Hemilabile‐coordinated copper promoted amination of aryl halides with ammonia in aqueous ethylene glycol under atmosphere pressure

Direct amination of aryl iodides and bromides with ammonia under 1 atm pressure has been effected using in situ‐generated hemilabile coordinated copper(I) species from copper(I) halides or copper metal in aqueous ethylene glycol, producing primary aromatic amines in good yields. Ammonia pressure and water were found to accelerate the copper‐mediated reaction while strong chelating ligands showed a suppression effect. A rationale for the copper‐mediated amination of aryl halides with ammonia is given based on a double‐face role of chelating effect. Copyright © 2009 John Wiley & Sons, Ltd.     

The analyses of alkyllead compounds in fish and environmental samples in Ontario,Canada (1981–1987)

Analyses of fish and other environmental samples (clams, macrophytes, sediments and waters) from areas upstream and downstream from two alkyllead manufactures beside the St Lawrence and St Clair Rivers, Ontario, show a clear indication of elevated alkyllead levels in samples near the industries. Most species of fish contained alkyllead compounds with tetraethyllead and triethyllead as the predominant forms. Most fish from the contaminated areas contained 50–75% of total lead as alkylleads. Carp, yellow perch and white sucker were generally the most contaminated species while pike, alewife and rock bass were the least contaminated. Average alkyllead levels varied from year to year but declined steadily after 1981. For example, the geometric mean of alkyllead compounds in carp from the St Lawrence River decreased from 4207 μg kg^?1 in 1981 to 2000 μg kg^?1 in 1982 and to 49 μg kg^?1 in 1987, reflecting the reduction of alkylleads in the effluents and the closure of one of the manufactures in 1985. Alkyllead levels were consistently lower in muscle and carcass samples in comparison with whole fish containing fatty intestines. However, muscle levels were generally equal to carcass levels. The concentrations of alkyllead compounds were generally low in clams, macrophytes, sediments and waters except from the immediate vicinity of the manufactures' final effluent discharges.     

Structure and acid-basic properties of the surface of titanium oxides modified by phosphorus and aluminum and prepared by the alkoxo method. 2. Study of the active surface of titanium oxides

The data of temperature-programmed desorption of ammonia from the surface of oxide systems and IR spectroscopy were used to demonstrate that the strength of the surface acid sites in titanium oxides prepared by the alkoxo method and modified by aluminum decreases with respect to that in nonmodified titanium oxide. Modification of titanium oxide with P³⁺ ions from ethriol phosphite almost completely suppresses the acid properties. Modified oxides are able to chemisorb water. XANES data suggest that modification of titanium oxide with phosphorus ions increases the electron density on the titanium atoms and, correspondingly, the basicity of the materials.     

Minimal dissipation rate approach to correlate phase inversion data

Phase inversion refers to the phenomenon whereby a small change in operational flow conditions causes an oil-in-water dispersed flow pattern to suddenly switch to a water-in-oil flow pattern, and viceversa. This paper proposes an interpretation of phase inversion in terms of minimal dissipation rate. To this end, the dissipation rate is computed by a simple homogeneous model together with available correlations for effective viscosity in dispersed flows. It is shown that the data available in the literature can be reasonably interpreted as a manifestation of minimal dissipation rate. Furthermore, if the assumed effective viscosity correlations take into account pipe wettability, the minimal dissipation rate approach is capable to interpret also the so-called ambivalent range (hysteresis effect) and correlate the available data.     

T2 relaxation measurement with solvent suppression and implications to solvent suppression in general

A number of suppression pulse sequences including Excitation Sculpting and WATERGATE were incorporated into the standard Carr‐Purcell‐Meiboom‐Gill (CPMG) program for T₂ measurement and experimentally evaluated. The chosen suppression schemes were of varying complexity encompassing pulse program elements, such as presaturation, gradients, and selective pulses, which are typically utilized for solvent suppression. The quality of the spectral data and the accuracy of T₂ measurements of the investigated suppression schemes were evaluated using three aqueous samples with increasing proton content in the water solvent, i.e. by volume 100% D₂O, 80/20% D₂O/H₂O, and 20/80% D₂O/H₂O. For signals removed from the water signal, the T₂ values were generally very consistent between all pulse sequences tested. T₂ measurements can be unreliable for signals too close to the water signal such that they are significantly suppressed as well. Their intensity may actually grow initially through cross relaxation that transfers magnetization back to the solute signal. In turn, this relaxation phenomenon can be exploited to improve the spectral quality of conventional solvent suppression schemes. In favorable cases, even signals that are completely masked by the water signal can be recovered by adding a carefully chosen number of spin echoes with optimized evolution time to conventional water suppression pulse programs, such as Excitation Sculpting or WATERGATE. Copyright © 2009 John Wiley & Sons, Ltd.     

