Synthesis of poly(ethylene oxide) with pending 2,2,6,6‐tetramethylpiperidine‐1‐oxyl groups and its further initiation of the grafting polymerization of styrene

A new stratagem for the synthesis of amphiphilic graft copolymers of hydrophilic poly(ethylene oxide) as the main chain and hydrophobic polystyrene as the side chains is suggested. A poly(ethylene oxide) with pending 2,2,6,6‐tetramethylpiperidine‐1‐oxyls [poly(4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl‐co‐ethylene oxide)] was first prepared by the anionic ring‐opening copolymerization of ethylene oxide and 4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl, and then the graft copolymerization of styrene was completed with benzoyl peroxide as the initiator in the presence of poly(4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl‐co‐ethylene oxide). The polymerization of styrene was under control, and comblike, amphiphilic poly(ethylene oxide)‐g‐polystyrene was obtained. The copolymer and its intermediates were characterized with size exclusion chromatography, ¹H NMR, and electron spin resonance in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3836–3842, 2006     

Asymmetric synthesis XXVII: Asymmetric catalytic trimethylsilylcyanation of aldehydes by novel Ti-chiral Schiff base complexes

Enantioselective catalytic trimethylsilylcyanations of aldehydes with 48% to 92% e.e. have been studied using the novel Ti-chiral Schiff base complexes. We have found that the catalyst led to high enantoselectivity when the molar ratio of the Schiff base 1 to Ti(O-i-Pr)₄ was 2:1.     

Preparation of Y2Ba4Cu7O15-δ Superconductor without High Oxygen Pressure

The synthesis of bulk Y₂Ba₄Cu₇O_15-δ superconductor at atmospheric oxygen pressure via solid state sintering is reported. Temperature ranging from 860 to 890 °C as well as time interval over 2 to 15 days were used to investigate the formation of the Y₂Ba₄Cu₇O_15-δ phase. A time-temperature profile characterizing the conditions for the preparation of Y₂Ba₄Cu₇O_15-δ phase suggests the optimal condition to be sintering at 890 °C for over 10 days. Detailed results of X-ray diffraction, electrical resistivity, iodometric titration and magnetization measurements are described.     

Guest sorption and desorption in the metal-organic framework [Co(INA)(2)] (INA=isonicotinate)--evidence of intermediate phases during desorption

The metal-organic framework [Co(INA)(2)]x0.5EtOH (INA = isonicotinate, NC(5)H(4)-4-CO(2)(-)), was synthesised under solvothermal conditions. Its X-ray crystal structure shows channels containing ethanol guests which are hydrogen-bonded to carboxylate oxygens of the framework. The pyridyl rings of the framework alternate between 'open' and 'closed' positions along the channels resulting in large variation in the channel cross-sectional area from ca. 1.4 by 2.3 A at the narrowest point to 4.9 by 5.3 A at the widest. Despite the very small windows, the ethanol guests (of van der Waals diameter ca. 4.2-6.1 A) may be reversibly desorbed and sorbed into the structure quantitatively, as shown by in situ variable-temperture IR spectroscopy and XRPD. The single-crystal structure of the desolvated form [Co(INA)(2)] shows that there is no change in the overall connectivity on desolvation, but the rotational positions of the pyridine rings are altered. This suggests that pyridyl rotation may occur to allow guests to pass in and out. When the synthesis was conducted in 1-propanol solvent [Co(INA)(2)]x0.5Pr(n)OHxH(2)O, was obtained, and a single-crystal X-ray structure revealed the same overall connectivity as in but with pyridine rings disordered over closed and open positions. There was no evidence of included guests from X-ray crystallography, suggesting that they are also highly disordered. Variable-temperature XRPD performed on bulk samples showed peaks which were unsymmetrical and exhibited shoulders, suggesting that for each pattern obtained the material actually consisted of several closely-related phases. The movements of the peaks during desolvation showed the presence of intermediate phases before the final desolvated product was formed. The peak positions of the intermediate phases matched more closely with the calculated pattern for than with or, suggesting that they may have disordered structures similar to. The results also suggest that the intermediate phase represents an initial increase in volume before a larger decrease in volume occurs to give the final desolvated material.     

