A novel amphotropic polymer based on cellulose nanocrystals grafted with azo polymers

A novel amphotropic polymer which could exhibit liquid-crystalline behavior both in the solvent and in the heating process was synthesized through azo polymers grafting from cellulose nanocrystals (CNCs). The CNCs, prepared by acid hydrolysis of filter paper, were characterized by Atomic Force Microscopy (AFM). Poly{6-[4-(4-methoxyphenylazo)phenoxy] hexyl methacrylate}(PMMAZO), which was a liquid-crystalline polymers (LCP), was successfully to graft from CNC via Atom transfer radical polymerization (ATRP). The structure and thermal properties of the PMMAZO-grafted CNC were investigated using Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analyses (TGA). Its phase structures and transitions were studied by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The experimental results showed that the PMMAZO-grafted CNC exhibited both types of liquid crystal formation, thermotropic and lyotropic.     

Immobilization of bismuth oxychloride on cellulose nanocrystal for photocatalytic sulfonylation of arylacetylenic acids with sodium arylsulfinates under visible light

As a promising semiconductor photocatalyst, BiOCl has been widely used in the field of environmental protection. However, due to its weak ability to absorb visible light, the application of BiOCl in other important photocatalytic fields has been significantly limited, such as organic synthesis. In this work, a facile method was used to prepare a highly efficient heterogeneous nano-photocatalyst BiOCl/cellulose nanocrystal (CNC). Subsequently, the BiOCl/CNC was verified by XPS, ESR, BET and other characterization methods. The results show that not only the strong interaction between BiOCl and CNC increases the visible light absorption intensity of the composite, but also the combination of BiOCl and CNC makes the specific area of the catalyst more than twofold. In addition, a large number of hydroxyl groups contained in CNC can be combined with the BO bond in BiOCl through hydrogen bonds, forming abundant oxygen vacancies on BiOCl/CNC. Excitedly, these changes enable BiOCl/CNC to exhibit excellent photocatalytic performance and regeneration performance in the sulfonation reaction of arylacetylene acid and sodium arylsulfinate, with a yield of up to 96%. This work represents a step towards a low-cost, environmentally friendly composite of cellulose and BiOCl, which will provide useful enlightenment for future exploration in related fields.     

Insight into the extraction and characterization of cellulose nanocrystals from date pits

This study aims to extract and characterize cellulose nanocrystals (CNCs) from date pits (DP), an agricultural solid waste. Two methods were used and optimized for the cellulose nanocrystals (CNCs) extraction, namely the mechanical stirrer method (CNCs₁) and the Soxhlet apparatus method (CNCs₂) in terms of chemical used, cost, and energy consumption. The results showed that scanning electron microscopy revealed the difference in the morphology as they exhibit rough surfaces with irregular morphologies due to the strong chemical treatments during the delignification and bleaching process. Moreover, transmission electron microscopy analysis for CNCs reveals the true modification that was made through sulfuric acid hydrolysis as it presents cellulose microfibrils with a packed structure. Fourier transform infrared proved that the CNCs were successfully extracted using the two methods since most of the lignin and hemicellulose components were removed. The crystallinity index of CNCs₁ and CNCs₂ was 69.99%, and 67.79%, respectively, and both presented a high yield of CNCs (≥10%). Ultimately, both techniques were successful at extracting CNCs. Based on their cost-effectiveness and time consumption, it was concluded that method 1 was less expensive than method 2 based on the breakdown of the cost of each step for CNCs production.     

Effect of microcrystalline and nanocrystals cellulose fillers in materials based on PLA matrix

The aim of this work was to compare the effects of microcrystalline cellulose (MCC) and cellulose nanocrystals (CNC) addition on the properties of PLA matrix. The CNC were obtained by acid hydrolysis of the MCC. Both MCC and CNC were separately incorporated in PLA at ratios of 3, 5 and 7 wt%. In some compositions, organophilic silica (R972) was added to improve the cellulose-matrix compatibility. The properties of the materials were evaluated by FTIR, XRD, NMR and mechanical tests. Functional groups and crystalline structure of MCC and CNC were determined by FTIR and XRD, respectively. NMR T₁H values showed that films containing CNC presented better interfacial interaction than those containing MCC, and indicated that R972 acts as compatibilizer. MCC and CNC acted as nucleating agents for PLA crystallization and there was an improvement in the mechanical performance of materials with the addition of CNC.     

