pH响应型星状聚合物胶束的制备及释药性能

以金刚烷为核设计合成了一种具有pH响应功能的四臂星状聚合物金刚烷-[聚(乳酸-共-羟基乙酸)-聚甲基丙烯酸二乙氨基乙酯-聚(乙二醇)单甲醚]₄(4sAd-PLGA-D-P), 制备了4sAd-PLGA-D-P自组装胶束, 考察了该胶束对抗癌药物阿霉素(Doxorubicin,DOX)的控释性能。结果表明: 改变聚甲基丙烯酸二乙氨基乙酯(PDEAEMA)的链段长度可实现对聚合物胶束性能的调控。PDEAEMA链段越长, 聚合物胶束的粒径越大, 载药量越高, 药物累计释放量越高。聚合物胶束具有良好的稳定性(临界胶束浓度(Critical Micelle Concentration,CMC)为0.0031 mg/mL)、pH响应性能和载药能力(载药量高达24.8%)。载DOX胶束在肿瘤微环境pH值(pH=5.0)的累计释放量(85.2%)明显高于正常组织pH=7.4条件下的累计释放量(20.9%), 可实现抗癌药物的可控释放。因此, pH响应型聚合物胶束4sAd-PLGA-D-P在抗癌药物递送领域具有潜在的应用前景。     

A Boronate Ester Driven Rechargeable Antibacterial Membrane for Fast Molecular Sieving

Membrane decorated with biocides is an effective way to suppress biofilm growth. However, their immediate biocidal effect usually suffers from a significant decline due to the irreversible consumption of the biocides. Here, a smart nanofiltration membrane is reported with rechargeable antibacterial capability that is fabricated by a facile interfacial polymerization via 3-aminophenylboronic acid and trimesoyl chloride on a polysulfone substrate. Biocides bearing diol groups can be grafted onto the membrane surface under neutral/alkaline condition and then released from the surface under acidic environment, due to the pH-responsive feature of boronate ester complexes. The resultant membrane exhibits integrated properties of fast bacterial inactivating efficiency, rechargeable antibacterial capability, and impressive stability. In addition, the achieved membrane shows remarkable separation efficiency to dye/monovalent salt system. The successful fabrication of the membrane with rechargeable anti-bacterial property provides new insights into the development of pH-responsive and sustainable antibacterial membranes.     

pH-responsive drug delivery system based on hollow silicon dioxide micropillars coated with polyelectrolyte multilayers

We report on the fabrication of polyelectrolyte multilayer-coated hollow silicon dioxide micropillars as pH-responsive drug delivery systems. Silicon dioxide micropillars are based on macroporous silicon formed by electrochemical etching. Due to their hollow core capable of being loaded with chemically active agents, silicon dioxide micropillars provide additional function such as drug delivery system. The polyelectrolyte multilayer was assembled by the layer-by-layer technique based on the alternative deposition of cationic and anionic polyelectrolytes. The polyelectrolyte pair poly(allylamine hydrochloride) and sodium poly(styrene sulfonate) exhibited pH-responsive properties for the loading and release of a positively charged drug doxorubicin. The drug release rate was observed to be higher at pH 5.2 compared to that at pH 7.4. Furthermore, we assessed the effect of the number of polyelectrolyte bilayers on the drug release loading and release rate. Thus, this hybrid composite could be potentially applicable as a pH-controlled system for localized drug release.     

Preparation and characterization of dual-responsive spiropyran-based random copolymer brushes via surface-initiated atom transfer radical polymerization

Silica nanoparticles (SiO₂) were grafted with the precursor random copolymer of 1′-(2-acryloxyethyl)-3′,3′-dimethyl-6-nitrospiro-(2H-1-benzopyran-2,2′-indoline) (SPMA) and tert-butyl methacrylate (tBMA) by surface-initiated atom transfer radical polymerization (SI-ATRP), and SiO₂-g-P(SPMA-co-methacrylic acid (MAA)) was obtained via chemical hydrolysis of the resulting precursor random copolymer in acidic conditions. From transmission electron microscopy, we observed the spherical morphology of monodispersed silica nanoparticles and core-shell structure of SiO₂-g-P(SPMA-co-MAA). Energy dispersive spectroscopy, Fourier transform infrared spectra, X-ray photoelectron spectroscopy, and the thermogravimetric analysis indicated that the polymer had been successfully grafted onto the surface of silica nanoparticles. The dual-responsive properties were characterized by means of ultraviolet-visible spectrophotometer and dynamic light scattering. The average hydrodynamic diameter of SiO₂-g-P(SPMA-co-MAA) increased from 185.7 to 212.7 nm under ultraviolet light irradiation for 5 min. Also, the particle size of SiO₂-g-P(SPMA-co-MAA) increased with the rising pH value of surrounding condition.     

