Sol-Gel and Ultrafine Particle Formation via Dielectric Tuning of Inorganic Salt-Alcohol-Water Solutions

Under some conditions, inorganic salts can be as good precursors for sol-gel-type processing as those obtained from expensive metalloorganic precursors such as alkoxides. In this work, the formation of monodispersed hydrous zirconia microsphere particles (particularly nanosized) and gels was achieved in solutions of zirconyl chloride dissolved in alcohol-water mixed solvents. The dielectric property of the mixed alcohol-water solvent directly affects the nucleation and growth of zirconia clusters/particles in homogeneous solutions. A lower dielectric constant of mixed solvent corresponds to a lower solubility of inorganic solute and, thus, a shorter induction period for nucleation as well as higher solid particle growth kinetics. Dynamic light scattering (DLS) was used to monitor the homogeneous nucleation and growth processes, while final particles and gels were studied by scanning electron microscopy (SEM) and high-temperature X-ray diffraction (HTXRD). The sol-gel processes in the mixed solvent system can be adjusted using the processing parameters, including the initial inorganic salt concentration (C), alcohol/aqueous medium volume ratio of the mixed solution (RH), incubation temperature (T), incubation time (t), concentration of hydroxypropyl cellulose (HPC), and ammonia neutralization. Monodispersed submicron and nanoscale (<100 nm) zirconia microspheres/powders were successfully synthesized under conditions of high RH (5) and using HPC (molecular weight of 100,000, 2.0x10(-3) g/cm(3)) and ammonia neutralization. Initial salt concentration affects the particle size significantly. Gel materials were obtained under conditions of low RH (1.0). Microstructure and transparency of gels changed significantly from low (0.05 M) to high (0.2 M) concentration of the metal salt. We have also demonstrated that monodispersed particle production can be achieved not only at low temperatures (<100 degrees C) but also at room temperature using an inorganic salt precursor. Copyright 2000 Academic Press.     

In situ preparation of protein-"smart" polymer conjugates with retention of bioactivity

Protein-polymer conjugates are widely used in biotechnology and medicine, and new methods to prepare the bioconjugates would be advantageous for these applications. In this report, we demonstrate that bioactive "smart" polymer conjugates can be synthesized by polymerizing from defined initiation sites on proteins, thus preparing the polymer conjugates in situ. In particular, free cysteines, Cys-34 of bovine serum albumin (BSA) and Cys-131 of T4 lysozyme V131C, were modified with initiators for atom transfer radical polymerization (ATRP) either through a reversible disulfide linkage or irreversible bond by reaction with pyridyl disulfide- and maleimide-functionalized initiators, respectively. Initiator conjugation was verified by electrospray-ionization mass spectroscopy (ESI-MS), and the location of the modification was confirmed by muLC-MSMS (tandem mass spectrometry) analysis of the trypsin-digested protein macroinitiators. Polymerization of N-isopropylacrylamide (NIPAAm) from the protein macroinitiators resulted in thermosensitive BSA-polyNIPAAm and lysozyme-polyNIPAAm in greater than 65% yield. The resultant conjugates were characterized by gel electrophoresis and size exclusion chromatography (SEC) and easily purified by preparative SEC. The identity of polymer isolated from the BSA conjugate was confirmed by (1)H NMR, and the polydispersity index was determined by gel permeation chromatography (GPC) to be as low as 1.34. Lytic activities of the lysozyme conjugates were determined by two standard assays and compared to that of the unmodified enzyme prior to polymerization; no statistical differences in bioactivity were observed.     

Improved preparation and new reactions of β -(1-phenylthio) cyclopropyl enones

β-(1-Phenylthio)cyclopropyl enones can be conveniently prepared via reaction of the lithium salts of α-hydroxymethylene ketones with 1-lithio-1-phenylthiocyclopropane and are converted efficiently by treatment with aqueous acid to γ-keto cyclobutanones and less successfully by thermolysis to -γ-keto phenylthiocyclopentenes.