Potential energy surfaces for HenNe+ ions: ab initio and diatomics-in-molecule results

The potential energy surface of He2Ne+ has been reinvestigated using a combination of ab initio and diatomics-in-molecule (DIM) calculations. In contrast to the reports of two recent studies the ion is found to have an asymmetric linear He-Ne-He structure, with no barrier to formation from the separated atoms on the ground-state surface. The He-Ne+ bond lengths at the potential minimum are 1.51 and 1.81 A, and the total bonding energy is 0.717 eV. Comparing the He2Ne+ energy to that of HeNe+, the bonding energy for the second helium atom is 0.06 eV, about 10% of that of the first He atom. The saddle point between the two equivalent minima is a symmetric structure, 0.0074 eV above the potential minimum. A symmetric geometry becomes the overall potential minimum if the 2s hole on the Ne is excluded from the reference states of a multireference configuration interaction calculation. A DIM potential was created for the HenNe+ family of ions. The DIM potential is consistent with the asymmetric He2Ne+ ion serving as a core; it predicts a slightly more asymmetric geometry than the ab initio results. Additional helium atoms form five-membered rings around the bonds of the core ion to fill the first shell and then add to the ends of the cluster. The asymmetric core ion and the highly compact structure help to account for the lack of apparent shell structure in the mass spectrometry of HenNe+ clusters. Finally, we recommend that the value De=0.63+/-0.04 eV be adopted for the ground state of HeNe+.     

WATER-BLOWN POLYURETHANE RIGID FOAMS MODIFIED BY CHEMICAL PLASTICATION

1. INTRODUCTIONThese years, HCFC-141b may be the most used blowing agent for its useful properties. But, because of its high global warming effect leading to the destruction of the ozone layer, production of HCFC141b has been forbidden. However, there are…     

Novel Rearrangements of 2,3-Dimercapto-1-propanol Derivatives: Formation of Dialkyl Sulfide, Dialkyl Disulfide, and 1,2,3-Tris(alkylthio)propane

The base alkylation of 2,3-dimercapto-1-propanol with alkyl halides leads in good yield to 2,3-bis(alkylthio)-1-propanol and dialkyl sulfide. The reaction of 2,3-bis(alkylthio)-1-propanol with catalytic concentrated sulfuric acid proceeds with rearrangement to give 1,2,3-tris(alkylthio)propane and dialkyl disulfide. The rearrangement reaction takes place through a common intermediate thiaranium intermediate 8.     

Novel Phenomenon of Oxygen-to-oxygen Silyl Migration in Directed Aldol Reaction

The phenomenon of migration of the silyl groups from α-oxygen to β-oxygen in sodium aldol reaction was observed for the first time in this paper.     

Study of the Fluorescence System of Europium–Enoxacin and its Applications

 This paper is the study of the fluorescence enhancement of Eu³⁺-1-ethyl-6-fluoro-4-oxo-7-(1-piperazinyl)-1,8-naphthyridin-3-carbonic acid (enoxacin, EFLX) system by surfactants. It was found that sodium dodecylbenzenesulfonate (SDBS) exhibits great enhancement on the fluorescence of the Eu-EFLX system. The molar ratio is 1:2:1 for Eu:EFLX: SDBS. Under the optimum conditions, the fluorescence intensity is a linear function of europium in the range of 1.0 × 10⁻⁸ ∼ 5.0 × 10⁻⁶ mol/L, the detection limit is 1.0 × 10⁻⁹ mol/L. The application of the Eu-EFLX-SDBS system for the determination of trace europium in rare earth samples gave satisfactory results. Received October 19, 2000. Revision August 10, 2001.