Towards recycling purpose: Converting PET plastic waste back to terephthalic acid using pH-responsive phase transfer catalyst

Converting polyethylene terephthalate (PET) wastes to its monomer and valuable chemicals via eco-friendly chemical method is still a challenge task. Previously, phase transfer catalysts used for alkaline hydrolysis were soluble in reaction media and hardly separated after reaction. Here, we reported several pH-responsive catalysts combined alkyl quaternary ammonium units with heteropolyacid anion for achieving stepwise product/catalyst separation and catalyst recycling. The properties of homogeneous/heterogeneous transfer behavior allow catalyst to be easily separated from reaction media by adjusting of pH value. Among them, [C₁₆H₃₃N(CH₃)₃]₃PW₁₂O₄₀ (abbreviated as [CTA]₃PW) exhibits the highest activity and the most suitable pH responsive values. Such a pH triggered switchable catalytic system not only shows good performance for depolymerization of pure PET, but also some real PET wastes such as coloured trays and PE/PET complex films could be completely degraded into terephthalic acid. Additionally, the reaction kinetics and activation energy of PET alkaline hydrolysis also studied with and without pH-responsive [CTA]₃PW.     

PEGylation and aqueous solution behaviour of pH responsive poly(l-lysine iso-phthalamide)

The effect of PEGylation on the aqueous solution properties of a pH responsive pseudopeptide, poly(l-lysine iso-phthalamide), has been investigated using UV and fluorescence spectroscopy, ¹H NMR spectroscopy and dynamic light scattering. It was demonstrated that the level of PEGylation had a critical effect on the pH response of the parent polymer. When the degree of PEGylation was less than 23.4 wt% the modified polymer exhibited a transition from an expanded structure at high degrees of ionization to a compact hydrophobically stabilised structure at low degrees of ionization. The specific pH at which the conformational transition occurred was dependent on the degree of PEGylation. At levels of PEGylation in excess of 25.6 wt% the polymer no longer displayed this pH dependent conformation and existed in a micellar form (100-200 nm) over the whole range of ionization. Both linear and micellar forms of the pseudopeptide have applications in drug delivery.     

Reversible pH-Responsive Hydrogels of Softwood Kraft Lignin and Poly[(2-dimethylamino)ethyl Methacrylate]-based Polymers

Softwood kraft lignin (SKL) pH-responsive hydrogels were prepared through controlled aggregation using poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) and poly(2-(dimethylamino)ethyl methacrylate)-block-poly(ethylene oxide)-block-poly(2-(dimethylamino) ethyl methacrylate) triblock copolymer (PDMAEMA-co-PEO-co-PDMAEMA). At low SKL concentrations, the SKL/polymer (PDMAEMA and PDMAEMA-co-PEO-co-PDMAEMA) aqueous solutions exhibited pH-dependent aggregation arising from the formation of strong intermolecular hydrogen bonds. Decreasing the SKL/polymer weight ratio resulted in the pH-reversible soluble-insoluble (S-I) transition to become a soluble-insoluble-soluble (S-I-S) transition, which upon increasing the SKL concentration resulted in hydrogel formation. Under neutral conditions relatively strong hydrogels were formed, which upon either increasing or decreasing solution pH resulted in the hydrogels collapsing to liquid solutions, but were readily reformed upon neutralization. The effects of polymer structure, concentration, and intermolecular interactions on solution behavior and gelation are thoroughly discussed.     

A pH and Redox Dual Responsive 4-Arm Poly(ethylene glycol)-block-poly(disulfide histamine) Copolymer for Non-Viral Gene Transfection in Vitro and in Vivo

A novel 4-arm poly(ethylene glycol)-b-poly(disulfide histamine) copolymer was synthesized by Michael addition reaction of poly(ethylene glycol) (PEG) vinyl sulfone and amine-capped poly(disulfide histamine) oligomer, being denoted as 4-arm PEG-SSPHIS. This copolymer was able to condense DNA into nanoscale polyplexes (<200 nm in average diameter) with almost neutral surface charge (+(5–10) mV). Besides, these polyplexes were colloidal stable within 4 h in HEPES buffer saline at pH 7.4 (physiological environment), but rapidly dissociated to liberate DNA in the presence of 10 mM glutathione (intracellular reducing environment). The polyplexes also revealed pH-responsive surface charges which markedly increased with reducing pH values from 7.4–6.3 (tumor microenvironment). In vitro transfection experiments showed that polyplexes of 4-arm PEG-SSPHIS were capable of exerting enhanced transfection efficacy in MCF-7 and HepG2 cancer cells under acidic conditions (pH 6.3–7.0). Moreover, intravenous administration of the polyplexes to nude mice bearing HepG2-tumor yielded high transgene expression largely in tumor rather other normal organs. Importantly, this copolymer and its polyplexes had low cytotoxicity against the cells in vitro and caused no death of the mice. The results of this study indicate that 4-arm PEG-SSPHIS has high potential as a dual responsive gene delivery vector for cancer gene therapy.     

Encapsulation of magnetic nanoparticles in a pH-sensitive poly(4-vinyl pyridine) polymer: a step forward to a multi-responsive system

A multiresponsive system that consists on pH-responsive polymer microspheres with encapsulated iron oxide magnetic nanoparticles that rendered the core magnetic to enable externally controlled actuation under magnetic induction has been developed. The inorganic nanoparticles were first prepared and, then, further encapsulated in a pH-sensitive poly(4-vinylpyridine). These spheres have been obtained by a modification of the simple, rapid and high-reproducible nanoprecipitation method. Magnetic measurements showed that the iron oxide nanoparticles are superparamagnetic and, therefore, able to undergo a local increase of the temperature when an oscillating magnetic field is applied. Magnetically triggered heating and pH sensitivity can be useful for biomedical applications.