Ruigang Liu

Modified native cellulose fibers—A novel efficient adsorbent for both fluoride and arsenic

Native cellulose fibers were surface modified by poly(N,N-dimethyl aminoethyl methacrylate) (PDMAEMA) to generate an anion adsorbent, which was characterized by scanning electron microscopy, fourier transform infrared spectroscopy and elemental analyzer. This adsorbent had high efficiency in removal of F(-), AsO(2)(-) and AsO(4)(3-) from aqueous solutions, even at low initial concentrations. Adsorption kinetics showed that the adsorption equilibrium could be reached within 1 min. The distribution coefficient did not change with adsorbent dose, indicating the adsorption was a homogenous process. Langmuir, Freundlich and Temkin models were used to fit the adsorption isotherms. Based on the parameters calculated from the models, the adsorption capacity was in the order of AsO(4)(3-)≫AsO(2)(-)>F(-), and the adsorption was a favorable process. Compared with Freundlich and Temkin models, the isotherms followed Langmuir model a little better.

Self-Assembly and Dual-Stimuli Sensitivities of Hydroxypropylcellulose-graft-poly(N,N-dimethyl aminoethyl methacrylate) Copolymers in Aqueous Solution

The self-assembly and pH- and thermo-sensitivities properties of hydroxypropyl cellulose-graft-poly(N,N-dimethyl aminoethyl methacrylate) (HPC-g-PDMAEMA) copolymers in aqueous solutions were investigated by transmittance, dynamic light scattering (DLS), and (1)H NMR spectroscopy. Micelles with different structure can be formed by varying either pH value or temperature. At low pH, e.g., 3.0, the HPC backbone of the copolymer collapse to form the core of micelles stabilized with protonated PDMAEMA side chains on the surface of the micelles upon heating. At the medium pH, e.g., 8.1, both HPC backbone and PDMAEMA side chains collapse upon heating to form unstable aggregates. At high pH, e.g., 12.3, PDMAEMA side chains collapse first to form the core of micelles stabilized with HPC chains upon heating. Further heating the copolymer solution at this pH leads to the aggregation of the micelles due to the collapse of the shell HPC chains. The thermal sensitivity of the HPC-g-PDMAEMA copolymers is reversible.

Dissolution mechanism of cellulose in N,N-dimethylacetamide/lithium chloride: revisiting through molecular interactions.

Understanding the interactions between solvent molecules and cellulose at a molecular level is still not fully achieved in cellulose/N,N-dimethylacetamide (DMAc)/LiCl system. In this paper, cellobiose was used as the model compound of cellulose to investigate the interactions in cellulose/DMAc/LiCl solution by using Fourier transform infrared spectroscopy (FTIR), (13)C, (35)Cl, and (7)Li nuclear magnetic resonance (NMR) spectroscopy and conductivity measurements. It was found that when cellulose is dissolved in DMAc/LiCl cosolvent system, the hydroxyl protons of cellulose form strong hydrogen bonds with the Cl(-), during which the intermolecular hydrogen bonding networks of cellulose is broken with simultaneous splitting of the Li(+)-Cl(-) ion pairs. Simultaneously, the Li(+) cations are further solvated by free DMAc molecules, which accompany the hydrogen-bonded Cl(-) to meet electric balance. Thereafter, the cellulose chains are dispersed in molecular level in the solvent system to form homogeneous solution. This work clarifies the interactions in the cellulose/DMAc/LiCl solution at molecular level and the dissolution mechanism of cellulose in DMAc/LiCl, which is important for understanding the principle for selecting and designing new cellulose solvent systems.