Reinforcement of hydroxypropylcellulose films by cellulose nanocrystals in the presence of surfactants

Hydroxypropylcellulose (HPC) films were prepared by casting with cellulose nanocrystals in the presence of anionic surfactant sodium dodecylsulphate (SDS) and cationic surfactant hexadecyltrimethyl ammonium bromide (CTAB). The cellulose nanocrystals were isolated from maize straw, a biomass source produced in huge quantities as an agrowaste in Brazil. These bionanocomposite films had good transparency and their surface hydrophilic character was evidenced by static contact angle measurements. Thermogravimetry (TGA) measurement revealed that nanocrystals and surfactants changed the thermal stability of the HPC films. Dynamic mechanical analysis (DMA) showed that the tensile storage and loss moduli of the HPC films increased by increasing the contents of cellulose nanocrystals and surfactants, especially in the case of CTAB. This good reinforcing effect of HPC matrix can be explained as due to electrostatic attractive interactions brought about by the presence of CTAB and the nanocrystals.     

Self-assembled micelles based on hydrophobically modified quaternized cellulose for drug delivery

Novel amphiphilic cationic cellulose (HMQC) derivatives carrying long chain alkyl groups as hydrophobic moieties and quaternary ammonium groups as hydrophilic moieties were synthesized. Structure and properties of the amphiphilic cellulose derivatives were characterized by elemental analysis, FT-IR, (1)H NMR, ζ-potential measurement, dynamic light scattering (DLS), fluorescence spectroscopy and transmission electron microscopy (TEM). The results revealed that HMQCs can be self-assembled into cationic micelles in distilled water with the average hydrodynamic radius of 320-430 nm. The cytotoxicity study showed that the HMQC exhibited low cytotoxicity. Prednisone acetate, a water insoluble anti-inflammation drug, was chosen as a model drug to investigate the utilization of self-assembled HMQC micelles as a delivery carrier for poorly water-soluble drugs. The study indicated that the prednisone acetate could be incorporated effectively in the self-assembled HMQC micelles and be controlled released.     

Novel cellulose acetate membrane blended with phospholipid polymer for hemocompatible filtration system

To improve the blood compatibility of cellulose acetate (CA) membranes for hemofiltration, a novel CA membrane blended with 2-methacryloyloxyethyl phosphorylcholine (MPC) copolymer was designed for a hemocompatible filtration system. The MPC copolymer (PMB30) was synthesized from MPC and n-butyl methacrylate. The polymer solution for making the membrane was prepared from a solvent mixture composed of N,N-dimethylformamide, acetone, and 2-propanol. The CA and CA/PMB30 blended membranes with an asymmetric and porous structure were prepared by a phase inversion process. The mechanical properties and solute permeability of the CA/PMB30 blended membrane could be controlled by preparation conditions such as the composition of the solvents and the solvent evaporation time. The CA/PMB30 blended membrane showed both good water and solute permeabilities in comparison with the CA membrane. Also, the molecular weight of the solute passed through the membrane was changed by the addition of PMB30, and good permselectivity could be obtained. Moreover, the CA/PMB30 blended membranes had excellent blood compatibility such as protein adsorption resistivity compared to the CA membrane due to location of the MPC units in the PMB30 at the surface.     

Development of sodium alginate-xanthan gum based nanocomposite scaffolds reinforced with cellulose nanocrystals and halloysite nanotubes

Sodium alginate (Alg) and xanthan gum (XG) based nanocomposite scaffolds reinforced with various amounts of cellulose nanocrystals (CNCs) and/or halloysite nanotubes (HNTs) were prepared by freeze-casting/drying method. In this study, the structure-property-performance relationship was mainly focused and analysed. Morphological analysis showed high porosity and pore-interconnectivity (pore channels) in all obtained scaffolds. Structural analysis demonstrates the good interfacial interactions and uniform dispersion of the CNCs and HNTs, involving partial orientation within the polymeric network. The water uptake capacity (from 14.73.7 ± 0.46 g/g to 11.34 ± 0.32 g/g) and porosity (from 91.7 ± 0.81% to 88.5 ± 0.64%) were reduced. The compressive strengths (in dry state from 91.1 ± 1.2 kPa to 114.4 ± 0.6 kPa and in wet state from 9.0 ± 0.8 kPa to 10.6 ± 0.8 kPa), thermal stability, cytocompatibility (MC3T3-E1 osteoblastic cells) of the nanocomposite scaffolds improved as compared to Alg and AlgX scaffolds without CNCs and/or HNTs. The obtained scaffolds may be appropriate as scaffolding material in bone tissue engineering.     

