Temperature-sensitive polypeptide brushes-coated mesoporous silica nanoparticles for dual-responsive drug release

A multifunctional nanohybrid based on mesoporous silica nanoparticle and biocompatible polypeptide was fabricated for targeted and dual-responsive therapy of tumor cells.     

呋喃西林水溶液在光和热作用下的稳定性

The influence of both light and heat on the stability of nitrofurazone aqueous solution was studied. Results show that in either heating experiments or the exposure to light at high temperatures, the degradation rate obeyed zero-order kinetics. The total rate constant ktotal caused by both light and heat can be divided into two parts: ktotal =kdark klight, where kdark and klight are the degradation rate constants caused by heat and light, respectively. The klight can be expressed as klight=Alight*exp(-Ea,light/RT)*E, where E is the illuminance of light, and Alight and Ea,light both are experimental constants. The values of these kinetic parameters were determined based on the experiments in the dark and upon exposure to three different light sources. Results show that the values of Alight and Ea, light varied with the light source. To save time, labor, and drugs, exponential heating experiments were employed and compared with the isothermal experiments. Results indicated that kinetic parameters obtained by exponential heating experiments are comparable to those obtained by isothermal experiments either in the dark or upon exposure to light.     

pH-sensitive modulation of the second hydration sphere in lanthanide(III) tetraamide-DOTA complexes: a novel approach to smart MR contrast media

The lanthanide(III) complexes of three tetraamide DOTA bearing pyridyl, phenolic and hydroxypyridyl substituents have been studied by NMR, luminescence and cyclic voltammetry. The relaxivity profiles of the gadolinium complexes of the pyridyl and phenolic ligands were flat and essentially the same between pH 2 and 8. The hydroxypyridyl ligand, however, exhibited two regions of enhanced relaxivity. The small relaxivity enhancement (25 %) at lower pH (pH 2-4) has been attributed to an increase in the prototropic exchange of the coordinated water molecule while the slightly larger enhancement (84 %) at higher pH (pH 6-9) reflects deprotonation of the ligand amide protons. Deprotonation of the amides results in the formation of an intramolecular acid-base pair interaction with the phenolic protons and this, in turn, causes a highly organized second hydration sphere to come into effect, thereby increasing the relaxivity. The water relaxivity of the Gd(3+)-hydroxypyridyl complex is further enhanced upon binding to serum albumin.     

腰果酚的紫外光固化机理和固化膜性能

研究了腰果酚在无光引发剂条件下的紫外光固化反应,并用IR、UV、元素分析、GPC等分析手段分析了腰果酚的紫外光固化机理及其固化膜性能。结果表明:在紫外光辐照下,腰果酚通过侧链发生氧化聚合反应,和酚羟基的邻对位失去质子形成的自由基引起的苯环缩合反应,最终形成体型高聚物。腰果酚的紫外光固化膜的常规物理机械性能、抗溶剂性、耐化学介质腐蚀性、热稳定性和抗紫外线性能均优于腰果酚醛缩聚物(PC)涂膜。     

Multi‐stimuli‐responsive self‐immolative polymer assemblies

Self‐immolative polymers (SIPs) undergo depolymerization in response to the cleavage of stimuli‐responsive end‐caps from their termini. Some classes of SIPs, including polycarbamates, have depolymerization rates that depend on environmental factors such as solvent and pH. In previous work, hydrophobic SIPs have been incorporated into amphiphilic block copolymers and used to prepare nanoassemblies. However, stimuli‐responsive hydrophilic blocks have not previously been incorporated. In this work, we synthesized amphiphilic copolymers composed of a hydrophobic polycarbamate SIP block and a hydrophilic poly(2‐(dimethylamino)ethyl methacrylate) (PDMAEMA) block connected by a UV light‐responsive linker end‐cap. It was hypothesized that after assembly of the block copolymers into nanoparticles, chain collapse of the PDMAEMA above its lower critical solution temperature (LCST) might change the environment of the SIP block, thereby altering its depolymerization rate. Self‐assembly of the block copolymers was performed, and the depolymerization of the resulting assemblies was studied by fluorescence spectroscopy, dynamic light scattering, and NMR spectroscopy. At 20 °C, the system exhibited a selective response to the UV light. At 65 °C, above the LCST of PDMAEMA, the systems underwent more rapid depolymerization, suggesting that the increase in rate arising from the higher temperature dominated over environmental effects arising from chain collapse. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1868–1877     

