Interpretation of Strengthening Mechanism of Densified Wood from Supramolecular Structures.

In this study, densified wood was prepared by hot pressing after partial lignin and hemicellulose were removed through alkaline solution cooking. The tensile strength and elastic modulus of densified wood were improved up to 398.5 MPa and 22.5 GPa as compared with the original wood, and the characterization of its supramolecular structures showed that the crystal plane spacing of the densified wood decreased, the crystallite size increased, and the maximum crystallinity (CI) of cellulose increased by 15.05%; outstandingly, the content of O(6)H⋯O(3') intermolecular H-bonds increased by approximately one-fold at most. It was found that the intermolecular H-bond content was significantly positively correlated with the tensile strength and elastic modulus, and accordingly, their Pearson correlation coefficients were 0.952 (p < 0.01) and 0.822 (p < 0.05), respectively. This work provides a supramolecular explanation for the enhancement of tensile strength of densified wood.

Study on the Preparation of Ionic Liquid Doped Chitosan/Cellulose-Based Electroactive Composites.

Electro-actuated polymer (EAP) can change its shape or volume under the action of an external electric field and shows similar behavioral characteristics with those of biological muscles, and so it has good application prospects in aerospace, bionic robots, and other fields. The properties of cellulose-based electroactive materials are similar to ionic EAP materials, although they have higher Young's modulus and lower energy consumption. However, cellulose-based electroactive materials have a more obvious deficiency-their actuation performance is often more significantly affected by ambient humidity due to the hygroscopicity caused by the strong hydrophilic structure of cellulose itself. Compared with cellulose, chitosan has good film-forming and water retention properties, and its compatibility with cellulose is very excellent. In this study, a chitosan/cellulose composite film doped with ionic liquid, 1-ethyl-3-methylimidazolium acetate ([EMIM]Ac), was prepared by co-dissolution and regeneration process using [EMIM]Ac as the solvent. After that, a conductive polymer, poly(3,4-ethylenedioxythiophene)/poly (styrene sulfonate) (PEDOT: PSS), was deposited on the surface of the resulted composite, and then a kind of cellulose-based electroactive composites were obtained. The results showed that the end bending deformation amplitude of the resulted material was increased by 2.3 times higher than that of the pure cellulose film under the same conditions, and the maximum deformation amplitude reached 7.3 mm. The tensile strength of the chitosan/cellulose composite film was 53.68% higher than that of the cellulose film, and the Young's modulus was increased by 72.52%. Furthermore, in comparison with the pure cellulose film, the water retention of the composite film increased and the water absorption rate decreased obviously, which meant that the resistance of the material to changes in environmental humidity was greatly improved.

Durable cellulose paper by grafting thiol groups and controlling silver deposition for ultrahigh electromagnetic interference shielding.

Electromagnetic interference (EMI) shielding paper with durability and high effectiveness is of significant importance to long-term service for preventing EMI pollution. Herein, we report a practical method for preparing cellulose paper/Ag composite with outstanding durable and ultrahigh EMI shielding performance by electroless silver plating. The silver deposition process, the surface morphology, the silver content and conductivity of the composite can be controlled by varying the amount of N-acetyl-L-cysteine (NAC) grafted onto the cellulose fibers and ammonia amount for silver-ammonia complex formation. Moreover, the grafted NAC with thiol groups on cellulose can enhance the adhesion between silver and cellulose paper, meanwhile, NAC as the reducing agent can result in a more complete flower-shaped silver structure and reducing the reflection of electromagnetic waves in silver layer. The composite exhibited excellent conductivity, EMI shielding effectiveness (SE) up to 106 dB and outstanding durability. After 10,000 bending times and 60 abrasion cycles respectively, the electrical resistance of the composite only increased from 0.030 Ω/sq. to 0.041 Ω/sq. and 0.050 Ω/sq., and the EMI SE decreased to 102 dB and 105 dB.

Chitosan/Montmorillonite Coatings for the Fabrication of Food-Safe Greaseproof Paper.

