Sorption and pervaporation properties of crosslinked membranes of poly(ethylene oxide imide) segmented copolymer to aromatic/nonaromatic hydrocarbon mixtures

Poly(ethylene oxide imide) segmented copolymer (PEO‐PI) membranes were crosslinked by the chemical reaction between ethylene glycol diglycidyl ether and benzylalcohol groups of diamine moieties in polyimide segments at high temperatures. Sorption and diffusion of penetrants took place in poly(ethylene oxide) segment microdomains. Sorption and desorption behavior of pure vapors such as benzene (Bz), cyclohexane (Cx) and n‐hexane (Hx) was classified as the Fickian diffusion. Sorption isotherms of binary liquid mixtures could be represented by the Flory–Rehner model, but the model overpredicted the sorption amounts of Cx and Hx, leading to small predictions of sorption selectivity α_S for Bz/Cx and Bz/Hx systems. UNIFAC‐FV model fairly well predicted the sorption amounts of aromatic hydrocarbons, but significantly overestimated those of nonaromatic ones, leading to too small predictions of α_S. Pervaporation (PV) behavior of PEO‐PI membranes was governed by sorption behavior followed by membrane swelling. Diffusion coefficient weakly depended on the minimum cross section of a penetrant. The diffusivity selectivity α_D hardly depended on the feed composition and was about 1.4 and 0.75 for Bz/Cx and Bz/Hx, respectively. PV selectivity α_PV was larger for Bz/Hx than for Bz/Cx because of larger α_S. PEO‐PI membranes displayed high specific permeation flux Ql and reasonably high α_PV for aromatic/nonaromatic hydrocarbons; for example, Ql = 60 Kg μm/(m² h) and α_PV = 8 for a feed mixture containing Bz, Tol, Hx, n‐Ot and i‐Ot of 20 wt % at 353 K. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1800–1811, 2000     

Numerical simulation of a metal diffraction grating-based SPR sensor with a water-immersion lens

Optical Review - We describe a metal diffraction grating-based surface plasmon resonance sensor (G-SPRS) that operates in a differential mode, the angular sensitivity of which would be 4.8 times...     

Three New Monoterpene Glucosides from Lamium amplexicaule

Three new monoterpene glucosides, lamiuamplexosides A–C ( 1 – 3 ), along with thirteen known glucosides, were isolated from the whole plant of Lamium amplexicaule L. The structures of 1 – 3 were elucidated on the basis of spectroscopic, chemical, and physicochemical evidence.     

Size-dependent reactivity of cobalt cluster ions with nitrogen monoxide: Competition between chemisorption and decomposition of NO

Reactions of NO molecules on cobalt cluster ions were studied in a beam-gas geometry by using a tandem mass spectrometer. Single-particle collision reactions of Co_mNO⁺ (m = 3–10) with NO were found to proceed in such a manner that NO decomposition dominates at m = 4–6 with the maximum reaction cross section at m = 5 and chemisorption dominates in m ≥ 7. On the other hand, in two-particle collision reactions of Co_n⁺ (n = 2–10) with NO, NO decomposition at n ≥ 5 and chemisorption of two NO molecules with Co atoms loss at n ≥ 8 were found to proceed. These results indicate that the size-dependency of the multiple collision reactions originates from secondary attacking of an NO molecule to primary products of the initial single collision reactions. The DFT calculation supports the scheme that both the decomposition and chemisorption of two-particle collision reactions proceed via a common intermediate, Co_mN₂O₂⁺, in which the two NO molecules are dissociatively chemisorbed on the cobalt cluster ion, and the size-dependency of the two-particle collision reactions is explained in terms of the structure of this reaction intermediate.     

Me‐bipam for Enantioselective Ruthenium(II)‐Catalyzed Arylation of Aldehydes with Arylboronic Acids

Ligand design by‐pam : A ruthenium‐catalyzed asymmetric arylation of aldehydes with arylboronic acids has been developed, giving chiral diarylmethanols in good yields. The use of a chiral bidentate phosphoramidite ligand ((R,R)‐Me‐bipam) led to excellent enantioselectivities.

     

On the existence of Burgers vortices for high Reynolds numbers

Axisymmetric or non-axisymmetric Burgers vortices have been studied numerically as a model of concentrated vorticity fields. Recently it has been rigorously proved that non-axisymmetric Burgers vortices exist for all values of the vortex Reynolds number if an asymmetry parameter is sufficiently small. On the other hand, several numerical results indicate that Burgers vortices have simpler structures as the vortex Reynolds number is increasing, even when the asymmetry parameter is not sufficiently small. In this paper we give a rigorous explanation for this numerical observation and extend the existence and stability results of Burgers vortices for high vortex Reynolds numbers.     

