Hydrolysis of polycarbonate using ionic liquid [Bmim][Cl] as solvent and catalyst

The hydrolysis of polycarbonate (PC) was studied using ionic liquid [Bmim][Cl] as solvent and catalyst. The effects of reaction temperature, water dosage and [Bmim][Cl] dosage on reaction results were examined. It was showed that the hydrolysis conversion of PC was almost 100 % and the yield of bisphenol A (BPA) was over 95 % under the reaction conditions of temperature 165 °C, time 3.0 h, m([Bmim][Cl]):m(PC)=1.5:1 and n(H₂O):n(PC)=10:1. The ionic liquid could be reused for 8 times without obvious decrease in the conversion of PC and yield of BPA. Therefore, an environmental friendly strategy for chemical recycling of PC was developed.     

Influence of residual ionic liquid on the thermal stability and electromechanical behavior of cellulose regenerated from 1-ethyl-3-methylimidazolium acetate

The regenerated cellulose films were prepared by dissolving cotton cellulose pulp directly in room temperature ionic liquid namely, 1-ethyl-3-methylimidazolium acetate at 80 °C, followed by washing/curing in different coagulants namely, methanol, deionized water, methanol-deionized water, and isopropyl alcohol-deionized water. It was found that the type of coagulants employed for curing the cellulose films has a significant influence on the amount of residual ionic liquid entrapped in the films. The amount of residual ionic liquids was 2.68, 1.01, 0.84, and 0.75 wt.% for the films cured with deionized water, isopropyl alcohol-deionized water, methanol, and methanol-deionized water, respectively. The DTG peaks of regenerated cellulose films showed two decomposition temperatures at 280 °C and 320 °C. Among all the cases studied, deionized water curing case showed the lowest decomposition temperature, attributed to entrapment of large residual ionic liquid in it. Electromechanical characteristic of the regenerated cellulose films was also investigated.     

Preparation of cellulose/multi-walled carbon nanotube composite membranes with enhanced conductive property regulated by ionic liquids

Cellulose/multi-walled carbon nanotubes (MWCNTs)- composite membranes applied in electrochemical and biomedical fields were prepared using 1-ethyl-3-methylimidazolium diethyl phosphate (EmimDEP) as solvent in this study. With the increasing of MWCNTs amount, the membrane conductivity increased, and the conductivity reached 9.1 S/cm as the mass ratio of MWCNTs to cellulose being 2:1. The additions of sodium dodecyl sulfate (SDS), 1-hexadecyl-3-methylimidazolium bromide (C₁₆mimBr) and 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF₄) efficiently improved the conductivity, mechanical property, and thermal stability by promoting the dispersion of MWCNTs. When the mass ratio of C₁₆mimBr to MWCNTs changed from 0 to 0.3:1, the conductivity increased from 0.08 S/cm to 0.14 S/cm, and the tensile strength increased from 13.3 MPa to 17.0 MPa. These results indicate that the binary ionic liquids (ILs) system can regulate the properties of the composite membranes, and is a feasible approach for preparing cellulose/MWCNTs composite membranes with enhanced properties.     

A new strategy for acid anhydrides-modified xylans in ionic liquids

Recently, homogeneous synthesis of functional carbohydrate polymers carried out in ionic liquids (ILs) has attracted extensive consideration because high reaction efficiency can be achieved. The objective of our work was to develop a new strategy to prepare acid anhydrides-modified xylan by the esterification of xylan with different types of acid anhydride such as acetic anhydride and succinic anhydride under the optimal dissolution condition of xylan in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) ionic liquid. Significantly, effect factors on the xylan dissolution in [BMIM]Cl ionic liquid such as the concentration of xylan and the temperature were comparatively investigated, and the dissolution mechanism of xylan in [BMIM]Cl ionic liquid was revealed The physical and chemical properties of regenerated xylan were characterized by with various techniques such as FT-IR and GPC as well as TGA. Under the optimal dissolution condition of xylan in [BMIM]Cl, different acid anhydrides-modified xylan was comparatively discussed in the presence and the absence of catalyst. It was found that catalyst has different role in the chemical modification of xylan with different types of acid anhydride due to the chemical structure of acid anhydride.     

