In contrast to conventional fluorescent polymers featured by large conjugation structures, a new class of fluorescent polymers without any conjugations is gaining great interest in immerging applications beyond the possibility to achieve by the conjugated polymers. Poly(ethylene glycol) (PEG), widely used in biomedical fields for a long time owing to its nontoxicity and nonimmunogenicity, is found to be fluorescence emissive in the solid state and in aqueous solution, though deemed as not fluorescent in numerous reports. Through systematic study under different conditions, the emission is ascribed to the cluster formation of its chains; thereby the blue-shift of the emission with the excitation wavelength was interpreted through the Forster resonance energy transfer. The clusterization was ascertained through size measurements, Fourier transform infrared spectroscopy, NMR analyses, and the dependence on temperature, pH, and nonsolvent presence. Tested in the presence of competitive metal ions, selective emission quenching by Fe 3+ and Cr 6+ was observed. PEG was used as a sensor for the detection of Cr 6+ , Fe 3+ , and H 2 O 2 , outperforming most of the reported sensors alike. Its uses for data encryption and cell imaging were also presented. This work provides therefore a novel face of PEG with great potential in a variety of emerging applications, in particular, as sensors in the biomedical area.
A theoretical analysis and a morphological prediction of polyacrylate (PA)/ polysiloxane (PSi) latex particles with core/shell morphologies were first conducted based on interfacial tensions and relative volumes of the two polymers in the latex system. The results indicated that the normal core/shell morphology particles (PSi/PA), with hydrophobic polysiloxane as the core and with hydrophilic polyacrylate as the shell, can be easily formed. Although the inverted core/shell morphology particles (PA/PSi) with polyacrylate as the core could not be formed in most cases, even if the fraction volume of polysiloxane was larger than 0.872, which is the smallest value of forming a PA/PSi particle, the PSi/PA particles were unavoidably formed simultaneously with PA/PSi particle formation. The synthesis of PA/PSi particles containing equal amounts of polyacrylate and polysiloxane was then carried out using seeded emulsion polymerization. Before the cyclosiloxane cationic polymerization, 3-methacryloyloxypropyl trimethoxysilane (MATS) was introduced into the polyacrylate seed latex to form an intermediate layer and chemical bonds between the core and the shell polymers. The characterization by transmission electron microscopy (TEM) demonstrated that the perfect PA/PSi core/shell particle is successfully synthesized when both the core and the shell polymers are crosslinked. The experiments showed that both the hardness and water adsorption ratio characteristics of latex films of the PA/PSi particles are in good agreement with those of the polysiloxane film.
The precipitation polymerization of styrene-trihydroxymethyl propane triacrylate has been carried out using ethanol and an ethanol/water mixture as the solvent. Uniform microspheres with high monomer conversion are achieved within 4 h, a much shorter polymerization time than that reported for the precipitation polymerization of divinyl benzene-styrene in acetonitrile. The results clearly demonstrate that use of water as a co-solvent is indeed very effective to promote the polymerization to high conversion and to obtain uniform microspheres. With no water under the otherwise same experimental conditions, only about 57% of monomer conversion is obtained; while the monomer conversion is remarkably increased to 96% when 12 vol.-% of water is used.
Porous polyurea is synthesized by reacting toluene diisocyanate with water in a water–acetone binary solvent. Materials characterization led to the likely conformations of the polymer chains owing to presence of intensive H-bonding.
• Toluene diisocyanate (TDI) based polyurea (TPU) is prepared by TDI reaction with H 2 O. • TPU shows strong fluorescent emission as solid powder and in its solution. • The emission in UV region is intrinsic due to its phenyl and the adjacent urea group. • The emission in visible zone is owing to the formation of molecule clusters. • Paper strip dipped in TPU solution is used for easy detections of Fe 3+ and H 2 O 2 .
A porous polyurea (PPU) was prepared through a simple protocol by reacting toluene diisocyanate with water in binary solvent of water-acetone. Its amine group was determined through spectrophotometric absorbance based on its iminization with p-nitrobenzaldehyde amines. PPU was then used as a novel polymer support for enzyme immobilization, through activation by glutaraldehyde followed by immobilization of an enzyme, lipase from Pseudomonas fluorescens (PFL), via covalent bonding with the amine groups of lipase molecules. Influences of glutaraldehyde and enzyme concentration and pH in the process were studied. The results revealed that the activity of the immobilized PFL reached a maximum at GA concentration of 0.17 mol/L and at pH 8. Immobilization rate of 60% or higher for PFL was obtained under optimized condition with an enzyme activity of 283 U/mg. The porous structure of PPU, prior to and after GA activation and PFL immobilization, was characterized. The activity of the immobilized PFL at different temperature and pH and its stability at 40 °C as well as its reusability were tested. The immobilized enzyme was finally used as enantioselective catalyst in kinetic resolution of racemic 1-phenylethanol (1-PEOH), and its performance compared with the free PFL. The results demonstrate that the enzyme activity and stability were greatly improved for the immobilized PFL, and highly pure enantiomers from racemic 1-PEOH were effectively achieved using the immobilized PFL. Noticeable deactivation of PFL in the resolution was observed by acetaldehyde in situ formed. In addition, the immobilized PFL was readily recovered from the reaction system for reuse. A total of 73% of the initial activity was retained after 5 repeated reuse cycles. This work provides a novel route to preparation of a polyurea porous material and its enzyme immobilization, leading to a novel type of immobilized enzyme for efficient kinetic resolution of racemic molecules.
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