The behaviour of cationic NanoFibrillar Cellulose in aqueous media

This paper deals, with cationically modified NanoFibrillar Cellulose (cat NFC), obtained by reacting a dissolving pulp with 2,3-epoxypropyl trimethylammonium chloride (EPTMAC). The cat NFC was thoroughly characterized in terms of morphology and physical properties. The dimensions of individual cellulose nanofibrils were determined by atomic force microscopy (AFM) imaging in water and in air. Fibrils as thin as 0.8–1.2 nm were observed in water. The fibril diameter changed upon drying and the average size was further quantified by image analysis. The experiments showed the importance of characterizing nanocellulosic materials in situ before drying. The fibril size in air was confirmed by cryogenic transmission electron microscopy (cryo-TEM), and it was found to be 2.6–3.0 nm. Smooth ultrathin films of cationic NFC were prepared by spincoating on silica substrates. The effect of electrolyte concentration and pH on swelling of the cationic NFC film was studied using a quartz crystal microbalance with dissipation. The results showed that at pH = 8 the cat NFC film was insensitive to electrolyte changes while at pH = 4.5, the water content of the film decreased with increasing ionic strength. The electrophoretic mobility measurements showed a cationic zeta potential for the cat NFC that decreased at increasing pH, verifying the swelling behaviour.     

Qualitative evaluation of microfibrillated cellulose using the crill method and some aspects of microscopy

It has been a challenge to develop rapid online characterisation techniques for nanocellulose given the fibrillar structure of the nanoparticles. The crill optical analyser uses optical response signals in the infrared (IR) and ultraviolet (UV) wavelength ranges to evaluate the particle size properties of micro/nanofibrillar cellulosic materials. In this work, the crill analyser was used to measure the projected areas of UV and IR light sources by measuring the light blocked by nanocellulosic particles. This work uses the crill methodology as a new, simplified technique to characterise the particle size distribution of nanocellulosic material based on chemi-thermomechanical pulp (CTMP), thermomechanical pulp (TMP), and sulphite pulp (SP). In the first part, hydrogen peroxide pretreatment of CTMP and TMP in a wing mill refiner followed by high-pressure homogenisation to produce microfibrillated cellulose (MFC) was evaluated using the crill method. In the second part, TEMPO oxidation of CTMP and SP combined with high-shear homogenisation to produce MFC was studied using the crill method. With 4 % hydrogen peroxide pretreatment, the crill values of the unhomogenised samples were 218 and 214 for the TMP and CTMP, respectively, improving to 234 and 229 after 18 homogenisation passes. The results of the TEMPO method indicated that, for the 5 mmol NaClO SP-MFC, the crill value was 108 units at 0 min and 355 units after 90 min of treatment, a 228 % improvement. The CTMP and TMP fibres and the MFC were freeze dried and fibrillar structure of the fibres and microfibrils was visualised using scanning electron and transmission electron microscopy.     

Water dispersion of cellulose II nanocrystals prepared by TEMPO-mediated oxidation of mercerized cellulose at pH 4.8

Mercerized wood cellulose was oxidized by 4-acetamide-TEMPO/NaClO/NaClO₂ system at 60 °C and pH 4.8 for 1–5 days. Mostly individual nanocrystals 4–7 nm in width and 100–200 nm in length were obtained by ultrasonication of the oxidized product in water. The nanocrystals had the cellulose II structure, and carboxylate contents of 2.0–2.4 mmol/g, indicating that these carboxylate groups were selectively formed on the cellulose II crystallite surfaces in mercerized cellulose. Moreover, the original wood cellulose and mercerized cellulose were acid-hydrolyzed, and then subjected to the TEMPO-mediated oxidation under the same conditions at pH 4.8 to prepare reference samples. TEM images, light transmittance and rheological properties of water dispersions showed that the nanocrystals prepared from mercerized cellulose by the TEMPO oxidation and sonication in water had the highest dispersibility of individual nanocrystals with less amounts of bundles in water, resulting from the highest carboxylate contents.     

Cellulose nanofibres by sonocatalysed-TEMPO-oxidation

The purpose of this work was to study the influence of acoustic cavitation on the oxidation of a mill bleached machine dried hardwood Kraft pulp. The oxidation of the pulp was carried out using 4-acetamido-TEMPO coupled with NaOCl/NaBr as co-oxidizer. The carboxylate content was increased by about 30% without any adverse impact on the degree of polymerization in the case of oxidations under acoustic cavitation compared to the reference without acoustic cavitation. A close correlation between the yield of nanocellulose and the carboxylate content of the oxidized pulps was observed. The individualized cellulose nanofibres were 3–4 nm in width and a few microns in length.     

