Synthesis of end-branched poly(ethylene glycol)s by aqueous atom transfer radical polymerization

Summary This article reports the synthesis of novel hydrophilic end-branched poly(ethylene glycol)s, in aqueous media by atom transfer radical polymerization (ATRP). Poly(ethylene glycol)s with molecular weights 10,000 and 16,000 were end-functionalized and used as bifunctional initiators for the polymerization of a poly(ethylene glycol) macromonomer with a molecular weight of 2,000 (PEGMA), either by aqueous ATRP or in a watedmethanol (l/l V/V) mixture. For both macroinitiators a DP of 10 was the target, giving an average of 5 branches in each end. The rates of polymerization were of the same order of magnitude when the polymerizations were initiated by either of the two macroinitiators in watedmethanol (l/l V/V). When a bifunctional oligo(ethy1ene glycol) initiator (M_n = 600) was used to study the polymerization of PEGMA in water/methanol a reduction in the rate of polymerization was observed indicating an influence of the molecular weight of the initiator on the rate of polymerization. Received 25 Maich 2002/Revised 8 November 2002/Accepted 8 November 2002 Correspondence to Jorgen Kops     

TEM Characterization of Single- and Multilayer Triol-Based Sol–Gel PZT (53/47) Thin Films

Integrated lead zirconate titanate thin films deposited on Pt/Ti/SiO₂/Si substrates using a novel triol-based route were characterized using X-ray diffraction and transmission electron microscopy. Crack-free single-layer PZT films of up to 200 nm thick were prepared by triol-based sol–gel processing onto Pt/Ti/SiO₂/Si substrates. Films ∼75 nm thick exhibited a microstructure free of pores and second phase. As film thickness increased, film texture changed from {100} to {111} perovskite. Essentially, single-phase multilayer films could be prepared by the deposition and pyrolysis of several 75 nm layers, followed by a single crystallization step. The influence of heat-treatment schedule on the microstructure and orientation of the multilayer films is discussed. Comparison has been made between multilayer films prepared using the triol-based sol and an inverted mixing order/acetic acid-based sol.     

Influence of Phenolic acids on microbial populations in the rhizosphere of cucumber

Experiments were conducted to determine whether changes in soil microbial populations that occur in response to additions of certain allelopathic phenolic acids to bulk soil also occur in the rhizosphere. Cucumber seedlings were transplanted into cups containing a nutrient-enriched mixture of Portsmouth B₁, soil and sand and were watered five times (once every 48 hr) with aqueous solutions of ferulic,p-coumaric, or vanillic acid (each at 0, 0.25, or 0.50ol/g soil material). Nutrient solution was applied on alternate days. Leaf growth was suppressed by up to 42% by phenolic acids, but changes in root growth varied with the compound and concentration in solution. Significant increases (over 600% relative to controls) in populations of fast-growing bacteria in the rhizosphere were detected after two but not after five treatments, and increases (400% relative to controls) in numbers of fungal propagules were detected after five treatments. Such increases suggested that chronic exposure to a phenolic acid might resuit in high populations of rhizosphere microorganisms that could metabolize the compounds and thus alter observable responses by the plant. To test this, plants were watered repeatedly with a low-concentration solution of ferulic acid (chronic treatments; 0.0 or 0.1mol/g soil material in one experiment, 0.000 or 0.025imol/g soil material in a second) and then once with a highconcentration solution (acute treatment; 0.0, 0.5, or 1.0mol/g soil material in the first experiment; 0.000, 0.125, or 0.250mol/g soil material in the second).Paper No. 12385 of the Journal Series of the North Carolina Agricultural Research Service, Raleigh, North Carolina. The use of trade names in this publication does not imply endorsement by the North Carolina Agricultural Research Service or the United States Department of Agriculture of the products named, nor criticism of similar ones not mentioned. Acute treatments and some chronic treatments suppressed leaf growth, but results were inconsistent for root growth. Acute treatments increased numbers of several types of bacteria in the rhizosphere but had inconsistent effects on fungi. Chronic treatments had no effect on numbers of bacteria or fungal propagules in the rhizosphere. Furthermore, chronic treatments did not alter responses of plants or microbial populations to the subsequent acute treatment. Results demonstrated that phenolic acids in soil, which must pass through the rhizosphere before interaction with plant roots can occur, alter the microbial ecology of the rhizosphere. However, microbially mediated acclimation of plants to relatively high concentrations of ferulic acid was not observed.     

