Guoping Yan

One-Step UV-Induced Synthesis of Polypyrrole/Ag Nanocomposites at the Water/Ionic Liquid Interface

Polpyrrole (PPy)/Ag nanocomposites were successfully synthesized at the interface of water and ionic liquid by one-step UV-induced polymerization. Highly dispersed PPy/Ag nanoparticles were obtained by controlling the experimental conditions. The results of Fourier-transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy revealed that the UV-induced interface polymerization leaded to the formation of PPy incorporating silver nanoparticles. It was also found that the electrical conductivity of PPy/Ag nanocomposite was about 100 times higher than that of pure PPy.

Self-assembly of polypyrrole/chitosan composite hydrogels.

Hydrogels based on the polypyrrole (PPy)/chitosan (CS) composite are self-assembled and characterized for their electrical and swelling properties. The static polymerization of pyrrole monomer in aqueous solution containing CS is accompanied with the formation of PPy/CS composite hydrogel. The feed order in the reaction process plays a key role in the formation of the hydrogels. The participation of one-dimensional PPy blocks in the formation of the hydrogel network avoids a possible migration of PPy from the hydrogel. The effect of pH and ionic strength on the physical properties of PPy/CS composite hydrogels are investigated in detail. The results indicate that the pH-sensitive PPy/CS composite hydrogels show good water absorbencies in distilled water and saline solution. This method may open a new opportunity for the fabrication of composite hydrogels associating the biomacromolecules and conducting polymers, and the improvement of the comprehensive performance of the resulting products.

Controlled growth of polypyrrole hydrogels

Tailoring the morphology and swelling–shrinking behaviors of the conducting polymer hydrogels is vital to realizing enhanced performance. Here, we demonstrate an effective approach for the controlled growth of polypyrrole hydrogels with both electrical properties and hydrogel characteristics. Under the static synthetic conditions, the polypyrrole nanotubes are self-assembled to form mesoscale networks of the hydrogels. The effect of the kind and amount of the oxidants on the morphology and swelling–shrinking behaviors of the polypyrrole hydrogels is investigated in detail. The strength of polypyrrole hydrogel is enhanced with the increase of the amount of the oxidant. In the case of Fe(NO3)3 as the oxidant, the swelling–shrinking properties of the polypyrrole hydrogels are improved due to the more polypyrrole granules as a mesoscale cross-linker on the surface of polypyrrole nanotubes.

Preparation of polyaniline-metal composite nanospheres by in situ microemulsion polymerization

Nanosized metal and polyaniline (PANi) composite spheres have been prepared via the polymerization of aniline using PdCl(2) or HAuCl(4) as the oxidant in a microemulsion system. The oxidization of aniline and the reduction of metal ion happened together during the reaction, yielding PANi and elemental metal simultaneously. The results of FTIR spectra suggested that the oxidation degree of PANi was affected by the initial ratio of metal ions to monomer in the microemulsion system. The PANi-metal nanospheres were characterized using X-ray photoelectron spectroscopy and the conductivity of the composite nanospheres was measured by conventional four-probe method. Scanning and transmission electron microscopy were used to show the morphology of the composites.

Tumor-selective macromolecular MRI contrast agents

Tumor-selective macromolecular ligands containing 5-(p-Carbonyloxyphenyl)-10,15,20-triphenylporphyrin (HPTP) moiety (PHEA-DTPAHPTP and PAEA-DTPA-HPTP) were prepared by the incorporation of diethylenetriaminepentaacetic acid (DTPA) and 5-(p-hydroxylphenyl)-10,15, 20-triphenylporphyrin (HPTP) as the tumor-selective group in poly [α,β-(N-(2-hydroxyethyl)-L-aspartamide)] (PHEA) and poly-[α-β-(N-(2-aminoethy1)-L-aspartamide)] (PAEA). These ligands were further complexed with gadolinium chloride to form two tumor-selective macromolecular MRI contrast agents PHEA-Gd-DTPA-HPTP and PAEA-Gd-DTPA-HPTP. Relaxivity studies showed that both the polyaspartamide-gadolinium complexes possess higher relaxation effectiveness than that of the clinically used Gd-DTPA. Magnetic resonance imaging of tumors in mice indicated that these two polyaspartamide MRI contrast agents containing 5-(p-Carbonlyoxyphenyl)-10,15,20-triphenylporphyrin moiety can significantly enhance the contrast MRIs of Hepatoma (H22) and Ehrlich ascites carcinoma after injection and are taken up selectively by these cancers in mice.

Dextran Gadolinium Complexes as Contrast Agents for Magnetic Resonance Imaging to Sentinel Lymph Nodes

ABSTRACTPurposeThe aim was to investigate three dextran gadolinium complexes Dextran-DTPA-Gd as the potential MRI contrast agents in lymphatic system.MethodsThree dextran gadolinium complexes Dextran-DTPA-Gd containing differing amounts of Gd-DTPA were synthesized by the incorporation of Gd-DTPA to the hydroxyl groups of dextran. These dextran ligands and gadolinium complexes were characterized, and their properties in vitro and in vivo were also evaluated.ResultsDextran-DTPA-Gd demonstrated obviously higher relaxation effectiveness than that of Gd-DTPA. The result of in vitro cytotoxicity assay showed that these macromolecular ligands and their corresponding gadolinium complexes had low cytotoxicity to HeLa cells. Dextran-DTPA-Gd greatly enhanced the contrast of MR images of normal politeal lymph nodes and reactive hyperplasia of politeal lymph nodes in rabbits and provided prolonged duration in lymphatic system with lower injection doses than that of Gd-DTPA. However, Dextran-DTPA-Gd displayed low signal enhancements in MR images of politeal lymph nodes with VX2 carcinoma in rabbits during the detection time.ConclusionsThese dextran gadolinium complexes Dextran-DTPA-Gd can be taken up selectively by lymphatic system and showed the potential as MRI contrast agents in lymphatic system.