Isolation of cellulose with ionic liquid from steam exploded rice straw

Isolation of cellulose from straw is a bottleneck for exploiting such biomass resources. In recent years, considerable concerns have arisen over new efficient and environmentally friendly way for this purpose. A novel method for cellulose isolation has been proposed by dissolving steam exploded rice straw in 1-allyl-3-methylimidazolium chloride ionic liquid (IL), following regeneration of crude cellulose by diluting the cellulose-ionic liquid solution adequately after separation of insoluble residues. The crude cellulose was then bleached by 2% hydrogen peroxide aqueous solution with low-flux ozone blowing into. No acid-insoluble lignin and only 0.85% hemicelluloses were detected in the bleached cellulose. The isolated cellulose was analyzed by SEM, FT-IR, ¹³C CP/MAS solid state NMR, XRD spectroscopes, and the results indicated that high quality cellulose preparation could be isolated in this manner from rice straw.     

Improvement of mechanical and electrical properties of poly(ethylene glycol) and cyanoresin based polymer electrolytes

Ionic conductivity and mechanical properties of a mixed polymer matrix consisting of poly(ethylene glycol) (PEG) and cyanoresin type M (CRM) with various lithium salts and plasticizer were examined. The CRM used was a copolymer of cyanoethyl pullulan and cyanoethyl poly(vinyl alcohol) with a molar ratio of 1:1, mixed plasticizer was ethylene carbonate (EC) and propylene carbonate (PC) at a volume ratio of 1:1. The conductive behavior of polymer electrolytes in the temperature range of 298∼338 K was investigated. The PEG/LiClO₄ complexes exhibited the highest ionic conductivity of ∼10⁻⁵ S/cm at 25°C with the salt concentration of 1.5 M. In addition, the plasticized PEG/LiClO₄ complexes exhibited improvement of ionic conductivity. However, their complexes showed decreased mechanical properties. The improvement of ionic conductivity and mechanical properties could be obtained from the polymer electrolytes by using CRM. The highest ionic conductivity of PEG/CRM/LiClO₄/(EC-PC) was 5.33×10⁻⁴ S/cm at 25°C.     

Capacitive behaviors and monomer concentration effects of poly(9-benzyl-9<Emphasis Type="Italic">H</Emphasis>-carbazole) on carbon fiber microelectrode

In this work, 9-benzyl-9H-carbazole (BzCz) monomer was chemically synthesized by a new process. It was electrocoated on carbon fiber microelectrode (CFME) as an active electrode material in 0.1 M sodium perchlorate (NaClO₄)/acetonitrile (ACN) solution. The electropolymerization process was successfully performed less amount of 3 mM. The characterization of Poly(BzCz)/CFME thin films was performed by Fourier transform infrared reflectance-attenuated total reflection spectroscopy (FTIR-ATR) and Electrochemical impedance spectroscopy (EIS). The effects of monomer concentrations (1, 2, and 3 mM) during the preparation of modified electrodes were examined by EIS. Capacitive behaviors of modified CFMEs were defined via Nyquist, Bode-magnitude and Bode-phase plots. Variation of capacitance values by initial monomer concentration and specific capacitance values are presented. The highest specific capacitance value for a potensiodynamically prepared polymer thin film in the initial monomer concentration of 1 mM with a charge of 4.54 mC cm⁻² was obtained about 221.4 μF cm⁻². An equivalent circuit model, R(C(R(QR)))(CR), for different concentrations of Poly(BzCz). CFME was proposed and experimental data were simulated to obtain the numerical values of circuit components.     