Equilibrium catalyst from a fluidized catalytic cracking unit separated by metal content by using carbon nanotubes and a biphasic system

During fluid catalytic cracking (FCC) operations FCC catalyst particles become contaminated with various metals. These metals impact FCC performance and currently requires equilibrium catalyst (ECAT) mixtures consisting of a blend of FCC particles with a time spent in the reactor ranging from minutes to several months to be continuously extracted and sold as low value products or sent to landfills. Here a unique method to recycle FCC ECAT particles is presented, which separates ECAT particles by metal content by synthesizing carbon nanotubes and nanofibers on the ECAT particles surface and using a biphasic system. ECAT with low metal content can be sent back to the FCC unit for further use while ECAT with high metal content can be used for other purposes. Further, we show these treated ECAT materials of high metals content will absorb oil on the surface of water and may prove useful for oil spill clean-up applications.     

Synthesis and characterization of photopolymerizable hydrogels based on poly (ethylene glycol) for biomedical applications

Hydrogels are polymeric materials widely used in medicine due to their similarity with the biological components of the body. Hydrogels are biocompatible materials that have the potential to promote cell proliferation and tissue support because of their hydrophilic nature, porous structure, and elastic mechanical properties. In this work, we demonstrate the microwave-assisted synthesis of three molecular weight varieties of poly(ethylene glycol) dimethacrylate (PEGDMA) with different mechanical and thermal properties and the rapid photo of them using 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184) as UV photoinitiator. The effects of the poly(ethylene glycol) molecular weight and degree of acrylation on swelling, mechanical, and rheological properties of hydrogels were investigated. The biodegradability of the PEGDMA hydrogels, as well as the ability to grow and proliferate cells, was examined for its viability as a scaffold in tissue engineering. Altogether, the biomaterial hydrogel properties open the way for applications in the field of regenerative medicine for functional scaffolds and tissues.     

Polystyrene and poly(methyl methacrylate) interfaces reinforced with diblock carbon nanotubes

An asymmetric double cantilever beam test was used to determine the ability of carbon nanotubes with varying chemistry along their lengths, that is, diblock nanotubes, to compatibilize the polystyrene/poly(methyl methacrylate) (PS/PMMA) interface. PS molecules were grafted primarily to one of the blocks to cause that block to migrate to the PS phase since otherwise both blocks would prefer to reside in PMMA. Fracture toughnesses increased monotonically with increasing diblock carbon nanotube concentration and maximum values were like those for block copolymer-reinforced interfaces while single-chemistry nanotubes showed no reinforcing effect. However, the abrupt increase in fracture toughness with added compatibilizer indicative of a transition to crazing was not found consistent with nanotubes suppressing crazing in homopolymers. Scanning electron microscopy images of the fractured surfaces show agglomerates of carbon nanotubes present which are likely limiting the efficacy of carbon nanotubes at toughening the interface.     

Calculation of film stress from pitch measurements in LCD panel manufacturing

A method based on inverting a finite element model is presented for determining film stress from pitch changes before and after a film deposition step in liquid‐crystal display panel manufacturing. It differs from the conventional methods by making use of in‐plane deformation rather than out‐of‐plane measurements to calculate film stress. The resulting film stress is confounded with glass structural relaxation. Measurements of out‐of‐plane deformation at the edge of the sheet can be used with the pitch measurements to separate the effects of glass structural relaxation and film stress.