Anticancer Drug-Loaded Nanospheres Based on Biodegradable Amphiphilic ε-Caprolactone and Carbonate Copolymers

ABSTRACTPurposeThe aim was to investigate anticancer drug-loaded poly(carbonate-ester) nanospheres as potential drug delivery systems for cancer therapy.MethodsFunctional poly(carbonate-ester) copolymers (HPCP-SD) were synthesized by the incorporation of sulfadiazine as the tumor-targeting groups to hydroxyl groups of poly(carbonate-ester) copolymers. Two types of anticancer drug-loaded poly(carbonate-ester) nanospheres I and II were further prepared by dialysis method and high-voltage electrostatic field-assisted atomization, respectively, using HPCP-SD as polymeric carriers. These carriers and anticancer drug-loaded nanospheres were characterized, and their properties in vitro and in vivo were evaluated.ResultsThese anticancer drug-loaded poly(carbonate-ester) nanospheres had steady drug release rates and good controlled release properties. Moreover, anticancer drug-loaded poly(carbonate-ester) nanospheres II had faster drug release rates than those of anticancer drug-loaded nanospheres I. These anticancer drug-loaded nanospheres possessed lower cytotoxicity to HEK 293 cells and exhibited obviously higher anticancer efficiencies to the HeLa tumor cells than that of 5-fluorouracil. Anticancer drug-loaded nanospheres I possessed lower cytotoxicity to HEK 293 cells and higher anticancer activity to HeLa cells than those of anticancer drug-loaded nanospheres II.ConclusionsThese anticancer drug-loaded poly(carbonate-ester) nanospheres showed the potential as drug delivery systems for cancer therapy.

Synthesis and evaluation of gadolinium complexes based on PAMAM as MRI contrast agents.

Diethylenetriaminepentaacetic acid (DTPA) and pyridoxamine (PM) were incorporated into the amine groups on the surface of ammonia‐core poly(amidoamine) dendrimers (PAMAM, Generation 2.0–5.0) to obtain dendritic ligands. These dendritic ligands were reacted with gadolinium chloride to yield the corresponding dendritic gadolinium (Gd) complexes. The dendritic ligands and their gadolinium complexes were characterized by 1HNMR, IR, UV and elemental analysis. Relaxivity studies showed that the dendritic gadolinium complexes possessed higher relaxation effectiveness compared with the clinically used Gd‐DTPA. After administration of the dendritic gadolinium complexes (0.09 mmol kg−1) to rats, magnetic resonance imaging of the liver indicated that the dendritic gadolinium complexes containing pyridoxamine groups enhanced the contrast of the MR images of the liver, provided prolonged intravascular duration and produced highly contrasted visualization of blood vessels.

Surface-initiated Atom-transfer Radical Polymerization from Polyimide Films and Their Anti-fouling Properties

A simple one-step method for the chloromethylation of polyimide (PI) under mild conditions was used to introduce benzyl chloride groups into PI film surface. Covalently tethered hydrophilic polymer brushes of poly(ethylene glycol) monomethacrylate (PEGMA) and glycidyl methacrylate (GMA) were prepared via surface initiated atom-transfer radical polymerization (ATRP) from the chloromethylated PI surfaces using benzyl chloride groups as the active ATRP initiators. A kinetics study indicated that the chain growth from the films was in agreement with a controlled process. The dormant chain ends of the grafted polymer on the PI films could reinitiate the consecutive surface-initiated ATRP to prepare surface-functionalized diblock copolymer brushes on the PI films. The modified surface was characterized by X-ray photoelectron spectroscopy (XPS) after each modification stage. Protein adsorption experiments indicated that the PI-P(PEGMA) membrane exhibited substantially improved anti-fouling properties compared to the pristine PI surface.

Evaluation of dendritic gadolinium complexes as MRI contrast agents

A series of dendritic gadolinium complexes based on dendrimers with 1,4,7,10-tetraazacyclododecane as the core were synthesized. Both diethylenetriaminepentaacetic acid and pyridoxamine were incorporated to the amine groups on the surface to give the dendritic ligands. These dendritic ligands were then reacted with gadolinium chloride to yield the corresponding dendritic gadolinium complexes. The dendritic ligands and their gadolinium complexes were characterized by 1HNMR, IR, UV and elemental analysis. Relaxivity studies showed that the dendritic gadolinium complexes have higher relaxation effectiveness than that of the clinically used small molecular gadolinium complexes. Magnetic resonance imaging of the liver in rats indicated that the dendritic gadolinium complex containing pyridoxamine enhances the image contrast of the liver, provides prolonged intravascular duration and produces highly contrasted visualization of blood vessels in the liver.