Wood cellulose nanofibrils prepared by TEMPO electro-mediated oxidation

A softwood bleached kraft pulp (SBKP) was subjected to electro-mediated oxidation in water with TEMPO or 4-acetamido-TEMPO without any chlorine-containing oxidant. Solid recovery ratios of water-insoluble fractions of the oxidized SBKPs were more than 80%, and C6-carboxylate contents increased up to approximately 1 mmol g⁻¹ after oxidation for 48 h. Significant amounts of C6-aldehyde groups (0.17–0.38 mmol g⁻¹) were also formed in the oxidized SBKPs. The degree of polymerization decreased from 2,200 to 520 and 1,400 by the oxidation for 48 h with TEMPO at pH 10 and 4-acetamido-TEMPO at pH 6.8, respectively. The original cellulose I crystal structure and crystallinity of SBKP were maintained after the oxidation, indicating that all C6-oxidized groups were selectively formed on crystalline cellulose microfibril surfaces. The oxidized SBKPs with carboxylate contents of more than 0.9 mmol g⁻¹ were convertible to individual cellulose nanofibrils in yields of more than 80% by disintegration in water.     

Enhancing the effectiveness of a laccase–TEMPO treatment has a biorefining effect on sisal cellulose fibres

Enhancing the effectiveness of a laccase–TEMPO treatment on sisal pulp by increasing pulp consistency was for the first time found to increase the biorefining potential of this enzyme–mediator system. The operating conditions used were those previously found to maximize oxidative functionalization and paper strength. Prior to the enzyme treatment, the pulp was refined at a variable intensity (0, 3,000 and 4,500 revolutions) in order to ascertain whether the increased surface area would lead to enhanced functionalization and boost the refining effect as a result. Increasing pulp consistency increased the contents in aldehyde and carboxyl groups by 130% and 94%, respectively. Also, it resulted in more marked reduction of pulp viscosity during the enzyme treatment, especially at a high refining intensity; this had a detrimental effect on fibre strength and significantly reduced tear strength in the refined pulp. Oxidized pulp exhibited a considerably increased water retention value with respect to the initial pulp, particularly after refining. Dry tensile index was increased by 21, 18 and 12%, and burst index by 23, 16 and 13% at 0, 3,000 and 4,500 rev, respectively, by the laccase–TEMPO treatment as a result of increased inter-fibre hydrogen bonding offsetting the loss of fibre strength, an effect that can provide substantial savings in refining energy. Based on the results, a laccase–TEMPO treatment is an enzymatic booster of mechanical refining with the added advantages of providing unaltered drainability and increased air permeability. The most salient effect of the laccase–TEMPO treatment was an increase in wet tensile strength (by 160, 553 and 588% at 0, 3,000 and 4,500 rev, respectively) that can be ascribed to inter-fibre covalent bonding through hemiacetal linkages promoted by aldehyde groups. The improvement was much greater than that obtained at a lower consistency under identical conditions.     

Polypyrrole–multi-walled carbon nanotube nanocomposites synthesized in oil–water microemulsion

An oil–water microemulsion system, having been successfully used for synthesizing polypyrrole (PPy) nanoparticles, is introduced for preparing PPy–multi-walled carbon nanotube (MWCNT) nanocomposites via in situ chemical oxidative polymerization. The structures and the physical properties of the PPy–MWCNT nanocomposites are also investigated. The studies show that PPy can coat MWCNTs to form core–shell structure. The backbone structure of PPy is not damaged by the introduction of MWCNTs, and the PPy in the PPy–MWCNT nanocomposites is still amorphous as pure PPy. The conductivities of PPy–MWCNT nanocomposites are higher than that of pure PPy and are enhanced with the increase in the MWCNT–monomer mass ratio. Furthermore, a model is supposed to be used for illustrating the mechanism for PPy–MWCNT nanocomposite formation via in situ microemulsion synthesis.     

