Differences in the reaction of electron deficient olefins with organocopper(I)-Lewis acid reagents and evidence for a dianionic equivalent

Treatment of diethyl fumarate and triethoxycarbonylethylene with Bu₂CuLi·AlCl₃ led to 1,4-addition to give butylated products in high yields. In sharp contrast, diethyl maleate and tetraethoxycarbonylethylene predominantly gave the respective reduction products. The first evidence for a presumed dianionic intermediate by trapping with some electrophiles was also presented.     

Swelling and deswelling kinetics of poly(N-isopropylacrylamide) gels

Swelling and deswelling kinetics was investigated for three types of cylindrical poly(N-isopropylacrylamide) (PNIPA) gels differing in crosslink density. The temperature dependence curves of the volume of the gel specimens were different from one another. One of the gel specimens was considered as a critical gel showing the continuous volume phase transition. The volume change process of the specimens after a temperature jump was examined. In the deswelling processes with temperature jumps to temperatures higher than 35 degrees C, a phase separation was observed in the gel specimens and the volume change slowed down due to the homogenization after the phase separation. The value of the diffusion constant obtained without the phase separation decreased rapidly as temperature approaches the transition temperature. The rapid decrease for the critical gel indicates the emergence of the critical slowing-down. The value of the critical exponent for the correlation length suggests that the universality class for the volume phase transition of the critical PNIPA gel belongs to the class for the classical theory.     

Droplet formation in a microchannel network

A method is given for generating droplets in a microchannel network. With oil as the continuous phase and water as the dispersed phase, pico/nanoliter-sized water droplets can be generated in a continuous phase flow at a -junction. The channel for the dispersed phase is 100 microm wide and 100 microm deep, whereas the channel for the continuous phase is 500 microm wide and 100 microm deep. For given experimental parameters, regular-sized droplets are reproducibly formed at a uniform speed. The diameter of these droplets is controllable in the range from 100-380 microm as the flow velocity of the continuous phase is varied from 0.01 m s(-1) to 0.15 m s(-1).     

A spot test for ammonium ion by the color band formation method

Removing nutrients from wastewaters is important in controlling eutrophication. Processes for removing nutrients require accurate control of operational conditions, and it is necessary to monitor nutrient concentrations during the removal process. For this purpose, a simple and accurate analytical method is especially important for small-scale wastewater treatment facilities. Here, we report a simple colorimetric method for determining NH₄⁺-N in wastewater. The method is to detect NH₄⁺-N by a color band length formed in a minicolumn, and similar methods for heavy metals detection were reported by Morosanova et al. In this study, the length of the color band of indonaphthol dye trapped on an adsorbent in a minicolumn was linearly correlated with NH₄⁺-N concentration in the range 1-10 mg NH₄⁺-N l⁻¹ under optimized conditions. This methods was developed on the basis of our previously reported color band methods for orthophosphate and nitrite determination, but the adsorbent used in this work consisted of an admixture of synthetic hydrotalcite particles and poly(vinyl chloride) particles coated with equal amounts of benzylcetyldimethylammonium chloride and biphenyl. When the method was applied to actual wastewaters, the results corresponded well with the results obtained by the standard method, and suspended solids (SS) and dissolved organic pollutants did not interfere with detection.     

Enhancement of the Catalytic Activity of Chiral H8‐BINOL Titanium Complexes by Introduction of Sterically Demanding Groups at the 3‐Position

The activity of chiral titanium catalysts derived from H₈‐BINOL ligands in the enantioselective arylation of an aldehyde with PhTi(OiPr)₃ is significantly enhanced by an increase of the size of the substituent at the 3‐position. High enantioselectivity (> 90 % ee) can be obtained even at a substrate/catalyst ratio (S/C) of 800 for DTBP‐H₈‐BINOL (DTBP=3,5‐di‐tert‐butylphenyl) and DAP‐H₈‐BINOL (DAP=3,5‐di(9‐anthraceny)phenyl). These titanium catalysts are successfully applied to the enantioselective arylation and heteroarylation of aldehydes at a S/C ratio of 400 by using organotitanium reagents generated in situ from bromide precursors. The remarkable weakening of the intramolecular aggregation of the two ?Ti(OiPr)₃ units in a DPP‐H₈‐BINOL (DPP=3,5‐diphenylpheny)‐derived bis‐titanium complex is revealed by X‐ray and variable‐temperature (VT)‐NMR studies. Based on these observations, a catalytic cycle, involving the rate‐limiting aryl group transfer followed by aldehyde complexation and enantioselective arylation, is proposed to account for the high activity of the 3‐substituted H₈‐BINOL catalyst system.