Smart Assembly Behaviors of Hydroxypropylcellulose-graft-poly(4-vinyl pyridine) Copolymers in Aqueous Solution by Thermo and pH Stimuli

Thermo- and pH-sensitive graft copolymers, hydroxypropylcellulose-graft-poly(4-vinyl pyridine) (HPC-g-P4VP), were synthesized via atom transfer radical polymerization (ATRP) and characterized. The thermo- and pH-induced micellization and stimuli-responsive properties of HPC-g-P4VP graft copolymers in aqueous solution were investigated by transmittance, (1)H NMR, dynamic light scattering (DLS), and so on. For the pH-induced micellization, the P4VP side chains collapse to form the core of the micelles, and the HPC backbones stay in the shell to stabilize the micelles. In the case of thermoinduced micellization, the HPC backbones collapse to form the core of the micelles that was stabilized by the P4VP side chains in the shell upon heating. Whats more, the cloud point of the HPC-g-P4VP copolymers in the aqueous solution could be finely tuned by changing the length of P4VP side chains or the pH values. In acidic water, the longer the side chains, the higher the cloud point. For those HPC-g-P4VP copolymers with short side chains, for example, HPC0.05-g-P4VP(3), the lower pH correlates a higher cloud point. The thermo- or pH-induced micelles also have the pH- or thermosensitivity due to their P4VP or HPC shells.

Controllable Aggregation and Reversible pH Sensitivity of AuNPs Regulated by Carboxymethyl Cellulose

A pH-sensitive gold nanoparticle-cysteamine/carboxymethyl cellulose (Au-CA/CMC) dispersion system was prepared by a simple approach. Gold nanoparticles (AuNPs) were first synthesized by directly reducing chloroauric acid (HAuCl(4)) with sodium carboxymethyl cellulose (CMC). Then the AuNPs were decorated by an electrostatic compound of cysteamine hydrochloride (CA) and sodium carboxymethyl cellulose (CMC) through ligand exchange to get the assembly of Au-CA/CMC. The Au-CA/CMC dispersion system exhibits strongly reversible pH-responsive behavior with the aggregation of AuNPs caused by the combined action of the chain conformation change of CMC and electrostatic interactions between CA and CMC at different pH values. Finally, the reversible aggregation mechanism of AuNPs in the Au-CA/CMC dispersion system has been investigated by transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy (UV-vis spectroscopy). This study provides a new method to fabricate a stimuli-responsive system free from complicated organic synthesis without using a toxic reducing agent.

Intermolecular interactions and 3D structure in cellulose-NaOH-urea aqueous system.

The dissolution of cellulose in NaOH/urea aqueous solution at low temperature is a key finding in cellulose science and technology. In this paper, (15)N and (23)Na NMR experiments were carried out to clarify the intermolecular interactions in cellulose/NaOH/urea aqueous solution. It was found that there are direct interactions between OH(-) anions and amino groups of urea through hydrogen bonds and no direct interaction between urea and cellulose. Moreover, Na(+) ions can interact with both cellulose and urea in an aqueous system. These interactions lead to the formation of cellulose-NaOH-urea-H2O inclusion complexes (ICs). (23)Na relaxation results confirmed that the formation of urea-OH(-) clusters can effectively enhance the stability of Na(+) ions that attracted to cellulose chains. Low temperature can enhance the hydrogen bonding interaction between OH(-) ions and urea and improve the binding ability of the NaOH/urea/H2O clusters that attached to cellulose chains. Cryo-TEM observation confirmed the formation of cellulose-NaOH-urea-H2O ICs, which is in extended conformation with mean diameter of about 3.6 nm and mean length of about 300 nm. Possible 3D structure of the ICs was proposed by the M06-2X/6-31+G(d) theoretical calculation, revealing the O3H···O5 intramolecular hydrogen bonds could remain in the ICs. This work clarified the interactions in cellulose/NaOH/urea aqueous solution and the 3D structure of the cellulose chain in dilute cellulose/NaOH/urea aqueous solution.

