Zwitterionic nanogels with temperature sensitivity and redox-degradability for controlled drug release.

Zwitterionic polymers play an attractive role in the application of stealthy nanocarriers for their excellent antifouling property. Herein, a zwitterionic nanogel with temperature sensitivity and redox-responsive degradability prepared by copolymerization of N-vinylcaprolactam (VCL) and 2-(methacryloyloxy) ethyldimethyl-(3-sulfopropyl) ammonium hydroxide (DMAPS) via aqueous precipitation polymerization. The prepared nanogels own ultra-high colloidal stability and non-specific protein adsorption resistance as a result of the incorporation of zwitterionic groups. Meanwhile, they exhibit sensitive temperature-induced swelling/collapse transition in aqueous solution and excellent redox-degradability ascribed to the presence of disulfide bonds. The nanogels loaded with anticancer drug doxorubicin (DOX) exhibit low leakage of DOX under physiological conditions (merely 23.8 % within 24 h), whereas striking release amount of DOX under reducing conditions combined with elevated temperature (93.4 % within 24 h). The measurement of cell viability showed that the cytotoxicity of blank nanogels to tumor cells (HeLa cells) was negligible, while the nanogels loaded with DOX had a prominent inhibitory impact on tumor cells.

g-C3N4/CeO2 Binary Composite Prepared and Its Application in Automobile Exhaust Degradation.

Vehicle exhaust seriously pollutes urban air and harms human health. Photocatalytic technology can effectively degrade automobile exhaust. This work prepared g-C3N4/CeO2 photocatalytic material by constructing heterojunctions. Four kinds of g-C3N4/CeO2 composite photocatalytic materials with different mass ratios were prepared. An indoor exhaust gas purification test was carried out under natural light and ultraviolet light irradiations. The optimum mass ratio of g-C3N4 material and CeO2 material was determined by evaluating the exhaust gas degradation effective. Moreover, the structure and morphology of the g-C3N4/CeO2 composite were investigated with microscopic characterization experiments (including XRD, TG-DSC, FT-IR, UV-Vis, SEM and XPS). The results obtained were that the optimum mass ratio of g-C3N4 material to CeO2 material was 0.75. The degradation efficiencies under ultraviolet irradiation in 60 min for HC, CO, CO2, NOX were 7.59%, 12.10%, 8.25% and 36.82%, respectively. Under visible light conditions, the degradation efficiency in 60 min for HC, CO, CO2 and NOX were 15.88%, 16.22%, 10.45% and 40.58%, respectively. This work is useful for purifying automobile exhaust in the future.

Polydopamine-Based Composite Nanoparticles with Redox-Labile Polymer Shells for Controlled Drug Release and Enhanced Chemo-Photothermal Therapy.

Photothermal therapy (PTT) that utilizes phSUPPotothermal conversion agents (PTC) to ablate tumor under NIR light irradiation has attracted increasing attention due to its excellent therapeutic efficacy and improved target selectivity. Herein, a novel core-shell nanoparticle based on disulfide-crosslinked poly(methacrylic acid) (PMAA) layer coated polydopamine (PDA) particle has been successfully synthesized by precipitation polymerization. For these PDA@PMAA composite nanoparticles, PDA core exhibits high photothermal efficacy, meanwhile, the redox-labile PMAA shell serves as carriers to encapsulate anticancer drugs and selectively release them. Due to the characteristic of the disulfide bond, PMAA shell occurs at selective degradation as well as controlled drug release upon entering cancer cells. Moreover, the DOX-loaded PDA@PMAA nanoparticles demonstrated a synergistic effect, which shows a significantly improved inhibition effect against cancer cells by the combination of photothermal therapy and traditional chemotherapy with low drug dosage and short laser irradiation in an in vitro study.

Novel polythiophene derivative for dual-channel cell imaging.

Fluorescent materials play an extremely important role in understanding the microbiological world. New fluorescent materials which have good photophysical properties, low cytotoxicity, and multi-channel fluorescent imaging capability are still urgently needed, even though many kinds of fluorescent materials have already been synthesized. In this work, a new polythiophene derivative (PT-OH-PPR) modified with a porphyrin group in its side chain was designed and fabricated through FeCl3 oxidative polymerization. The obtained PT-OH-PPR has wide absorption and emission spectral range, good water solubility and low cytotoxicity. Importantly it could be enriched in the cytoplasm of A549 cells and be excited by two excitation wavelengths (488 nm and 559 nm), which provides a promising application in dual-channel cell imaging.