Melt‐blending of unmodified and modified cellulose nanocrystals with reduced graphene oxide into PLA matrix for biomedical application

In this article, we successfully fabricated the bionanocomposites using cellulose nanocrystals (CNCs) and reduced graphene oxide (rGO) reinforced into biodegradable polylactic acid (PLA) matrix through melt‐mixing method. Due to the affinity difference between hydrophilic CNC and hydrophobic PLA, the surface modification of CNC was employed using quaternary ammonium salts (CTAB) as a surfactant. The nanocomposites were developed using different blend ratios of CNC/modified CNC (1, 2, and 3) wt% and (0.5 wt%) rGO into the polymer matrix. The morphology of CNC, q‐CNC (modified CNC), and nanocomposites were inspected by atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM). It is demonstrated from tensile tests that, the nanocomposite with 1 wt% CNC and rGO showed maximum tensile strength compared with PLA and its nanocomposites. Moreover, the nanocomposite with 1 wt% CNC and rGO was also having maximum thermal stability. From cytotoxicity evaluation, it is observed that all the nanocomposites are nontoxic and cytocompatible to HEK293 cells. In addition to this, the nanocomposite with q‐CNC showed enhanced barrier properties compared with PLA and PLA/CNC/rGO nanocomposite. The results obtained from different characterizations showed that the incorporation of surfactant onto CNC improved the dispersion in PLA but at the same time deteriorated the PLA matrix.     

Poly(acrylamidoglycolic acid) nanocomposite hydrogels reinforced with cellulose nanocrystals for pH-sensitive controlled release of diclofenac sodium

In this study, a non-cytotoxic and pH-sensitive poly(acrylamidoglycolic acid) based nanocomposite (PAGA-NC) hydrogels reinforced with cellulose nanocrystals (CNCs) was synthesized using redox free radical polymerization. The successful formation and crystalline behaviour of PAGA-NC hydrogels was verified by fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) analyses. The results showed that morphological, rheological and mechanical properties of the PAGA-NC hydrogels were strongly influenced by the CNCs content. Moreover, swelling properties were investigated, and the results suggested that they behaved as pH sensitive manner. The in vitro MTT assay showed that the PAGA-NC hydrogels are cytocompatibile to NIH-3T3 fibroblast cells. In addition, diclofenac sodium (DCF) model drug was successfully encapsulated into these PAGA-NC hydrogels via equilibrium swelling method. The in vitro release of DCF from PAGA-NC hydrogels was retained at pH 1.2 and maximum release was observed at 7.4, revealing as potential candidates for controlled release carriers for oral drug delivery applications.     

Preparation of poly(glutamic acid) shielding micelles self-assembled from polylysine-b-polyphenylalanine for gene and drug codelivery

A novel amphiphilic cationic block copolymer polylysine-b-polyphenylalanine(PLL-b-PPhe) was synthesized and self-assembled into micelles in aqueous solution,then shielded with poly(glutamic acid)(marked as PG/PLL-b-PPhe) to codeliver gene and drug for combination cancer therapy.Here,doxorubicin(DOX) was selected to be loaded into PLL-b-PPhe micelles and the drug loading efficiency was 8.0%.The drug release studies revealed that the PLL-b-PPhe micelles were pH sensitive and the released DOX could reach to 53.0%,65.0%,72.0% at pH 7.4,6.8 and 5.0,respectively.In order to reduce positive charge and cytotoxicity of PLL-b-PPhe micelles,PG was used as shelding,simultaneously condensed with Bcl2 siRNA to form gene carrier system.Compared with PEI,PG/PLL-b-PPhe had excellent gene transfection efficiency,especially when the molar ratio of PLL to PPhe was 30:60 and the mixed mass ratio of PLL-b-PPhe to gene was 5:1.More importantly,DOX and Bcl2 siRNA gene codelivery system displayed remarkable cytotoxicity against B16 F10 cells.Confocal laser scanning microscopy(CLSM) and flow cytometry were used to characterize endocytosis of the codelivery system,and confirmed that both DOX and Bcl2 siRNA had been endocytosed into B16 F10 cells.The above results indicated that gene and drug codelivery was a promising strategy in future cancer therapy.     

