Liping Zhang

Preparation and pH controlled release of polyelectrolyte complex of poly(L-malic acid-co-D,L-lactic acid) and chitosan.

The copolymer of poly(L-malic acid-co-D,L-lactic acid) (PML) was synthesized through a direct polycondensation of L-malic acid (MA) and D,L-lactic acid (LA). Then, a new polyelectrolyte complex (PEC) based on the complexation between the copolymer (PML) and chitosan (CS) was prepared. The PEC formed stable nano particles in aqueous solutions with pH 3-5, and the nano particles had the diameters in a range of 316-590 nm (varied with the components of PML and CS). Doxorubicin (DOX) as a model drug was loaded on the nano particles through the physical adsorption and complexation, and part of DOX formed the secondary particles by self-aggregation. The high drug loading efficiency (16.5%) and the sustained release patterns in acidic media were observed, and the release accelerated in alkaline solutions. The nano particles could be potentially applied as pH sensitive drug vehicles for controlled release.

Zwitterionic pH/redox nanoparticles based on dextran as drug carriers for enhancing tumor intercellular uptake of doxorubicin

Zwitterionic nanoparticles have excellent serum stability. In this study, pH/redox responsive polymer was synthesized through a modification of dextran using succinic acid, followed by crosslinking with cystamine. The polymer could self-assemble into stable nanoparticles (NPs) in aqueous solution. The NPs carried certain amount of free carboxyl and amino groups on the surface, which endowed the NPs excellent anti-protein adsorption ability. The surface charge was negative at pH7.4 and was converted to positive at pH5.0. It was revealed that the NPs showed little non-specific protein adsorption and had excellent serum stability, and the NPs could be internalized in Hela cells rapidly. This result was ascribed to the charge reversible feature of the NPs. Doxorubicin (DOX) was loaded in the NPs for release studies in vitro. The DOX-loaded NPs exhibited obvious pH and reduction sensitivities in response to the environment in tumor cells due to the introduction of carboxyl groups, amino groups and disulfide bonds in the NPs. The NPs were biocompatible, biodegradable, and could be potentially applied as anticancer drug carriers for enhancement of tumor intercellular uptake of doxorubicin.

Preparation of polyelectrolyte complex nanoparticles of chitosan and poly(2-acry1amido-2-methylpropanesulfonic acid) for doxorubicin release

A new kind of polyelectrolyte complex (PEC) based on cationic chitosan (CS) and anionic poly(2-acry1amido-2-methylpropanesulfonic acid) (PAMPS) was prepared using a polymer-monomer pair reaction system. Chitosan was mixed with 2-acry1amido-2-methylpropanesulfonic acid) (AMPS) in an aqueous solution, followed by polymerization of AMPS. The complex was formed by electrostatic interaction of NH3(+) groups of CS and SO3(-) groups of AMPS, leading to a formation of complex nanoparticles of CS-PAMPS. A series of nanoparticles were obtained by changing the weight ratio of CS to AMPS, the structure and properties of nanoparticles were investigated. It was observed that the nanoparticles possessed spherical morphologies with average diameters from 255 nm to 390 nm varied with compositions of the nanoparticles. The nanoparticles were used as drug vehicles for doxorubicin, displaying relative high drug loading rate and encapsulation rate. The vitro release profiles revealed that the drug release could be controlled by adjusting pH of the release media. The nanoparticles demonstrated apparent advantages such as simple preparation process, free of organic solvents, size controllable, good biodegradability and biocompatibility, and they could be potentially used in drug controlled release field.

Titanium Oxide/Silicon Moth-Eye Structures with Antireflection, p–n Heterojunctions, and Superhydrophilicity

By employing KOH etching of silicon and hydrothermal growth of titanium oxide (TiO2), TiO2 nanorods assembled on the silicon micropyramids to form biomimetic composite coating, similar to moth-eye structures. The biomimetic composite coating possessed not only the micro-nano hierarchical structures but also the p-n heterojunctions, resulting in a decrease in the reflection of incident light and an increase in the separation efficiency of photogenerated carriers. Meanwhile, the structures showed excellent superhydrophilicity, making for the self-cleaning of the material surface. We further demonstrate that by exploiting the advantages of this method, the application of such structures in the photocatalysis field is thus straightforward.

Fabrication of 3D biomimetic composite coating with broadband antireflection, superhydrophilicity, and double p-n heterojunctions

The traditional single material with two-dimensional (2D) biomimetic moth-eye structures is limited by its narrowband antireflection and single functional capability. To overcome these disadvantages, we exploited wet etching and hydrothermal synthesis coupled with chemical oxidation for fabricating a three-dimensional (3D) biomimetic moth-eye coating with ternary materials (polypyrrole nanoparticles, TiO2 nanorods, and Si micropyramids, i.e., PPy/TiO2/Si-p). This coating reduced the reflectivity to <4% at wavelengths ranging from 200 to 2,300 nm and exhibited remarkable superhydrophilicity with a low water contact angle of 1.8°. Moreover, the composite coating had double p-n heterojunctions, allowing the high-efficiency separation of photogenerated carriers. The photo-current density of PPy/TiO2/Si-p was more than three times higher than that of TiO2/Si-p at a positive potential of 1.5 V. The proposed method provides a means to enhance solar energy conversion.