Enhancement of cellulose dissolution in water-based solvent via ethanol–hydrochloric acid pretreatment

Cellulose dissolution in water-based solvents is essential for processing of regenerated cellulose products such as fibres, films and particles. Cellulose dissolution in NaOH–urea aqueous solution has emerged as a simple and attractive alternative for processing cellulose solutions. However, this solvent requires energy intensive pretreatments such as milling or refining. In this paper we investigate a one step chemical pretreatment method using ethanol–hydrochloric acid prior to the dissolution of cellulose in NaOH–urea–water. The dissolution mechanism of the pretreated sample was initially examined in diluted cupri-ethylenediamine and 7% NaOH–12% urea–water solvent using optical microscopy methods and field emission scanning electron microscopy. The apparent energy of activation for the viscous flow of ethanol–acid pretreated pulp in NaOH–urea–water was calculated using rheological methods. Our results showed that the dissolution of pretreated pulp was achieved up to 4% cellulose concentration. We suggest that the enhancement of dissolution was due to a combination of degradation of remnant primary fibre wall layer and reduction of degree of polymerization of cellulose.     

Cellulose nanofibrils as filler for adhesives: effect on specific fracture energy of solid wood-adhesive bonds

Cellulose nanofibrils were prepared by mechanical fibrillation of never-dried beech pulp and bacterial cellulose. To facilitate the separation of individual fibrils, one part of the wood pulp was surface-carboxylated by a catalytic oxidation using (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) as a catalyst. After fibrillation by a high pressure homogenizer, the obtained aqueous fibril dispersions were directly mixed with different urea–formaldehyde-(UF)-adhesives. To investigate the effect of added cellulose filler on the fracture mechanical properties of wood adhesive bonds, double cantilever beam specimens were prepared from spruce wood. While the highest fracture energy values were observed for UF-bonds filled with untreated nanofibrils prepared from wood pulp, bonds filled with TEMPO-oxidized fibrils showed less satisfying performance. It is proposed that UF-adhesive bonds can be significantly toughened by the addition of only small amounts of cellulose nanofibrils. Thereby, the optimum filler content is largely depending on the adhesive and type of cellulose filler used.     

Properties of spruce sulfite pulp and birch kraft pulp after sorption of cationic birch xylan

In this study, correlations between the charge density of adsorbed cationic xylans and the mechanical properties of selected pulps are discussed. Hand-sheet experiments were carried out using birch sulfate pulp and spruce sulfite pulp after the adsorption of 2-hydroxypropyl-trimethylammonium-4-O-methylglucuronoxylans (HPMAGXs) with different molar degrees of substitution (MS) in the range of 0.06–0.19. The charge density of the HPMAGX in water was determined by polyelectrolyte titration. Properties such as the tensile and burst index increased after HPMAGX addition and showed an optimum depending on the MS, which was 0.1 for both pulps. Other properties like the tear-index or the specific volume changed depending on the pulp. Beating experiments were also performed and showed an increasing tensile index of birch kraft pulp in the range of 53.7 to 85.7 N m g⁻¹ for a beating time of 10 min. The adsorption of HPMAGXs with different MS onto thiol-based self-assembled monolayers (SAMs) on gold and regenerated cellulose surfaces were studied using surface plasmon resonance (SPR). Electrostatic interactions were found to be the most important factors affecting HPMAGX adsorption, and a strong correlation between HPMAGX adsorption onto carboxyl-terminated SAMs (SAM-COOH) and paper strength when HPMAGX was used as a papermaking additive was observed.     

Thermoanalytical study of some anti-inflammatory analgesic agents

Thermogravimetry (TG), differential thermal analysis (DTA), differential scanning calorimetry (DSC) as well as X-ray diffraction powder (DRX) patterns and Fourier transformed infrared spectroscopy (FTIR) were used to study ketoprofen, ibuprofen, and naproxen. The chemical or physical properties of the studied compounds were established and when possible by X-ray powder diffractometry and/or infrared spectroscopy were used. In this investigation, quantum chemical approach was used to determine the molecular structures using Becke three-parameter hybrid method and the Lee–Yang–Par (LYP) correlation functional. The performed molecular calculations in this work were done using the Gaussian 03 routine. Theoretical calculations help in interpretations of FTIR spectra supplying structural and physicochemical parameters.     