Biodegradable phosphorylcholine-based zwitterionic polymer nanogels with smart charge-conversion ability for efficient inhibition of tumor cells.

Zwitterionic polymer nanocarriers have attracted much attention in recent years due to their desirable biocompatibility and anti-fouling properties. However, the super-hydrophilic and neutral charge of zwitterionic polymer results in weak interactions with negatively charged cell membranes, which leads to suboptimal uptake by tumor cells. Herein, a series of biodegradable poly(2-methacryloyloxyethyl phosphorylcholine-s-s-vinylimidazole) (PMV) nanogels with uniform spherical shape was fabricated by one-step reflux precipitation polymerization, which was clean and efficient. The PMV nanogels remained in zwitterionic state at physiological pH (pH 7.4) and were converted rapidly to positive charged state at tumor extracellular pH (pH 6.5). Proton nuclear magnetic resonance spectra and acid-base titration experiment proved that the charge-conversion ability of PMV nanogels was attributed to protonation of the imidazole ring in an acidic environment. Protein stability experiment showed that PMV nanogels exhibited a protein-adsorption resistance at pH 7.4 for as long as 7 days while adsorbed protein rapidly at pH 6.5. Moreover, PMV nanogels showed a reducing-labile property, which was able to degrade into short linear polymer chains in the presence of reduction agents. Therefore, the doxorubicin (DOX) release profile was controlled finely with a low DOX leakage under physiological conditions (7.8% in 48 h) and a rapid DOX release in 10 mM glutathione at pH 7.4 (78.9% in 48 h). Confocal laser scanning microscope and flow cytometry showed that the PMV nanogels exhibit an enhanced cellular uptake by tumor cells at pH 6.5 compared with pH 7.4, which allows for a severe cytotoxic effect of DOX-loaded PMV nanogels against tumor cells.

Carbon-Dot-Based Nanosensors for the Detection of Intracellular Redox State.

Carbon-dot-based nanosensors are prepared through sequentially assembling a polymer/carbon dot multilayer shell on mesoporous silica nanoparticles with different crosslinking densities of disulfide bonds; they can be utilized to evaluate the gluthathione (GSH) concentration. In vitro cell assays demonstrate the feasibility of using such nanosensors in evaluating the intracellular redox state of different cells.

Acid degradable poly(vinylcaprolactam)-based nanogels with ketal linkages for drug delivery.

To improve the biocompatibility and biodegradability of nanocarriers, well-defined poly(vinylcaprolactam)-based acid degradable nanogels were fabricated for drug delivery via precipitation polymerization in water, where synthetic ketal-based 2,2-dimethacroyloxy-1-ethoxypropane (DMAEP) acted as a cross-linker, and N-(2-hydroxypropyl)methacrylamide (HPMA) served as a co-monomer. Expectedly, we observed that the temperature and pH of the environment play important roles in the performance of the nanogels. The nanogels were reduced in size upon increasing the temperature and showed higher volume phase transition temperature (VPTT) with higher concentration of HPMA. With the incorporation of ketal linkages, the nanogels showed accelerated degradation profiles by lowering the pH and increasing temperature of the incubation medium. When used as nanocarriers of anticancer drug doxorubicin (DOX), compared to non-degradable nanogels with similar components, the acid-degradable nanogels displayed more effective drug controlled release behaviour, low drug leakage of DOX at neutral pH while rapid and sufficient release from the nanogels under acidic conditions. The results of the cytotoxicity and hemolysis assays further highlighted that the acid-degradable nanogel produced no hemolysin but showed excellent viability to normal cells, and the DOX-loaded nanogel exhibited higher proliferation inhibition against tumor cells.

The study on the degradation and mineralization mechanism of ion-doped calcium polyphosphate in vitro.

Doping with different trace elements can significantly change the original degradability, mineralization, and biological properties of bone repair material. According to the fundamental research on prepared calcium polyphosphate (CPP) as a bone repair material by our group, this article began further exploration on the effect of doping different trace elements (K, Na, Mg, Zn, Sr) into CPP on its degradability and mineralization soaking in simulated body fluids. The results indicated that doped elements significantly changed the lattice parameters and cell volume of crystal, resulted in different types of crystal defect and surface charge distribution, and consequently changed the original degradability and mineralization of CPP. The conclusion is that doped ions with relatively smaller ionic radius and equivalent positive charge compared with Ca(2+) can greatly promote the degradability and mineralization of CPP, whereas doped ions with equivalent ionic radius and diverse positive charges compared with Ca(2+) provide less contribution on promoting the degradability and mineralization or even counteract.