Functionalizing cellulose scaffold prepared by ionic liquid with bovine serum albumin for biomedical application

The present study reports the preparation of a cellulose scaffold for tissue engineering directly from cellulose fiber using ionic liquid (IL) by the NaCl leaching method with bovine serum albumin (BSA), which is well known protein utilized for biomedical applications like degradation of polymer, cell attachment and proliferation on scaffold. The 1-n-allyl-3-methylimidazolium chloride (AmimCl) IL was used as a solvent for cellulose. The morphology of the scaffold was studied by scanning electron microscopy (SEM) and the images showed that the pore sizes of the scaffolds were about 200 µm. In addition, the water uptake (WU) and degree of degradation of the cellulose scaffold were measured. Meanwhile, the biocompatibility and bioactivity of the scaffold were determined via 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenytetrazolium bromide (MTT) assay and the Live/Dead viability test. The various results demonstrated the ability of the Mesenchymal stem cells (MSC) to attach to the surface of the scaffolds amplified as percentage of BSA increased in cellulose scaffold.     

High-intensity ultrasound irradiated modification of sugarcane bagasse cellulose in an ionic liquid

This current work is concerned with the glutarylation of sugarcane bagasse cellulose in ionic liquid 1-butyl-3-methylimidazolium chloride by ultrasound irradiation without catalyst. The degree of substitution ranging from 0.22 to 1.20 was obtained in one-step homogeneous modification, which increased with ultrasound irradiation time, temperature, and the molar ratio of glutaric anhydride/anhydroglucose unit in cellulose. The structural characterization of the glutarylated cellulose was carried out by using FT-IR and CP/MAS ¹³C NMR and the results showed that the glutarylation reaction occurred. The thermal stability of the glutarylated cellulose decreased upon chemical modification.     

Highly conductive cellulosic nanofibers for efficient water desalination

Electrically conducting nanofibers based on cellulosic materials offer cheap and safe class of materials that can be used for water desalination. In the present work, high conducting cellulose triacetate (CTA) nanofibers containing multiwall carbon nanotubes (MWCNTs) with very low percolation threshold concentration (0.014 wt%) were produced by electrospinning. Unprecedentedly, a hydrophilic ionic liquid consists of 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) was used to dissolve CTA producing a solution of 10 wt%. This CTA solution was used to engineer both bare CTA nanofibers and CTA nanofibers impregnated with MWCNT. The fabricated nanofibers were characterized by the field emission-scanning electron microscopy (FE-SEM) and the high-resolution transmission electron microscopy (HR-TEM). Both FE-SEM and HR-TEM images showed that the MWCNTs were inserted and uniformly distributed inside electrospun nanofibers. Furthermore, mechanical properties such as tensile strength of MWCNTs loaded-CTA electrospun nanofibers was significantly improved by up to 280 % and 270 % for the Young modulus, when compared with the bare CTA fibers. In addition, the surface properties as the hydrophilicity of electrospun nanofibers membrane was enhanced due to the presence of MWCNTs. Moreover, the electrical conductivity of MWCNT loaded-CTA electrospun nanofibers was greatly enhanced after the implementation of the MWCNTs inside the CTA fiber. The performance of composite nanofiber for water desalination was examined in a lab-scale classic capacitive deionization (CDI) unit, at different concentrations of salt. The obtained data revealed that the electro-adsorption of anions and cations on the surface of MWCNTs loaded-CTA electrospun nanofibers electrodes were monitored with time and their concentration were decreased progressively with time and reaches equilibrium.     

A comparison study on phase transition and structure of cornstarch in dimethyl sulfoxide and ionic liquid systems

A comparison study of the phase transition and structure of waxy cornstarch in DMSO and AMIMCl systems was conducted using a differential scanning calorimeter, an optical microscope, a scanning electron microscope, X-ray diffraction and thermogravimetric analysis. A full disruption and dissolution of starch granules was completed in 10 h at room temperature in pure DMSO, which was faster and more effective than that in ionic liquid 1-allyl-3-methylimidazolium chloride (AMIMCl). When dispersed in DMSO/water and AMIMCl/water at various ratios, respectively, different phase transitions were clearly exhibited, and the appearance and crystal structure of starch granules were significantly damaged with an increase in the concentration. Basing on the study of the decomposition temperature change through TGA measurements, a decreased temperature was observed in both DMSO and AMIMCl system, meaning starch degradation occurred with different levels. The huge temperature change from 357 to 328 °C were found in AMIMCl system, which most likely induced the distinct exothermic phenomenon in the DSC observation due to a significant depolymerization of starch.     

