Yanzhu Guo

Preparation of cellulose-graft-poly(ɛ-caprolactone) nanomicelles by homogeneous ROP in ionic liquid.

Self-associating cellulose-graft-poly(ɛ-caprolactone) (cellulose-g-PCL) copolymers were successfully synthesized via homogeneous ring-opening polymerization (ROP) of ɛ-CL onto softwood dissolved pulp substrate in ionic liquid 1-N-butyl-3-methylimidazolium chloride ([Bmim]Cl). An organic catalyst N,N-dimethylamino-4-pyridine (DMAP) was compared with the traditional metal-based catalyst (Sn(Oct)(2)) as the catalyst of the reaction, and exhibited higher catalytic activity. By controlling the cellulose:ɛ-CL feed ratio and reaction temperature, the molecular architecture of the copolymers can be altered, as evidenced by FT-IR, (1)H NMR, (13)C NMR, TGA and XRD. The self-assembly behavior of the copolymers in water was investigated and characterized using fluorescence probe, dynamic light scattering (DLS) and SEM. The results showed that the cellulose-g-PCL copolymers could form nanosized micelles (approximately 20-100 nm) in water, and the micelle size and critical micelle concentration (CMC) can be controlled by varying the grafting ratio of PCL. These cellulose-based nanomicelles are expected to be useful in broad application fields.

Self-Assembly and Paclitaxel Loading Capacity of Cellulose-graft-poly(lactide) Nanomicelles

A series of amiphiphilic cellulose-based graft copolymers (MCC-g-PLA) with various molecular factors were synthesized in ionic liquid BmimCl and characterized by FT-IR, (1)H NMR, (13)C NMR, XRD, and TGA. Their solubility in a variety of solvents was compared. The prepared MCC-g-PLA copolymers can self-assemble into spherical nanomicelles (10-50 nm) in aqueous solution. The self-assembly behaviors of the MCC-g-PLA copolymers were systematically investigated by fluorescence probe. Furthermore, the hydrophobic antitumor drug paclitaxel (PTX) was successfully encapsulated into the MCC-g-PLA micelles. The drug encapsulation efficiency and loading content were found to be as high as 89.30% (w/w) and 4.97%, respectively. Results in this study not only suggest a promising cellulose-based antitumor drug carrier but also provide information for property-directed synthesis of the cellulose graft PLA copolymers.

Synthesis and characterization of hydrophobic long-chain fatty acylated cellulose and its self-assembled nanoparticles

In this paper, a series of cellulose-based hydrophobic associating polymers were prepared by homogeneous acylation of microcrystalline cellulose with long-chain acyl chlorides including octanoyl, lauroyl, and palmitoly chlorides in the solvent of N,N-dimethylacetamide/lithium chloride (DMAc/LiCl) using pyridine as acid scavenger. Through controlling the chain length of fatty acyl chlorides and the molar ratio of acyl chlorides vs anhydroglucose unit, the hydrophobic cellulose derivatives with degrees of substitution in the range of 0.02–1.75 were successfully obtained. The chemical structures and properties of these hydrophobic derivatives were characterized by elemental analysis, FT-IR, CP/MAS 13C NMR, X-ray diffraction, and the thermogravimetry analysis. It was also found that, the cellulose-based polymers achieved an excellent solubility in organic solvents, such as benzene, methylbenzene, and pyridine, with the introduction of hydrophobic side chain into the cellulose backbone. Furthermore, it was found that these hydrophobic cellulose derivatives could self-assemble into spherical nanoparticles in aqueous solution, which indicates a tremendous potential of applications in pharmaceutical and medical fields.

Self-assembly and β-carotene loading capacity of hydroxyethyl cellulose-graft-linoleic acid nanomicelles

A series of linoleic acid conjugated hydroxyethyl cellulose polymers (HEC-g-LA) were synthesized and characterized. And their solubilities in a variety of solvents were compared. The prepared HEC-g-LA polymers showed typical properties of amphiphilic polymers and were able to self-assemble into spherical nanomicelles in aqueous solution. The micelle sizes and critical micelle concentrations (CMC) were found correlated with the molecular structure of polymers, and were varied in the range of 20-50nm and 1.92-21.76μg/ml, respectively. Furthermore, the hydrophobic active component β-carotene (β-C) was successfully encapsulated into the HEC-g-LA micelles by sonication-dialysis method. The β-C encapsulation efficiency and loading content were found to be as high as 84.67% (w/w) and 4.23%. The results of in vitro release showed that the encapsulated β-C was continuously released from the micelles in phosphate buffered saline (PBS) medium for about 7days. The self-assembled HEC-g-LA nanomicelles are potential nanocarriers of hydrophobic active compounds for functional food applications.

Structural changes of poplar wood lignin after supercritical pretreatment using carbon dioxide and ethanol–water as co-solvents

To delineate the structural changes of lignin during supercritical carbon dioxide pretreatment with ethanol–water as co-solvents (SCEP), enzymatic hydrolysis lignin (EHL) in original poplar chips, residual lignin in SCEP pretreated residues (SCEP-RL) and lignin dissolved in the SCEP liquors (SCEP-DL) were sequentially isolated and systematically characterized by GPC, quantitative 13C-NMR, 31P-NMR, 2D-HSQC NMR and TGA. After SCEP process, 19.2% of lignin was degraded and dissolved into SCEP liquors, while 4.8% of lignin was still present in the pretreated residues. It was also convinced that parts of the β-O-4 aryl ether linkages were cleaved and some of the stilbene, resinol (β–β) and phenylcoumaran (β-5) units were increased during SCEP process. Furthermore, the contents of free phenolic hydroxyl groups and carboxylic acids in SCEP-RL and SCEP-DL were higher than that of EHL.

