation and properties of a new type of comb-shaped, amphiphilic cellulose derivative

Comb-shaped, amphiphilic O-(2- hydroxy-3-butoxypropyl) cellulose (HBPC) was prepared by a homogeneous reaction of cellulose with butyl glycidyl ether (BGE) in a 10% (w/w) LiCl--DMAc solution. It was found that: (a) the molar substitution (MS) of water-soluble HBPC ranges from 0.4 to 1.0, and is nearly equal to its degree of substitution (DS), indicating that the HBPC derivatives obtained are comb-shaped polymers; (b) the water-soluble HBPC shows a thermally reversible sol-gel transition in aqueous solution; and (c) the derivative having a DS of 0.6 shows surface activity with critical micelle concentration (cmc) in the order of 0.8 g/l and surface tension of 31.5 dyn/cm     

Medium Initial pH and Carbon Source Stimulate Differential Alkaline Cellulase Time Course Production in Stachybotrys microspora

The production profile of cellulases of the mutant strain A19 from the filamentous fungus Stachybotrys microspora was studied in the presence of various carbon sources (glucose, lactose, cellulose, carboxymethylcellulose (CMC), and wheat bran) and a range of medium initial pH (5, 7, and 8). Two extracellular cellulases from the Stachybotrys strain (endoglucanases and β-glucosidases) were monitored by enzymatic assay, sodium dodecyl sulfate–polyacrylamide gel electrophoresis, and zymogram analysis. Glucose and lactose repressed CMCase time course production while they permitted a strong β-glucosidase one. On Avicel cellulose, CMC, and wheat bran, both activities were highly produced. Wheat bran (WB) is the best carbon source with an optimum of production at days 5 and 6. The production kinetics of both activities were shown to depend on the medium initial pH, with a preference for neutral or alkaline pH in the majority of conditions. The exception concerned the β-glucosidase which was much more produced at acidic pH, on glucose and cellulose. Most interestingly, a constitutive and conditional expression of an alkaline endoglucanase was revealed on the glucose-based medium at an initial pH of 8 units. The zymogram analysis confirmed such conclusions and highlighted that carbon sources and the pH of the culture medium directed a differential induction of various endoglucanases and β-glucosidases.     

Enhancement of naringenin solution concentration by solid dispersion in cellulose derivative matrices

Naringenin (Nar) is an important bioactive flavonoid with poor organic solubility and oral bioavailability. It is highly promising for treatment of conditions including diabetes, hyperlipidemia, and hepatitis C infection. Amorphous solid dispersion (ASD) of Nar is an appealing way to enhance its solubility, and carboxylated cellulose esters are attractive polymers for this purpose because of their ability to stabilize drugs against crystallization in both solid and solution phases, while restricting drug release to the pH of the small intestine (ca. 6.8). We demonstrate that ASDs of Nar can be formed using such carboxylated cellulose derivatives as cellulose acetate adipate propionate (CAAdP), carboxymethylcellulose acetate butyrate (CMCAB) and hydroxypropylmethylcellulose acetate succinate (HPMCAS). We compare Nar solution concentrations and release profiles from these cellulosic ASDs to those from pure crystalline Nar, and to Nar ASD in poly(vinylpyrrolidinone) (PVP). We show that all polymers in this study form ASDs with Nar, that the PVP ASDs release Nar at both gastric (1.2) and small intestine (6.8) pH, and that the cellulosic polymers release Nar selectively at neutral pH. Solution concentrations of Nar are significantly enhanced from these ASDs. These preliminary studies indicate that HPMCAS, CAAdP, and CMCAB are practical ASD polymers for Nar due to their ability to generate and stabilize high solution concentrations, and their pH-triggered drug release.     

Crystalline transformation of native cellulose from cellulose I to cellulose ID polymorph by a ball-milling method with a specific amount of water

We have demonstrated for the first time that a mechano-chemical treatment of native cellulose with a specific amount of water (30 wt%) present ID the cellulose solid state caused the crystalline transformation from cellulose I into cellulose ID polymorph. X-ray diffractometry was used to show that the extent of transformation into cellulose ID increased with milling time. This specific phenomenon can be explained by considering the chain mobility ID the cellulose–water system, because ₁ ^1H measurement shows that cellulose molecules are most mobile when the water content ID around 30 wt%, and thus are favorable for molecular rearrangement under external forces.     

Physical and mechanical testing of essential oil-embedded cellulose ester films

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 (Cybopogon citratus), rosemary pepper (Lippia sidoides) and basil (Ocimum gratissimum) at concentrations of 10 and 20% (v/w). Results obtained showed that, in all films, the addition of the essential oil caused a decrease in the water vapor permeability due to the hydrophobic nature of the oil. The use of 20% of EO caused lower transparency of the films, although the change was not observed visually. Mechanical testing was done on cellulose acetate, cellulose acetate propionate and cellulose acetate butyrate. It was found that incorporation of lemongrass, basil and rosemary pepper EO significantly affected the Young's modulus, tensile strength and elongation at break of the cellulose ester films. The results suggested that the essential oils interacted with the polymers like plasticizers. The results were confirmed with thermal and microscopic studies.     

Determination of carboxymethyl-D-glucoses in the product of hydrolytic depolymerization of carboxymethylcellulose by isotachophoresis

Optimal conditions for isotachophoretic separation of carboxymethyl-D-glucoses formed by acidic depolymerization of carboxymethylcellulose were found. 6-O-carboxymethyl-D-glucose, 2-O-carboxymethyl-D-glucose and 3-O-carboxymethyl-D-glucose were identified and determined in the reaction mixture after carboxymethylcellulose hydrolysis. Relative reactivity of hydroxy groups in the glucopyranose unit of cellulose decreased in the following order: O(6)H greater than O(2)H much greater than O(3)H. This was found to be in agreement with the data published by other authors.     

Multi-layer nanopaper based composites

Native cellulose nanofibrils (CNF) were prepared from bleached birch pulp without any chemical or enzymatic pretreatment. These CNF were modified by adsorption of a small amount of water-soluble polysaccharides and used to prepare nanopapers, which were processed into composites by lamination with an epoxy resin and subsequently cured. The results were compared to the properties of composites prepared using bacterial cellulose nanopapers, since bacterial cellulose constitutes highly pure and crystalline cellulose. It was found that both types of nanopapers significantly improved both the thermal stability and mechanical properties of the epoxy resin. As anticipated, addition of only 2 wt% of water-soluble polysaccharides efficiently hindered crack-propagation within the nanopaper and significantly improved the tensile strength and work of fracture compared to composites containing a conventional nanopaper reinforcement. The mechanical properties of the composites thus reflected the improvement of the nanopaper properties by the polysaccharides. Moreover, it was possible to predict the properties of the final composite from the mechanical performance of the nanopapers.     

Chitosan based polyelectrolyte complexes

Polyelectrolyte complexes (PECs) are formed through the electrostatic interactions between polymers carrying opposite charges. Here are presented results of basic studies on the PECs of chitosan with other polysaccharides such as sodium alginate, carboxymethyl cellulose, polygalacturonic acid and κ‐carrageenan. An extensive study on chitosan/carboxymethyl cellulose membranes, regarding its swelling characteristics and water vapour sorption is offered. Also the interaction of chitosan with polyacrylic acid has been examined from the thermodynamic point of view.