Synthesis and electropolymerization of 9-(4-vinylbenzyl)-9H-carbazole on carbon fiber microelectrode: Capacitive behavior of poly(9-(4-vinylbenzyl)-9H-carbazole)

The synthesis of 9-(4-vinylbenzyl)-9H-carbazole (VBCz) monomer and surface characterizations of thin film coating of poly(9-(4-vinylbenzyl)-9H-carbazole), P(VBCz) homopolymer on carbon fiber microelectrode (CFME) was performed. Coatings of polymer thin films obtained, with different initial monomer concentrations, were characterized by cyclic voltammetry, scanning electron microscopy and Fourier transform infrared reflectance-attenuated total reflection spectroscopy. Different initial monomer concentrations (1, 3, 5, and 10 mM) were electrodeposited in 0.1 M lithium perchlorate/acetonitrile solution. The characterization of the thin polymer films was performed on the surface of carbon fiber, and composition of polymeric structure was proposed. Capacitor behavior of modified CFME was studied by electrochemical impedance spectroscopy. The deposition charge of polymer growth affected the redox parameters of resulting coated CFME.     

Modification of ramie with 1-butyl-3-methylimidazolium chloride ionic liquid

For a long time, alkali is the main modification reagent for ramie modification due to its good effect and low cost. However, the large consumption of alkali in the processing leads to a serious pollution to the environment. To develop a new eco-friendly modification method, a mixed green solvent composed of 95 wt% 1-butyl-3-methylimidazolium chloride ionic liquid and 5 wt% water was employed in the paper. The swelling ratio, surface composition and crystal index was studied in detail with video microscope, FTIR and XRD analysis. Results showed that the solvent system had a distinct swelling effect on ramie. The crystal index of ramie fiber decreased from 74.2 % to 54.5 % after the treatment. Otherwise, the modification also removed some gummy substances including 75 % content of pectin in ramie. These changes improved the wetability and dyeing properties of ramie. However, the treatment also did much harm to the tensile strength.     

Characterization and electrochemical properties of poly(aniline-co-o-methoxyaniline)/multi-walled carbon nanotubes composites synthesized by solid-state method

The composites of copolymers of aniline (An) and o-methoxyaniline (OMA) with multi-walled carbon nanotubes, named as copolymers/MWNT, (poly(An-co-OMA)/MWNT) were prepared by solid-state synthesis method at room temperature. The homopolymers/MWNT composites were synthesized for comparison. The structure and morphology of these composites were characterized by FT-IR spectroscopy, UV-Vis absorption spectroscopy, X-ray diffraction (XRD) and TEM. The electrochemical performances of the composites were investigated by galvanostatic charge-discharge, cyclic voltammetry (CV) and cycle life measurements. The results from FT-IR and UV-Vis spectra showed that different molar ratio of [An]/[OMA] in reaction system has great influence on the oxidation degree, conjugation length and doping level of the copolymers in these composites. The presence of MWNT in the composites was confirmed from the characteristic peaks of MWNT in XRD patterns and the enwrapped MWNT in TEM images. The TEM images further indicates that the MWNT uniformly distributed and enwrapped with polymer in the case of composite from molar ratio of [An]/[OMA]=1:1. The results also showed that the morphology, crystallinity and solubility of composites were highly affected by the incorporation of OMA unit copolymer chain. The results from electrochemical performances suggested that the molar ratio of [An]/[OMA]=3:1 in reaction system can make the obtained composites displayed a higher specific capacitance, good rate ability and cycling stability.     