Preparation,characterization and activity evaluation of p–n junction photocatalyst p-NiO/n-ZnO

In this paper, p–n junction photocatalyst NiO/ZnO was prepared by the sol–gel method using Ni (NO₃)₂ and zinc acetate as the raw materials. The structural and optical properties of the p–n junction photocatalyst NiO/ZnO were characterized by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) analysis, UV–Vis diffuse reflection spectrum (DRS) and the fluorescence emission spectra. The photocatalytic activity of the photocatalyst was evaluated by photocatalytic reduction of Cr₂O₇ ²⁻ and photocatalytic oxidation of methyl orange (MO). The results showed that the photocatalytic activity of the p–n junction photocatalyst NiO/ZnO is much higher than that of ZnO on the photocatalytic reduction of Cr₂O₇ ²⁻. However, the photocatalytic activity of the photocatalyst is much lower than that of ZnO on the photocatalytic oxidation of methyl orange. Namely, the p–n junction photocatalyst NiO/ZnO has higher photocatalytic reduction activity, but lower photocatalytic oxidation activity. The heat treatment condition also influences the photocatalytic activity strongly, and the best preparation condition is about 400 °C for 2 h. Effect of the heat treatment condition on the photocatalytic activity of the photocatalyst was also investigated. The mechanisms of influence on the photocatalytic activity were discussed by the p–n junction principle.     

Synthesis of transparent silica aerogels with low density and better hydrophobicity by controlled sol–gel route and subsequent atmospheric pressure drying

In the present paper, attempts have been made to produce transparent silica aerogels with low density and better hydrophobicity by controlled sol–gel route and subsequent atmospheric pressure drying. The hydrogels were prepared by hydrolysis and polycondensation of sodium silicate (Na₂SiO₃) in the presence of acetic acid catalyzed water followed by several washing steps with water, methanol and hexane, respectively. The surface modification of the wet gel was carried out using a mixture of hexamethyldisilazane (HMDS) in hexane. Since, the sol–gel chemistry provides a straightforward method to control the physical and optical properties of the aerogels, the influence of various sol–gel parameters viz. gel washing time, molar ratios of CH₃COOH/Na₂SiO₃ and HMDS/Na₂SiO₃ and silylation period on the physical and optical properties of the aerogels have been investigated. The aerogels have been characterized by bulk density, Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetric and Differential Thermal Analysis (TG-DTA), Atomic Absorption Spectroscopy (AAS), Scanning Electron Microscopy (SEM) studies and Contact angle measurements.     

Modified chitosan 4. Superabsorbent hydrogels from poly(acrylic acid-co-acrylamide) grafted chitosan with salt- and pH-responsiveness properties

Graft copolymerization of mixtures of acrylic acid (AA) and acrylamide (AAm) onto chitosan was carried out by using potassium persulfate (KPS) as a free radical initiator in the presence of methylenebisacrylamide (MBA) as a crosslinker. The effect of reaction variables, such as MBA concentration and AA/AAm ratio on the water absorbency capacity have been investigated. The polymer structures were confirmed by FTIR spectroscopy. Water absorbencies were compared for the hydrogels before and after alkaline hydrolysis. In the non-hydrolyzed hydrogel, enhanced water absorbency was obtained with increasing AA in monomer feed. However, after saponification, the sample with high AAm ratio exhibited more water absorbency. These behaviors were discussed according to structural parameters. The swelling kinetics of the superabsorbing hydrogels was studied as well. The hydrogels exhibited ampholytic and reversible pH-responsiveness characteristics. The swelling variations were explained according to swelling theory based on the hydrogel chemical structure. The hydrogels exhibited salt-sensitivity and cation exchange properties. The pH-reversibility and on-off switching properties of the hydrogels make the intelligent polymers as good candidates for considering as potential carriers for bioactive agents, e.g. drugs.     

Acid–base interactions and swelling of cellulose fibers in organic liquids

Drago’s acid–base approach was used to quantify the hydrogen bonding interactions in solvent swelling of cellulose fibers. The fiber swelling was correlated with acid–base, dispersive interactions and solvent molar volume. The acid–base interaction potentials of solvents were expressed in terms of their electron pair donor and acceptor numbers. The acid–base interaction terms of cellulosic materials were determined by using: (1) Flory–Huggins; (2) multiple regression models. We have used the swelling data of Mantanis and coworkers, which were based on the equilibrium liquid holding capacities of various compressed fibers in water and series of organic solvents. According to our interpretations, acid–base interactions and molar volume parameters were the major contributors to the overall solubility parameter. Acid–base interaction terms were balanced in alpha-cellulose sample. However spruce wood and sulfite pulp samples were more acidic than basic and therefore swollen better in organic basic solvents. For a good swelling behavior solvent must have high electron pair donor number/acceptor number ratio and high electron pair donor number–acceptor number difference.     