Here, we report a non-toxic method for improving the oil-resistant performance of chitosan coated paper by coating the mixture of chitosan and montmorillonite (MMT) instead of coating chitosan solution only. Through combining MMT into the chitosan coatings, the coated paper exhibited a lower air permeability and enhanced oil resistance under a lower coating load. For coated papers C2.5 and C3 by coating 2.5% (w/v) and 3% (w/v) chitosan without adding MMT in the chitosan coating, the coating load was 3.76 g/m2 and 3.99 g/m2, respectively, and the kit rating values were only 7-8/12. Regarding the sample C2M0.1 coated by the mixed solution containing 2% (w/v) chitosan and 0.1% (w/v) MMT, its coating load was only 3.65 g/m2, the paper permeability after coating was reduced to 0.00507 µm/Pa·s, owing to the filling of MMT into the cellulosic fibers network, and the kit rating reached 9/12. Moreover, C2M0.1 showed improved mechanical properties, whereby its tearing resistance was 5.2% and 6.6% higher than that of the uncoated paper in the machine direction and the cross direction, respectively.

Physicochemical Properties of Nanocellulose Isolated from Cotton Stalk Waste.

In recent years, nanocellulose has become an attractive and high-value-added product. The cotton stalk is a waste product with a high cellulose content. Therefore, nanocellulose can be isolated from the cotton stalk. Properties of nanocellulose are affected by its nanoscale. In this study, the characteristics of cellulose in nanoscale were investigated. A series of cotton stalk nanocelluloses were prepared by sulfuric acid hydrolysis to study their physicochemical properties and the differences of nanocelluloses on different nanoscales. The obtained nanocelluloses were analyzed by atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TA), and X-ray diffractometry (XRD). From the morphology analysis, the mean length and width of nanocelluloses were decreased to 90.5 and 7.0 nm, respectively. From the FTIR analysis, with the particle size decreasing, hydrogen bonds were broken and recombined. Acid hydrolysis mainly acted on intramolecular hydrogen bonds of cellulose macromolecules, especially on O(3)H···O(5) bonds. The crystal arrangement model of nanocellulose was investigated. From the TA analysis, the thermal property was decreased with a reduction of nanocellulose particle size. The CrI of the cotton stalk nanocellulose was the highest at up to 87.10%. The differences of cotton stalk nanocelluloses give significant changes to physicochemical behaviors at the nanoscale. The research would provide a theoretical basis for the future application of nanocelluloses.

Preparation of conductive cellulose fabrics with durable antibacterial properties and their application in wearable electrodes.

Electroless silver plating on fabrics can obtain conductive and antibacterial bifunctional materials which can be used as electrodes in wearable electronic products. However, these activities are deteriorated easily after washing because of the falling off of silver coating resulted from the weak adhesion. In order to improve the binding force between silver and cellulose fabrics, 3-mercaptopropytrimethoxysilane (MPTS) was applied to modify cellulose fabrics before silver electroless plating to develop the durable conductive fabrics with excellent antibacterial. The silver nanoparticles (Ag NPs) deposition process was observed via field emission scanning electron microscopy (FESEM), thermal properties were evaluated by thermogravimetric analysis (TGA). A dense and uniform silver layer was formed on the fabric. The initial electrical resistance of the conductive fabric was 0.04 Ω/sq and lowered than 2 Ω/sq after 200 washing cycles. The antibacterial efficiency of the fabric after 200 washing cycles remained 92.82%, compared to 100% with the fabric before washing. Moreover, the inhibition rate was determined by optical density of bacteria suspension at 260 nm and further substantiated by releasing of Ag+ from the fabric. The conductive fabrics were applied as wearable electrodes to capture electrocardiogram (ECG) signals of human in static states and running states.

Probing Effect of Papirindustriens Forskningsinstitut (PFI) Refining on Aggregation Structure of Cellulose: Crystal Packing and Hydrogen-Bonding Network.

Supramolecular structure is the critical factor that affects the properties of cellulosic fibers. This article studied the action of Papirindustriens forskningsinstitut (PFI) refining on the molecular aggregation and hydrogen bonding network, and tried to explore the relationship between the crystal packing and hydrogen-bonding network in cellulosic fibers. The results showed that the polymorph, H-bonding distance, and H-bonding energy of various H-bonds remained almost unchanged, while the crystalline index, crystallite size, and content of various H-bonds changed with refining. Therein, the content of the inter-molecular O(6)H⋯O(3') H-bonds was significantly correlated with the crystalline index that was obtained in intensities of the XRD peaks. The Pearson correlation coefficient between them was 0.888 (p < 0.05) for softwood fibers and 0.889 (p < 0.05) for hardwood fibers, respectively. It can be concluded that the variations of accessibility, swelling, and fibrillation were closely related to the supramolecular structure and the intermolecular H-bonds play an important role in the crystal packing of cellulose.

Preparation of Novel Nano-Sized Hydrogel Microcapsules via Layer-By-Layer Assembly as Delivery Vehicles for Drugs onto Hygiene Paper.