Dissolving lignocellulosic biomass in a 1-butyl-3-methylimidazolium chloride-water mixture

An ionic liquid (IL)-water mixture employed to treat lignocellulosic biomass is promising. The addition of water decreases viscosity and process cost so as to improve the IL practical application. In this work, effects of temperature (50-170 °C), water content (0-80 wt%), treating duration (0.5-4 h) and pressure (0.1-3.2 MPa) on treating legume straw process using a 1-butyl-3-methylimidazolium chloride ([C₄mim]Cl)-water mixture were experimentally investigated. Legume straw was found to be partially dissolved, and the dissolved substances can be flocculated by adding the coagulating agent—water (equal to volume of the solution). For this process at 0.1 MPa, the maximum 29.1 wt% legume straw is dissolved in the [C₄mim]Cl-water mixture with water content of 20 wt% at 150 °C during 2 h, which is much higher than 9.8 wt% using pure [C₄mim]Cl. A hemicellulose-free lignin-rich material (64.0 wt% lignin and 35.3 wt% cellulose) is obtained by adding the water. Even for 0.5 h, 22.3 wt% of legume straw is dissolved in the case of water content of 20 wt%, 150 °C and 0.1 MPa. High pressure favors the dissolution of legume straw but lignin content in the residue has no obvious change. The addition of proper amount of water facilitates the dissolution of legume straw and a relative rapid dissolving rate can be achieved in a [C₄mim]Cl-water mixture. There are great differences in chemical and physical properties between legume straw and the obtained samples (residue and floc) due to the dissolution and reconstitution.     

Synthesis and electropolymerization of 9-tosyl-9<Emphasis Type="Italic">H</Emphasis>-carbazole,electrochemical impedance spectroscopic study and circuit modelling

This work reports on the newly synthesized 9-tosyl-9H-carbazole (TsCz) monomer. Capacitive properties of the electrochemically grown homopolymer, poly(TsCz) film on carbon fibre microelectrode (CFME), are characterised by cyclic voltammetry (CV), Fourier transform infrared reflectance-attenuated total reflection spectroscopy (FTIR-ATR), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). Different monomer concentrations (1, 3 and 10 mM) were used for electrodeposition in 0.1 M sodium perchlorate (NaClO₄)/acetonitrile (ACN) solution. The capacitive behaviour of modified CFMEs was defined via Nyquist, Bode-magnitude and Bode-phase plots. An equivalent electrical circuit R(CR)(QR)(CR) for different concentrations of poly(TsCz)/CFME was proposed and experimental data were simulated to obtain the numerical values of the circuit components. The Nyquist plot for poly(TsCz) shows the highest specific capacitance (50.0 mF cm⁻²) at frequency of 0.01 Hz in the initial monomer concentration of 10 mM.     

Secondary Metabolites of a Mangrove Endophytic Fungus Aspergillus terreus (No. GX7-3B) from the South China Sea

The mangrove endophytic fungus Aspergillus terreus (No. GX7-3B) was cultivated in potato dextrose liquid medium, and one rare thiophene compound (1), together with anhydrojavanicin (2), 8-O-methylbostrycoidin (3), 8-O-methyljavanicin (4), botryosphaerone D (5), 6-ethyl-5-hydroxy-3,7-dimethoxynaphthoquinone (6), 3β,5α-dihydroxy-(22E,24R)-ergosta-7,22-dien-6-one (7), 3β,5α,14α-trihydroxy-(22E,24R)-ergosta-7,22-dien-6-one (8), NGA0187 (9) and beauvericin (10), were isolated. Their structures were elucidated by analysis of spectroscopic data. This is the first report of a natural origin for compound 6. Moreover, compounds 3, 4, 5, 7, 8 and 10 were obtained from marine microorganism for the first time. In the bioactive assays in vitro, compounds 2, 3, 9 and 10 displayed remarkable inhibiting actions against α-acetylcholinesterase (AChE) with IC₅₀ values 2.01, 6.71, 1.89, and 3.09 μM, respectively. Furthermore, in the cytotoxicity assays, compounds 7 and 10 exhibited strong or moderate cytotoxic activities against MCF-7, A549, Hela and KB cell lines with IC₅₀ values 4.98 and 2.02 (MCF-7), 1.95 and 0.82 (A549), 0.68 and 1.14 (Hela), and 1.50 and 1.10 μM (KB), respectively; compound 8 had weak inhibitory activities against these tumor cell lines; compounds 1, 2, 3, 4, 5, 6 and 9 exhibited no inhibitory activities against them.     