Osmium Bipyridine-Containing Redox Polymers Based on Cellulose and Their Reversible Redox Activity

Thermo-, pH-, and electrochemical-sensitive cellulose graft copolymers, hydroxypropyl cellulose-g-poly(4-vinylpyridine)-Os(bipyridine) (HPC-g-P4VP-Os(bpy)), were synthesized and characterized. The electrochemical properties of the resulting material were investigated via cyclic voltammetry by coating the graft copolymers on the platinized carbon electrode. The results indicated that the electrochemical properties of the graft copolymer modified electrode were responsive to the pH values of the electrolyte solution. The reversible transformation between the active and inactive state originated from the changes in the architecture of the HPC-g-P4VP-Os(bpy) graft copolymer at different pH values. At high pH (e.g., above the pK(a) of P4VP), the chains of P4VP collapsed, and the electrochemical activity of the electrode was reduced. With immobilization of glucose oxidase (GOx) on the graft copolymer decorated electrode, a biosensor for glucose detection was prepared. The current of the biosensor depended on the glucose concentration in the detected solution and increased with the successive addition of glucose.

Regulation of the thermal sensitivity of hydroxypropyl cellulose by poly(N-isopropylacryamide) side chains

Hydroxyproyl cellulose graft poly(N-isopropylacryamide) (HPC-g-PNIPAm) copolymers were synthesized by single-electron transfer living radical polymerization (SET-LRP) in water and THF mixture solvent and characterized. The controllability and polymerization rate of SET-LRP can be adjusted by the water/THF ratio in the mixture solvent. The monomer conversion rate is relatively low in the solvent with low water content. The thermal responsive property of HPC-g-PNIPAm copolymers in aqueous solution depends on the length of the graft chains. The relatively short PNIPAm side chains (<150 repeat units) can effectively regulate the low critical solution temperature (LCST) of the HPC-g-PNIPAm copolymers in aqueous solution due to the hydrophilic properties of the short PNIPAm chains. This work provides an approach for the regulation of the LCST to body temperature region by graft copolymerization.

Dual effects of dimethylsulfoxide on cellulose solvating ability of 1-allyl-3-methylimidazolium chloride

Polar aprotic solvents are considered to act as cosolvents with ionic liquids (ILs) for cellulose, strengthening the solvating ability of ILs by improving their cellulose solvating kinetics without influencing the solubility of cellulose in ILs. In this work, it was found that dimethylsulfoxide (DMSO) at low concentration improves the cellulose solvating ability of [AMIM][Cl], but weakens it at high concentration. To clarify the mechanism of these dual effects of DMSO on the cellulose solvating ability of [AMIM][Cl], the [AMIM][Cl]/DMSO system was investigated using excess infrared spectroscopy, nuclear magnetic resonance (NMR) T2 relaxometry, 1H NMR, 35Cl NMR, and dynamic light scattering. The results indicate that the tight association between the cation and anion in the [AMIM][Cl] network is loosened at low DMSO concentration. As a result, mass transport is accelerated due to the enhanced dynamics of [AMIM][Cl], promoting the cellulose solvating kinetics of [AMIM][Cl]. However, ion clusters of [AMIM][Cl] start to form when the molar fraction of DMSO (xDMSO) exceeds 0.5. The hydrogen bonds between cations and anions in the ion clusters become much stronger than in pure [AMIM][Cl], leading to decreased ability of [AMIM][Cl] to form hydrogen bonds with cellulose and thus decreased cellulose solubility in the [AMIM][Cl]/DMSO mixture.

Effect of microgel content on the shear and extensional rheology of polyacrylonitrile solution

Crosslinked polyacrylonitrile (cPAN) particles with uniform size were synthesized through precipitation polymerization. The as-formed cPAN nanoparticles were dispersed in polyacrylonitrile (PAN) solutions to form microgels with various contents, which were used as model to study the influence of the microgels on the shear and extensional rheology of PAN solutions. Flow curves of steady shear viscosity displayed shear thinning and followed time–temperature superposition principle. The dependency of activation energy on the content of cPAN microgels indicated that introduction of microgels weakened the temperature sensitivity of PAN solutions. For extensional rheology study, we utilized the capillary thinning rheometry to characterize the elongation relaxation time and apparent extensional viscosity. Study of filament thinning dynamics with a series of system strains confirmed that the higher content of cPAN microgels the lower extensional strength and worse spinnability of the PAN solution.