Hydrogel microcapsules are improved transplantation delivery vehicles for pharmaceuticals by effectively segregating the active ingredients from the surroundings and delivering them to a certain target site. Layer-by-layer (LbL) assembly is an attractive process to fabricate the nano-sized hydrogel microcapsules. In this study, nano-sized hydrogel microcapsules were prepared through LbL assembly using calcium carbonate nanoparticles (CaCO3 NPs) as the sacrificial inorganic template, sodium alginate (SA) and polyethyleneimine (PEI) as the shell materials. Ciprofloxacin was used to study the encapsulation and release properties of the hydrogel microcapsules. The hydrogel microcapsules were further adsorbed onto the paper to render antimicrobial properties. The results showed that the mean size of the CaCO3 template was reduced after dispersing into sodium n-dodecyl sulfate (SDS) solution under sonication. Transmission electron microscope (TEM) and atomic force microscope (AFM) revealed that some hydrogel microcapsules had a diameter under 200 nm, typical creases and collapses were found on the surface. The nano-sized PEI/SA hydrogel microcapsules showed high loading capacity of ciprofloxacin and a sustained release. PEI/SA hydrogel microcapsules rendered good antimicrobial properties onto the paper by the adsorption of hydrogel microcapsules, however, the mechanical properties of the hygiene paper were decreased.

Novel Wearable Electrodes Based on Conductive Chitosan Fabrics and Their Application in Smart Garments.

Smart garments, which can capture electrocardiogram signals at any time or location, can alert others to the risk of heart attacks and prevent sudden cardiac death when people are sleeping, walking, or running. Novel wearable electrodes for smart garments based on conductive chitosan fabrics were fabricated by electroless plating of silver nanoparticles onto the surfaces of the fibers. The electrical resistance, which is related to the silver content of the composite fabrics, can be as low as 0.0332 ± 0.0041 Ω/sq due to the strong reactivity between amine groups and silver ions. After washing these fabrics eight times, the electrical resistance remained below 1 Ω/sq. The conductive chitosan fabrics were applied to smart garments as wearable electrodes to capture electrocardiogram signals of the human body in static state, jogging state, and running state, which showed good data acquisition ability and sensitivity.

[Measurement of triglyceride content of resin in masson pulp by UV spectral method].

Pitch deposit is one of the most troublesome problems for the paper mills in South China that use the masson pine as a raw material to make paper. The triglyceride has been identified as the main composition accounting for pitch problem. in order to set down effective pitch control scheme, the triglyceride content in papermaking process must be measured quantitatively. A method to measure the content of triglyceride in masson wood pulp was developed based on UV spectrophotometer in the present work. The UV spectrogram and characteristic peak location of standard glycerol trioleate as well as the effect of measuring time on absorbency were discussed. The results showed that at 412 nm the relation between absorbency and consistency of glycerol trioleate was linear and the pertinent coefficient reached 0. 971 in the range of reagent dosage and consistency in this experiment. The absorbency decreased linearly with measuring time and the pertinent coefficient reached 0. 990 2. The results of reproductive experiment showed that the recoveries were 98%-104%0 and the accuracy was 1. 27%-4. 03% for the samples in consistency 1. 25-0. 50 g x L(-1). With this method, the content of triglyceride in hexane extractive of masson TMP and acid SP were measured respectively. The degradative effect of triglyceride before and after enzyme treatment for masson wood pulp was also evaluated. The results showed that the triglyceride content was relatively high, about 50% both in the total extractive of masson TMP and acid SP. After enzyme treatment, the content of triglyceride in masson TMP and acid SP was reduced by 46. 31% and 35. 55% respectively.

Microwave Assisted Preparation of Antimicrobial Chitosan with Guanidine Oligomers and Its Application in Hygiene Paper Products.

Guanidinylated chitosan (GCS) was prepared by grafting guanidine oligomers onto chitosan under microwave irradiation. The structure of GCS characterized by FT-IR and ¹H NMR verified the covalent bonding between the guanidine oligomers and chitosan; the effects of molar ratio, reaction temperature, and time were investigated and the degree of substitution of GCS reached a maximum of 25.5% under optimized conditions in this work. The resulting GCS showed significantly enhanced antimicrobial activities. The results obtained from the dynamic UV absorption of Escherichia coli (E. coli) and atomic force microscopy (AFM) revealed that the deactivation of E. coli by GCS was due to the destructing of the cell membrane and the prompt release of cytoplasm from the bacterial cells. The adsorption of GCS onto cellulose fibers and the antimicrobial efficiency of the hygiene papers with GCS were also investigated. Microwave irradiation as a green assisted method was applied to promote this reaction. This facile approach allowed chitosan to be guanidinylated without tedious preparation procedures and thus broadened its application as a biocompatible antimicrobial agent.