Preparations and doxorubicin controlled release of amino-acid based redox/pH dual-responsive nanomicelles

Terpolymers of poly (Lysine-co-N, N-Bis (acryloyl) cystamine-co-β-Phenethylamine) (PLBP) were synthesized in one-pot by Michael addition terpolymerization. The terpolymers self-assembled into nano-sized spherical micelles (84-123nm) with narrow distributions. The surface charge of the nanomicelles (NMs) was depended on solutions pH and showed negative values under physiological conditions (pH7.4), which was beneficial for long circulation without non-specific protein adsorption. Doxorubicin (DOX) was effectively loaded into the NMs for controlled release. The in vitro release profiles exhibited obvious pH and reduction sensitivities in response to the environment mimicking tumor cells. The MTT assays demonstrated that blank NMs were biocompatible, and drug-laden NMs showed a significant cytotoxicity on Hela cells. The NMs could be potentially applied as smart drug delivery systems in cancer therapy.

Enhanced photoactivities of ternary composite coating by antireflection and double P–N heterojunctions

In this paper, we present a convenient and universal strategy to sequentially assemble titania (TiO2) nanorods and polyaniline (PANI) nanoparticles on the Si wafers through hydrothermal synthesis and chemical oxidation. On the one hand, the composite coatings (PANI/TiO2/Si) with hierarchical structures reduced the reflectivity to less than 5xa0% at the wavelengths from 200 to 2500xa0nm, namely increasing the absorption efficiency of incident light. On the other hand, the double P–N heterojunctions that the composite coatings developed could suppress the recombination of photogenerated carriers, namely enhancing utilization efficiency of absorbed light. The photocurrent density of PANI/TiO2/Si was above two times higher than that of TiO2/Si at 1.5xa0V of positive potentials. The application of such coatings in the photocatalysis area, which are fabricated with this method, is thus straightforward.

Reduction-responsive zwitterionic nanogels based on carboxymethyl chitosan for enhancing cellular uptake in drug release

Stimuli-responsive nanoparticles as drug carriers have promising applications in chemotherapy. To increase stability of nanogels in the bloodstream and to enhance intracellular drug uptake, reduction-responsive zwitterionic nanogels were prepared using carboxymethyl chitosan as a material. The preparation included modification of carboxymethyl chitosan and crosslinking by of N,N-Bis(acryloyl) cystamine. The nanogels possessed zwitterions of carboxyl and amino groups, and showed excellent non-fouling behavior against protein adsorption. In the presence of a reduction agent such as glutathione (GSH), the nanogels were dissociated due to scission of disulfide bonds in the crosslinking structure, leading to drug release in tumor cells. The nanogels were non-cytotoxic, biocompatible, biodegradable, and would be potentially used as anticancer drug delivery carriers in controlled release for enhancing cellular drug uptake.

A new kind of polyion complex nanoparticles and the covalent drug-loading pattern for doxorubicin and pH-controlled release

The one-pot synthesis method was developed for the preparation of complex nanoparticles with a narrow size distribution and stable morphology. The vinyl monomers of (2-dimethylamino)ethyl methacrylate (DEMA) and diacetone acrylamide (DAA) were copolymerized in the presence of alginic acid in an aqueous solution without any organic solvents or surfactants, yielding stable complex nanoparticles in one-pot synthesis. The nanoparticle was composed of the complex of poly(DEMA-co-DAA) and alginic acid. The complex was formed via electrostatic interaction between polycations of DEMA and polyanions of alginate. The residual alginate segment around the core formed the shell of the nanoparticles. The average diameter of the nanoparticles varied from 120 to 213xa0nm when the molar percentage of DAA changed from 0.5 to 0 with respect to DEMA. The anti-cancer drug doxorubicin could be loaded onto the nanoparticles with a high-loading efficiency through the formation of polymer–drug conjugate. The drug release could be controlled by adjusting the pH value of the medium.

Preparations of hyperbranched polymer nano micelles and the pH/redox controlled drug release behaviors

Hyperbranched polymer nano micelles (NMs) were prepared through a nucleophilic ring opening polymerization between cystamine and polyethylene glycol diglycidyl ether, followed by a reaction of amino groups and dimethyl maleic anhydride. The NMs showed spheric morphologies with hydrodynamic diameters of 106-120nm. Doxorubicin was loaded in the NMs with loading rate as high as 15.38wt%; The NMs possessed negative zeta potentials in aqueous solutions of pH7.4 due to the carboxyl ions on the particle surfaces, but the zeta potentials were converted to positive ones due to the hydrolysis of amide bonds at pH5.0-6.5, leading to the leaving of carboxyl groups and remaining of amino groups. The disulfide bonds in cystamine were designed in the hyperbranched polymer structures of the NMs, and bonds could be broken by a reducing agent l-glutathione (GSH) (10mM), resulting in a targeted drug release. The smart NMs displayed good biodegradability and biocompatibility, and they could be potentially used in drug controlled release field.