Junjun Tan

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.

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.

Dual-stimuli sensitive nanogels fabricated by self-association of thiolated hydroxypropyl cellulose

A new type of cellulose derivative was synthesized by means of conjugating cysteamine to hydroxypropyl cellulose (HPC) and the degree of thiol groups could be controlled by the feed ratio of the reactants. The thiolated HPC (HPC–SH) maintains the thermosensitivity of HPC and the thiol groups on the HPC chain can be oxidized to disulfide bonds. Cytotoxity tests performed on MG-63 cells proved that HPC–SH is not harmful to the cells. Nanogels can be fabricated by the self-association of HPC–HS in the solution at 45 °C and then oxidation of thiol groups to disulfide bonds occurs to stabilize the associated structure. The crosslinking degree of the nanogels could be controlled by the substitution degree of thiol groups (–SH) in the thiolated HPC. The hydrodynamic radius of the nanogels can be tuned by adjusting the degree of crosslinking and the concentration of the initial thiolated HPC solution in the self-association process. The hydrodynamic radius of the nanogels can be changed with the temperature and the dissociation process can happen by adding the reducing agent dithiothreitol (DTT). The dual-stimuli sensitive nanogels may have potential applications in controlled drug release, transfer switch device and sensors.

Investigation of deformation instability of Au/Cu multilayers by indentation

Plastic deformation behavior of Au/Cu multilayers with individual layer thicknesses of 25–250 nm was investigated via microindentation experiments. It was found that plastic instability of the Au/Cu multilayer exhibits strong length scale (individual layer thickness and grain size) dependence. The smaller the length scale, the easier shear bands form. In other words, plastic deformation becomes unstable with decreasing length scale. Cross-sectional observation along with plan-view indicates that the occurrence of plastic deformation instability corresponds to transformation of the deformation mechanism associated with geometrical configuration and length scale of the material. At nanometer scale, buckling-assisted interface crossing of dislocations results in local shear band, while, at submicron scale or above, local dislocation pileup-induced interface offset leads to plastic instability. Theoretical analysis is conducted to understand the length scale-dependent plastic deformation behavior of the multilayer.

Two different types of shear-deformation behaviour in Au-Cu multilayers

Localised shear deformation of a material is usually identified as a particular feature of deformation inhomogeneity. Here, we show two different types of shear deformation-behaviour that occurred in Au–Cu multilayers subjected to microindentation load, namely, a cooperative-layer-buckling-induced shear banding in a nanoscale multilayer and a direct localised shearing across a layer interface along a shear plane in a submicron-scale multilayer. Theoretical analysis indicates that the formation of the two different types of shear deformation in the multilayers depends on a competition between the dislocation-pile-up-induced stress concentration at the layer interface and the barrier strength of the layer interface for glissile dislocation transmission.

Synthesis, characterization, and in vivo biodistribution of 125I-labeled Dex-g-PMAGGCONHTyr.

Dextran graft poly (N-methacryloylglycylglycine) copolymer-tyrosine conjugates (dextran-g-PMAGGCONHTyr) were synthesized and characterized. Dynamic light scattering (DLS) results indicated that the graft copolymers are soluble in pH 7.4 PBS and 0.9% saline solutions. The graft copolymers were labeled with (125)I, and the labeling stability in 0.9% saline solution was investigated. Pharmacokinetics studies showed a rapid clearance of (125)I-labeled graft copolymers from the blood pool. Biodistribution images confirmed the preferable liver and spleen accumulation within 1 h after injection and rapid clearance from all the organs over time. The graft copolymer with molecular weight of 9.8 kDa was eliminated from the kidney significantly faster than those with higher molecular weight. The effect of the numbers of -COOH groups on the graft copolymers on the biodistribution was also investigated. It was found that the graft copolymers with the average number of -COOH groups per glucopyranose unit (DS(-COOH)) of 0.57 and 0.18 are mainly distributed in liver and spleen at 1 h after injection, whereas the graft copolymer with DS(-COOH) of 0.07 is mainly accumulated in kidney.