Immobilization of pectinase on oxidized pulp fiber and its application in whitewater treatment.

Modified pulp fiber was originally used as a new type of carrier for pectinase immobilization. Pulp fiber was oxidized by sodium periodate to produce aldehyde groups for covalently binding with amino groups of pectinase. Results showed that the enzymatic activity of immobilized pectinase on pulp fiber reached 65 µgg(-1)min(-1) when immobilization pH value, temperature and time were of 7.0, 20 °C and 15 min, respectively. The immobilized pectinase showed higher thermo stability in a wider temperature range of 40-70 °C than its free type and its optimal pH shifted from 8.0 to 8.8. Furthermore, the immobilized pectinase exhibited good operational stability. When employed in whitewater treatment of papermaking industry, it still efficiently decreased the cationic demand after operating repeatedly for six batches. The results obtained demonstrate a promising route to prepare available, cheap and biodegradable carrier for immobilizing enzymes with potential application in wastewater treatment in papermaking industry.

Immobilization of pectinase and lipase on macroporous resin coated with chitosan for treatment of whitewater from papermaking.

Anionic residues and pitch deposits in whitewater negatively impact the operation of paper-forming equipment. In order to remove these substances, a macroporous resin based on a methyl acrylate matrix was synthesized and coated with chitosan of various molecular weights through glutaraldehyde cross-linking. Pectinase from Bacillus licheniformis and lipase from Thermomyces lanuginosus were immobilized on the resin coated with chitosan by a Schiff base reaction. The highest hydrolysis activities of the immobilized enzymes were achieved by using chitosan with 10×10(5)DaMW for coating and 0.0025% glutaraldehyde for cross-linking chitosan. The cationic demand and pitch deposits in whitewater were reduced by 58% and 74%, respectively, when treating whitewater with immobilized dual-enzymes for 15min at 55°C and pH 7.5. This method is useful for treatment of whitewater in the papermaking industry.

Synthesis of modified guanidine-based polymers and their antimicrobial activities revealed by AFM and CLSM.

Modified guanidine-based polymers with chain extension were synthesized by condensation and cross-linking polymerizations in an attempt to increase molecular weight and charge density of the antimicrobial polymers. The antimicrobial activity and the corresponding mechanisms were investigated by several approaches. The results indicated that the antimicrobial activities of the modified guanidine-based polymer, based on the minimum inhibition concentration (MIC) against E.coli, varied with alkyl monomer ratios. UV absorption at 260 nm further quantified the amount of intracellular components leaked into bacteria suspension. The UV absorption measurements were also used to monitor inhibition processes dynamically. It was found that the modified guanidine-based polymer inhibited the growth of bacteria by causing membrane compromised and intracellular leaked. Dual fluorescent dyes were used to stain all bacteria including the dead ones, which enabled us to utilize CLSM to visualize the viability of bacteria in the presence of various modified guanidine-based polymers without causing any damage. The morphologies of bacteria untreated and treated with modified guanidine-based polymer were observed using an atomic force microscope (AFM), which further demonstrated the damage of E.coli membrane and the leakage of intracellular component induced by the modified guanidine-based polymers.

Synergistic effects of chitosan-guanidine complexes on enhancing antimicrobial activity and wet-strength of paper.

Chitosan-guanidine complexes were prepared by reacting chitosan and polyhexamethylene guanidine hydrochloride or crosslinked polyhexamethylene guanidine hydrochloride in the presence of sodium tripolyphosphate as a crosslinking agent. The complexes, used as functional additives for paper, synergistically improved wet-strength and antimicrobial activities. In comparison with the control sample, the wet/dry strength ratio of hand-sheets treated with the complexes was increased from 2.65% up to 23.3%. The MIC values of the chitosan-PHGH and chitosan-PHGHE complexes against Escherichia coli were 15.6 and 31.2 microg mL(-1), respectively, thus demonstrating excellent antimicrobial activity. Hand-sheets treated with the complexes exhibited antibacterial activity against E. coli and Staphylococcus aureus. The release of the guanidine polymers included in the complexes was dynamically monitored using UV and the results showed the amount released exceeded 80%. Atomic force microscopy images indicated that the antimicrobial mechanism of the complexes was likely due to membrane damage.