Aptamer based strategy for cytosensing and evaluation of HER-3 on the surface of MCF-7 cells by using the signal amplification of nucleic acid-functionalized nanocrystals

The electrochemical detection of cell lines of MCF-7 (human breast cancer) has been reported, using magnetic beads for the separation tool and high-affinity DNA aptamers for signal recognition. The high specificity was obtained by using the magnetic beads and aptamers, and the good sensitivity was realized with the signal amplification of DNA capped CdS or PbS nanocrystals. The ASV (anodic stripping voltammetry) technology was employed for the detection of cadmic cation and lead ions, for electrochemical assay of the amount of the target cells and biomarkers on the membrane of target cells, respectively. This electrochemical method could respond to as low as 100 cells mL⁻¹ of cancer cells with a linear calibration range from 1.0 × 10² to 1.0 × 10⁶ cells mL⁻¹, showing very high sensitivity. Moreover, the amounts of HER-3 which were overexpressed on MCF-7 cells were calculated correspond to be 3.56 × 10⁴ anti-HER-3 antibody molecules. In addition, the assay was able to differentiate between different types of target and control cells based on the aptamers and magnetic beads used in the assay, indicating the wide applicability of the assay for early and accurate diagnose of cancers.     

Electrospinning of magnetic cellulose tris‐(4‐methylbenzoate) microparticles for enantioselective adsorption of racemic drug

In this work, we introduce electrospinning to prepare magnetic enantioselective material for the first time. Multianalytical tools were used to characterize the resulted magnetic cellulose tris‐(4‐methylbenzoate) particles including transmission electron microscopy, SEM, FTIR spectroscopy, thermogravimetric analysis, X‐ray diffractometer. Under the optimum conditions, the resulted particles were well‐shaped sphere with a diameter range of 800 nm to 2 μm and high magnetic sensitivity. The enantioselectivity of the adsorbents was evaluated using racemic ibuprofen as a model drug; an e.e. value of ?4.78% (where e.e. is enantiomeric excess) was achieved in a single adsorption stage. We hope that our finding provides an efficient and economical procedure for the preparation of magnetic enantioselective materials with high selectivity and reproducibility.     

Functionalization of cellulose dialysis membranes for chiral separation using beta-cyclodextrin immobilization

A membrane-based chiral separation system for the separation of racemic tryptophan solutions is developed by the covalently binding beta-cyclodextrin onto the surface of commercial cellulose membranes. The immobilization process is monitored by XPS. AFM demonstrates the evolutionary transition of membrane surface morphology before and after the CD immobilization. Due to their different complexation with immobilized CD, dialysis transport experiments show d-tryptophan preferential permeability through the immobilized CD membranes, and the enantioselectivity is 1.10. A model based on the existence of a thin chiral solution layer of amino acid at the interface between the feed solution and the membrane has been proposed. This chiral separation model has been verified using the chiral separation results of racemic amino acids and binding constants of amino acids with CD. The effect of membrane's pore size on enantioselectivity has also been investigated. The immobilized CD membrane, having MWCO 1000, exhibits the highest enantioselectivity to the racemic tryptophan solution.     

A simple method for functionalization of cellulose membrane for covalent immobilization of biomolecules

Activated cellulose membrane was prepared by a simple photochemical reaction at 365 nm in 12 min using a photolinker, 1-fluoro-2-nitro-4-azidobenzene. XPS analysis of the activated cellulose membrane confirmed the presence of nitrogen and fluorine in the ratio of 2:1. Immobilization of a protein molecule onto the activated membrane occurred in 2 h at 37 °C. In contrast, no appreciable immobilization occurred onto the untreated surface. Disappearance of the fluorine peak in the XPS spectra of membrane having immobilized HRP confirmed covalent binding of the protein onto the activated membrane. Invertase was also immobilised onto the activated membrane and used in a flow through reactor system for conversion of sucrose to glucose and fructose. Immobilized invertase was found to be stable for at least 72 h of continuous run. The kinetic parameters of the enzyme reaction, Michaelis constant (K_m) and V_max value of immobilized invertase was studied. The activated membrane when used in an ELISA procedure to detect immunoglobulins in human sera, showed around 2.6-fold higher sensitivity than the untreated membrane. The activated cellulose membrane has the potential for versatile applications such as in diagnostics, in flow reactor system for an enzyme-catalysed reaction and in membrane based affinity chromatography.     