Structural diversity in poly(disulfide)s

This article reports a synthetic methodology for single step preparation of telechelic poly(disulfide)s (PDS) by step‐growth polymerization between a di‐thiol and a commercially available monomer 2,2′‐dithiodipyridine in presence of a functional group appended pyridyl disulfide moiety as the “mono‐functional impurity” (MFI). Redox‐destructible well‐defined segmented PDSs with functional chain terminal, predicted and tunable degree of polymerization and narrow polydispersity index (<2.0) could be synthesized under a mild reaction condition. Using an appropriate MFI, PDS could be synthesized with trithiocarbonate chain terminals in a single step, which could be further used as macro chain‐transfer agent (CTA) for chain growth polymerization under RAFT mechanism producing ABA type tri‐block copolymer wherein the B block consists of the degradable PDS chain. By copolymerization between a hydrophobic di‐thiol monomer and a hydroxyl group appended di‐thiol monomer, PDS could be prepared with pendant hydroxyl functional group which was utilized to initiate ring opening polymerization of cyclic lactide monomers producing well‐defined degradable graft‐copolymer. The pendant hydroxyl groups were further utilized to anchor a polar carboxylic group to the degradable PDS backbone which under basic condition showed aqueous self‐assembly generating micelle‐like structure with hydrophobic guest encapsulation ability and glutathione responsive sustained release. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 194–202     

Synthesis and characterization of silica-supported Preyssler nano particles and its catalytic activity for photodegradation of methyl orange

Abstract

Heteropolyacid (H₁₄ [NaP₅W₃₀O₁₁₀])/SiO₂ nano particles were synthesized by a micro emulsion technique. The morphology and size of these nano particles were characterized using, transmission electron microscopy and X-ray diffraction. In a designed photo reactor, the photo degradation of methyl orange as common azo dye pollutants in the environment was selected as a test reaction to estimate the catalytic activity of the synthesized nano particles and found to be excellent.     

Singlet Oxygen Photo‐Oxygenation in Water/Pluronic F‐127 Hydrogels: Increased Reaction Efficiency Coupled with a Switch in Regioselectivity

Pluronic F‐127 hydrogels are highly efficient microenvironments for photochemical reactions, as demonstrated for singlet oxygen reactions of monoalkenes. Nonpolar substrates are localized in the nanosized polymer compartment, which can be visualized by neutron scattering. The efficiency of ¹O₂ reactions is strongly increased for tiglate derivatives and the regioselectivity of the ene reaction of trisubstituted alkenes is completely switched in comparison with solution phase and inverted in comparison with intrazeolite photo‐oxygenations.     

Synthesis and Characterization of Lu3N@C80O

Oxygenated hollow cage fullerenes have been intensively studied due to their applications in biomedicine in recent years. Clusterfullerenes have become a focus of endohedral fullerene researches for their exceptionally high yield and thermal stabilities. However, oxide derivatives of clusterfullerene remain unexplored to date. Herein, we present the photochemical synthesis of an oxide derivative of clusterfullerene, Lu₃N @C₈₀O , for the first time. The compound was characterized by matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry, UV –vis‐NIR , cyclic voltammetry, and FTIR spectroscopy. The results suggest that one oxygen atom bridges with the fullerene cage after the oxidation of Lu₃N @C₈₀ . Moreover, the oxidation has a major impact on the electrochemical behavior of Lu₃N @C₈₀ .