基于分布参数模型的CO_2蒸发器结构参数研究

在设计工况下,建立了用于跨临界二氧化碳热泵热水器的套管式蒸发器的稳态分布参数模型,对其结构参数进行了敏感性分析,指出了它们的合理变化范围:管内套1根管时,内管外径应至少大于11.00mm,低于13.00mm,外管内径应在20.00mm以上,23.00mm以下;管内套多根管时,以管内套3根管的性能为最优。优化设计结果对开发二氧化碳蒸发器产品具有一定的指导意义。     

TVD scheme for computing open channel wave flows

For the shallow water equations in the first approximation (Saint-Venant equations), a TVD scheme is developed for shock-capturing computations of open channel flows with discontinuous waves. The scheme is based on a special nondivergence approximation of the total momentum equation that does not involve integrals related to the cross-section pressure force and the channel wall reaction. In standard divergence difference schemes, most of the CPU time is spent on the computation of these integrals. Test computations demonstrate that the discontinuity relations reproduced by the scheme are accurate enough for actual discontinuous wave propagation to be numerically simulated. All the qualitatively distinct solutions for a dam collapsing in a trapezoidal channel with a contraction in the tailwater area are constructed as an example.     

Micelles possessing mixed cores and thermoresponsive shells fabricated from well‐defined amphiphilic ABC miktoarm star terpolymers

Amphiphilic ABC miktoarm star terpolymers consisting of polystyrene, poly(ε‐caprolactone), and poly(N‐isopropylacrylamide) arms, PS(‐b‐PNIPAM)‐b‐PCL, were synthesized via a combination of atom transfer radical polymerization, ring‐opening polymerization (ROP), and click chemistry. Difunctional PS bearing an alkynyl and a primary hydroxyl moiety at the chain end, PS‐alknyl‐OH, was prepared by reacting azido‐terminated PS with an excess of 3,5‐bis(propargyloxy)benzyl alcohol (BPBA) under click conditions. The subsequent ROP of ε‐caprolactone using PS‐alknyl‐OH macroinitiator afforded PS(‐alkynyl)‐b‐PCL copolymer bearing an alkynyl moiety at the diblock junction point. Target PS(‐b‐PNIPAM)‐b‐PCL amphiphilic ABC miktoarm star terpolymers were then prepared via click reaction between PS(‐alkynyl)‐b‐PCL and an excess of azido‐terminated PNIPAM (PNIPAM‐N₃). The removal of excess PNIPAM‐N₃ was accomplished by “clicking” onto alkynyl‐functionalized Wang resin. All the intermediate and final products were characterized by gel permeation chromatography, ¹H NMR, and FTIR. In aqueous solution, the obtained amphiphilic ABC miktoarm star terpolymer self‐assembles into micelles possessing mixed PS/PCL cores and thermoresponsive shells, which were further characterized by dynamic laser light scattering and transmission electron microscopy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1636–1650, 2009     

Compression elastic modulus of neutral,ionic, and amphoteric hydrogels based on N‐vinylimidazole

Several hydrogels of N‐vinylimidazole and sodium styrenesulfonate have been prepared by radical cross‐linking copolymerization in aqueous solution, using N,N′‐methylene‐bisacrylamide as crosslinker. Depending on composition, these hydrogels were neutral, amphoteric, cationic or anionic. Compression‐strain measurements were performed on samples as‐synthesized and swollen in deionized water or in acid aqueous solutions, with and without salt. It was thus found that the cross‐linking densities determined by compression measurements on as‐synthesized samples are in good accordance with those calculated by means of the model of polymer networks with pendant vinyl groups. A non‐Gaussian parameter (β) was introduced to explain that the elastic moduli (G) of samples swollen at equilibrium are larger than predicted by the Gaussian model. The β values of the neutral or ionized systems increase with swelling and fall into a single curve, which denotes a common behavior. Swelling has two opposite effects on G; on the one hand G decreases because the polymer volume fraction diminish and the system shifts from the affine limit to the phantom one; on the other, β increases and contributes to increasing G. The balance of those two opposite effects determines the variation of G with swelling. The possible contribution of ionic crosslinks to ν_e for the polyampholyte and for the polycation wearing divalent counteranions was discussed. A peculiar system is poly(sodium styrenesulfonate), whose cross‐linking density is much lower than expected. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1078–1087, 2009