Eu2O3及其添加方式对马铃薯愈伤组织的诱导

以马铃薯幼嫩茎段为外植体,在相同激素条件下,于固体和液体培养基中附加不同浓度的氧化铕,探讨氧化铕的浓度及添加方式对马铃薯愈伤组织诱导及生长的影响。结果表明：不同浓度的氧化铕对马铃薯愈伤组织的诱导和生长的影响不同。统计学分析结果表明：固体培养基中氧化铕浓度为20.0~35.0 mg/L时,液体-固体双层培养时固体培养基中氧化铕浓度为10.0 ~ 30.0 mg/L时,液体-固体双层培养时液体培养基中氧化铕浓度为20.0~40.0 mg/L时,3种情况均适合马铃薯愈伤组织的诱导及生长。氧化铕在液体培养基中存在     

Controlled release of diclofenac from matrix polymer of chitosan and oxidized konjac glucomannan

The controlled release of diclofenac sodium (DFNa) from a chitosan-oxidized konjac glucomannan (CTS-OKG) polymer film was studied. Konjac glucomannan (KGM) was initially oxidized by sodium periodate and then cross-linked to CTS via imine bonds (-C=N-) to form the new CTS-OKG copolymer. The DFNa loaded CTS-OKG polymers were characterized by Fourier transformed infrared spectroscopy (FT-IR) and X-ray diffractometry (XRD). Finally, the release profiles of DFNa from the CTS-OKG polymer matrices were evaluated in a simulated gastrointestinal fluid system comprised of two hours in simulated gastric fluid (SGF; pH 1.2) followed by 24 h in simulated intestinal fluid (SIF; pH 7.4). A 1:2:1 (w/w/w) ratio of CTS:OKG:DFNa prepared at room temperature for 3 hours gave the highest % encapsulation efficiency (EE) of 95.6 ± 0.6 and resulted in a minimal release of DFNa (<1% over 2 h) in SGF (pH 1.2) and a significantly improved sustained release in SIF (pH 7.4) with ~6% and 19% release over 8 and 24 h, respectively), some 15- and five-fold lower than that of the two commercial DFNa preparations, Diclosian and Voltaren. This formulation may be used for further study as a long term intestine controlled release drug model (at least 3 days).     

Antibacterial blend films of cellulose and chitosan prepared from binary ionic liquid system

A new hybrid ionic liquids solvent, 1-allyl-3-methylimidazolium chloride (AMIMCl) and glycine hydrochloride (Gly·HCl) was utilized to dissolve chitosan and fabricate chitosan/cellulose (Cs/Ce) blend films with chitosan proportion varying from 2 to 35 wt.% through solution casting method. FTIR, XRD, TG, SEM and EA were used to evaluate the prepared composites. Besides, the mechanical property and antibacterial activity were also analyzed. The shifting of the characteristic peaks of -NH and C=O for chitosan, similar crystal pattern with low intensity diffraction peaks at 2θ of around 20°, superior thermal stability (increased T_onset) with chitosan ratio below 10 wt.% in the composites suggested that the interactions via hydrogen bonds formed between chitosan and cellulose. Besides, the elemental analysis showed that the actual N% contents from the chitosan in the blend films were roughly equivalent to the theoretical value though the inevitable residue of ionic liquids. Furthermore, the blends not only presented compact structure but also processed high bacterial reduction to E. coli and S. aureus at pH 6.3, which indicated that the Cs/Ce blend films prepared via the Gly·HCl/AMIMCl dissolution method were suitable for production of degradable antibacterial materials.