Cellulosic micelles as nanocapsules of liposoluble CdSe/ZnS quantum dots for bioimaging

Nanostructures encapsulating multiple quantum dots (QDs) are of special interests for live cell imaging and biomolecular recognition due to their inherent signal amplification. In this study, a novel type of biomass-based nanomicelles was prepared and characterized for facile loading and solubilization of fluorescent hydrophobic CdSe/ZnS QDs in water. The biobased nanomicelles were formed by the self-assembly of amphiphilic cellulose-graft-poly (p-dioxanone) (MCC-g-PPDO) synthesized via homogeneous ring-opening polymerization in an ionic liquid. Through a simple physical loading method, multiple lipophilic CdSe/ZnS QDs can be simultaneously encapsulated in one MCC-g-PPDO micelle showing an obviously enlarged micelle size, whereas the loaded QDs exhibited a negligible change in their size and size distribution. The QDs-loaded cellulosic micelles exhibited good optical stability, narrow emission bandwidth as well as an acceptable quantum yield of ∼27%. Successful tumor cell internalization and negligible cytotoxicity were observed with these light-emitting cellulosic micelles. It was found that over 90% of the cells were viable after 24 h of exposure and the fluorescent signal inside the cells reached a maximum after 2 h of exposure. These QDs-loaded cellulosic nanomicelles derived from biomass are a promising candidate for bioimaging or other functional applications.

Preparation of Long-Chain Fatty Acyl-Grafted Chitosan in an Ionic Liquid and Their Self-Assembled Micelles in Water

Controllable synthesis of self-associating lauroyl-grafted chitosan with high molecular weight was realized in ionic liquid reacting media. The obtained lauroyl chitosan with different grafting degrees was characterized by FT-IR and 1H-NMR spectra. The chitosan derivatives were able to self-assemble into spherical polymeric micelles in water. The onset of micellization or critical micelle concentration (CMC) was estimated by fluorescence spectroscopy. The hydrodynamic diameters of various lauroyl chitosan micelles, determined by dynamic light scattering, were in the range of 122–295 nm. The morphology of the micelles was observed by scanning electron microscopy. The self-assembly behavior and the size of the assembled micelles of lauroyl chitosan were affected by the grafting degree of lauroyl groups. Generally, higher grafting degree resulted in lower CMC and smaller micelle size. These lauroyl chitosan nano-micelles may have potential applications in biological and medical fields.

Preparation, characterization and the adsorption characteristics of lignin/silica nanocomposites from cellulosic ethanol residue

The preparation, characterization, and adsorption characteristics of lignin/silica nanocomposites are described. The nanocomposites were obtained from cellulosic ethanol residue (CER) by an in situ method. The lignin was used as a structure directing reagent, and sulfuric acid as precipitating reagent during the synthesis of lignin/silica nanocomposites. The effects of pH on the properties of the nanocomposites have been investigated in detail. The prepared nanocomposites were characterized by the FT-IR, SEM, TG-TGA, XPS and low-temperature nitrogen sorption methods. Adsorption capacities and adsorption behaviors of selected lignin/silica nanocomposite, lignin, and silica for Methylene Blue (MB) were also studied, respectively. The results indicated that the lignin/silica nanocomposite is a good candidate for a biosorbent, providing a potential route for the high value-added utilization of CER.

Self-assembly of cationic amphiphilic cellulose-g-poly (p-dioxanone) copolymers

Cationic amphiphilic cellulose copolymers were prepared through grafting hydrophobic poly (p-dioxanone) (PPDO) chains onto hydrophilic quaternized cellulose derivatives (QC) via ring-opening polymerization (ROP) reaction, which was performed in 1-butyl-3-methylimidazolium chloride (BmimCl) and using 4-dimethylaminopyridine (DMAP) or 1,8-diazabicyclo (5.4.0) undec-7-ene (DBU) as catalyst. Their chemical structures and physical properties were confirmed by FT-IR, 1H-, 13C-, 2D HSQC-NMR, X-ray diffraction (XRD), and thermal stability (TGA) techniques, while self-assembly behavior was characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM) and fluorescence techniques. Both of the sizes and critical micelle concentration (CMC) values of micelles were decreased with increasing grafting contents of PPDO in the copolymers, which were in the ranges of 110-246 nm and 64-253 μg/mL, respectively. The ζ-potentials of micelles were cationic andranged from 39.1 mV to 45.4 mV. The highest encapsulation efficiencyof paclitaxel (PTX) into the micelles was 61.8% and 92.0% of loaded PTX was continuously released from micelles in phosphate buffered saline medium for 36 h.

Lignin Structure and Solvent Effects on the Selective Removal of Condensed Units and Enrichment of S-Type Lignin

This study focused on the structural differences of lignin after pyridine–acetic acid–water (PAW) and dioxane–acidic water (DAW) purification processes. These structural differences included the S/G ratio, condensed structure, weight-average (MW) molecular weights, β-O-4 linkages and sugar content. The chemical structure of the isolated crude lignin (CL), PAW purified lignin (PPL) and DAW purified lignin (DPL) was elucidated using quantitative 13C NMR, 2D-HSQC NMR spectra, thermogravimetric analysis (TGA), gel permeation chromatography (GPC) and Fourier transform infrared spectroscopy (FTIR). The results showed that the PPL fractions contain fewer condensed structures, higher S/G ratios, more β-O-4 linkages, higher average MW and lower thermal degradation properties compared to the CL and DPL fractions. Furthermore, the PAW process was more selective in removing condensed units and enriching S-type lignin from CL compared to the DAW process. These results provide valuable information for understanding which purification process is more suitable to be applied for lignin.