High-dimensional asymptotic expansions for the distributions of canonical correlations

This paper examines asymptotic distributions of the canonical correlations between and with q≤p, based on a sample of size of N=n+1. The asymptotic distributions of the canonical correlations have been studied extensively when the dimensions q and p are fixed and the sample size N tends toward infinity. However, these approximations worsen when q or p is large in comparison to N. To overcome this weakness, this paper first derives asymptotic distributions of the canonical correlations under a high-dimensional framework such that q is fixed, m=n−p→∞ and c=p/n→c₀∈[0,1), assuming that and have a joint (q+p)-variate normal distribution. An extended Fisher’s z-transformation is proposed. Then, the asymptotic distributions are improved further by deriving their asymptotic expansions. Numerical simulations revealed that our approximations are more accurate than the classical approximations for a large range of p,q, and n and the population canonical correlations.     

Reactions of 26-iodopseudodiosgenin and 26-iodopseudodiosgenone with various nucleophiles and pharmacological activities of the products

26-Iodopseudodiosgenin (8) and 26-iodopseudodiosgenone (9) were reacted with various nucleophiles (KSCN, KOCN, NaCN, NaN(3) and various amines) to give pseudodiosgenin derivatives (4, 12, 16-20, 26) and pseudodiosgenone derivatives (5, 13, 21-25, 27), respectively. The reactions of 8 and 9 with KOCN gave the elimination products (10) and (11), respectively. The reaction of 9 with NaCN gave 5alpha,26- (14) and 5beta,26-dicyanocholestan-3-one (15). The reaction of 8 with NaN3 gave triazepine derivative (30), while that of 9 gave 26-azidopseudodiosgenone (31). Compound 31 was converted into triazepine derivative (32) by heating at 120 degrees C. The cytotoxicity of the pseudodiosgenins and pseudodiosgenones on P-gp-underexpressing HCT 116 cells and P-gp-overexpressing Hep G2 cells was examined by MTT assay. Pseudodiosgenins 2, 4, 12 and 30 showed strong cytotoxic activity (IC50 values: 2.6+/-0.3-6.7+/-1.4 microM), as did pseudodiosgenones 3, 5, 11, 13, 21-25 and 27 (IC50 values: 1.3+/-0.3-6.4+/-0.3 microM) toward HCT 116 cells. Pseudodiosgenins 12, 16 and 30 (IC50 values: 1.2+/-0.7-2.2+/-0.6 microM) and pseudodiosgenones 22, 23, 25 and 27 (IC50 values: 0.6+/-0.1-2.5+/-0.3 microM) were highly cytotoxic to Hep G2 cells. Compounds 3 and 27 showed efficient antibacterial activity (MIC: 15.6, 10.4 microg/ml) and (MIC: 7.8, 15.6 microg/ml) against Bacillus subtilis and Staphylococcus aureus, respectively.     

Me‐BIPAM for the Synthesis of Optically Active 3‐Aryl‐3‐hydroxy‐2‐oxindoles by Ruthenium‐catalyzed Addition of Arylboronic Acids to Isatins

A chiral O‐linked C₂‐symmetric bidentate phosphoramidite (Me‐BIPAM) was found to be efficient for the ruthenium‐catalyzed addition of arylboronic acids to isatins. Asymmetric synthesis of 3‐aryl‐3‐hydroxy‐2‐oxindoles by 1,2‐addition of arylboronic acids to isatins was carried out in the presence of [RuCl₂(PPh₃)₃]/(R,R)‐Me‐BIPAM and KF, resulting in an enantioselectivity as high as 90 % ee. It was found that the reaction with N‐protected isatins proceeds with high yields and good enantioselectivities. The best protective groups on the nitrogen atom were different depending on the substituents on the aromatic ring. The use of a N‐benzyl group resulted in excellent enantioselectivities in many substrates compared with other groups.     

Strong and selective binding of amiloride to an abasic site in RNA duplexes: thermodynamic characterization and microRNA detection

Firmly tied: The binding affinity of amiloride for an abasic (AP) site-containing RNA duplex is two orders of magnitude superior to the affinity of the corresponding AP site-containing DNA duplex. The observed high binding affinity for the RNA duplex arises from a favorable enthalpy gain. The binding-induced fluorescence response of amiloride is applicable to microRNA detection.