Super-assembled highly compressible and flexible cellulose aerogels for methylene blue removal from water

Physical adsorption is a common method to solve the contamination of methylene blue in dyeing wastewater. As a kind of adsorption material, cellulose aerogels with high porosity and surface areas have great potential application in methylene blue removal. However, the week hydrogen bonding between cellulose nanofibers making the cellulose aerogels with the poor mechanical properties and can be easily destroyed during adsorption. Hence, the preparation of cellulose aerogels with high mechanical strength is still a great challenge. Here, we report a robust super-assembly strategy to fabricate cellulose aerogels by combining cellulose nanofibers with PVA and M-K10. The resulting cellulose aerogels not only has a robust chemically cross-linked network, but also has strong H-bonds, which greatly enhance the mechanical properties. The resulting cellulose aerogels possess a low density of 19.32 mg/cm3.Furthermore, the cellulose aerogel shows 93% shape recovery under 60% strain(9.5 k Pa under 60% strain)after 100 cycles, showing excellent mechanical property. The adsorption capacity of cellulose aerogel to methylene blue solution of 20 mg/L is 2.28 mg/g and the adsorption kinetics and adsorption isotherms have also been studied. Pseudo-second-order kinetic model and Freundlich isotherm model are more acceptable for indicating the adsorption process of methylene blue on the cellulose aerogel. Thus, this compressible and durable cellulose aerogel is a very prospective material for dyeing wastewater cleanup.     

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.     

Radiation effect studies on anticancer drugs, cyclophosphamide and doxorubicin for radiation sterilization

Two anticancer drugs, cyclophosphamide (CPH) and doxorubicin hydrochloride (DOXO), in powder form were exposed to a range of doses of ⁶⁰Co gamma and electron beam radiation to study the effects of ionizing radiation. Pharmacopoeia tests, discolouration, degradation products, effect of irradiation temperature and dose rate were investigated. CPH undergoes less than 2% degradation at 30 kGy. Chromatographic studies revealed formation of several trace level degradation products, discolouration and free radicals in the irradiated CPH. N,N-bis (2-chloroethyl) group in the molecule is particularly sensitive to radiation degradation. Irradiation to 5 kGy at low temperature (77 K) did not result in significant changes. DOXO was observed to be quite radiation resistant and did not undergo significant changes in its physico-chemical properties and degradation product profile. It can be radiation sterilized at normal sterilization dose of 25 kGy.     

Tetramethylammonium hydroxide thermochemolysis for the analysis of cellulose and free carbohydrates in a peat bog

We have compared TMAH thermochemolysis with the classical method using acid hydrolysis for carbohydrates analysis in a peat core. Even if TMAH thermochemolysis does not analyse hemicellulosic carbohydrates and discriminate each individual carbohydrate sensu stricto, it allows the analysis of a cellulose pool hidden to acid hydrolysis and the specific analysis of free and terminal carbohydrates. Simple direct comparisons of thermochemolysis data with data generated from acid hydrolysis cannot be done because of the different mechanisms involved in each process. TMAH thermochemolysis must be viewed and used as a pertinent and complementary method for the analysis of carbohydrates protected and trapped by the organic matter in complex environmental systems.     

In-capillary preconcentration of proteins for capillary electrophoresis using a cellulose acetate-coated porous joint

This work describes the in-capillary preconcentration of proteins using a cellulose acetate-coated porous joint. The capillary wall near the inlet end of a capillary was made porous by HF etching. During the etching process, a voltage was applied across the capillary wall and the electric current across it was monitored. As the current passed through the capillary wall, it became porous. A solution of cellulose acetate in acetone was added to the etched porous joint. After the acetone was evaporated off, a cellulose acetate-coated porous joint was formed. To preconcentrate the protein ions, an electric voltage was applied between the inlet end of the capillary and the coated porous joint; the protein ions electromigrated to the porous joint but could not pass through it, while the buffer ions could pass easily through the joint. After allowing a certain amount of time for protein preconcentration, a separation voltage was applied across the two ends of the capillary, and normal capillary electrophoresis was carried out. The preconcentration factors for cytochrome c, lysozyme, ribonuclease, and chymotrypsinogen were 65, 155, 705, and 800, respectively. The cellulose acetate-coated porous joint was shown to be strong and stable over time, and was used to analyze trace proteins and macromolecules in biological samples.