Molecularly thin nanoparticles from cellulose: isolation of sub-microfibrillar structures

We have succeeded in isolating nanostructures from never-dried cellulose wood pulp, in sheet-form that have sub-microfibril dimensions (single to double digit Å thickness with 100’s of nm in length). A recently developed oxidation procedure by Saito and co-workers (Biomacromolecules 2006, 7:1687–1691) combined with extensive ultrasonication was used to liberate nanoscale cellulose fibrils. We show structures, as determined with atomic force microscopy, that compose the well-known cellulose microfibril, which are tenfold thinner than previous reports on nanoscale celluloses. This work provides indirect evidence in support of, and is consistent with, the hypothesis that the intersheet van der Waals bonding of the cellulose fibril is significantly weaker than the intrasheet hydrogen bonding of the cellulose microfibril. The structures are facile to isolate, contain enormous specific surface area with rich chemical functionality providing potential for numerous novel applications.     

Dispersive liquid-liquid microextraction based on the solidification of a floating organic droplet for simultaneous analysis of diethofencarb and pyrimethanil in apple pulp and peel

A method for analysis of diethofencarb and pyrimethanil in apple pulp and peel was developed by using dispersive liquid–liquid microextraction based on solidification of a floating organic droplet (DLLME-SFO) and high-performance liquid chromatography with diode-array detection (HPLC–DAD). Acetonitrile was used as the solvent to extract the two fungicides from apple pulp and peel, assisted by microwave irradiation. When the extraction process was finished, the target analytes in the extraction solvent were rapidly transferred from the acetonitrile extract to another extraction solvent (1-undecanol) by using DLLME-SFO. Because of the lower density of 1-undecanol than that of water, the finely dispersed droplets of 1-undecanol collected on the top of aqueous sample and solidified at low temperature. Meanwhile, the tiny particles of apple cooled and precipitated. Recovery was tested for a concentration of 8 μg kg⁻¹. Recovery of diethofencarb and pyrimethanil from apple pulp and peel was in the range 83.5–101.3%. The repeatability of the method, expressed as relative standard deviation, varied between 4.8 and 8.3% (n = 6). Detection limits of the method for apple pulp and peel varied from 1.2–1.6 μg kg⁻¹ for the two fungicides. Compared with conventional sample preparation, the method has the advantage of rapid speed and simple operation, and has high enrichment factors and low consumption of organic solvent.     

Titanium-supported nickel-copper oxide catalysts for oxidation of carbon(II) oxide

Nickel-copper compositions for catalytic oxidation of carbon(II) oxide to carbon(IV) oxide were prepared by impregnation of oxide films on titanium surface, obtained by plasma electrolytic oxidation followed by annealing. Plasma electrolysis oxide coatings with a layer thickness of 5 to 50 μm were generated using different electrolytes. The compositions were studied by X-ray powder diffraction, X-ray spectral analysis, and electron microscopy, and moisture absorption of the initial plasma electrolytic structures was estimated. A linear correlation was found between the overall concentration of nickel and copper (4 to 25 mol %) in the surface layer of ∼2–5-μm compositions and their catalytic activity. The overall concentration of nickel and copper was found to increase in parallel with the moisture absorption of plasma electrolytic oxidation coatings. Nickel-copper compositions based on plasma electrolytic oxidation coatings generated in a silicate electrolyte displayed the best catalytic, mechanical, and adhesion properties.     

Porphyrins incorporated to SiO<Subscript>2</Subscript> gels as fluorescent materials and efficient catalysts in biomimetic photocatalytic systems

Two types of porphyrins (water-soluble and water-insoluble) were encapsulated in transparent monolithic silica gels. Their properties in solutions and at various steps of the sol–gel process were studied by absorption and emission electron spectroscopy. A photocatalytic system containing porphyrins immobilized in powdered silica gel for α-pinene biomimetic oxidation to pinocarveol, pinocarvone and myrtenol is reported. The impact of several parameters (visible light irradiation time, organic solvent, the presence of an electron acceptor/donor, and substrate concentration) on this biotransformation process was investigated and optimized. It was established that photochemical excitation of sol–gel immobilized metal-free porphyrins is crucial for catalyzed oxidation of monoterpenes.     

Improved stability of water clusters (H<Subscript>2</Subscript>O)<Subscript>30–48</Subscript>: a Monte Carlo search coupled with DFT computations

The growing structural patterns of water clusters with 30–48 water molecules were investigated by means of a combined Monte Carlo search algorithm and density functional theory computations. The (H₂O)_30–48 clusters with amorphous core–shell structures are lower in energy than the previously reported fused cage and the tubular configurations. The significant differences in infrared spectra of these three different structural patterns provide some clues to identify the structural properties of these medium-sized water clusters in experiments.