Resolution of lymphocyte subpopulations derived from rat spleen by polyamine-graft-PHEMA copolymer

The retention behavior of lymphocyte subpopulations, B cell, T cell and null cell, derived from rat spleen to polyamine-graft-poly(2-hydroxyethyl methacrylate) copolymer (HA) surface was investigated, focusing on the conformational transition of the polyamine side chain as well as the protonation of amino groups in the polyamine grafts. Furthermore, the availability of HA was discussed as a column adsorbent for separation of lymphocyte subpopulations derived from spleen. The conformational transition of polyamine grafts significantly influenced the mode of retention of lymphocyte subpopulations. When polyamine grafts existed in an aggregated conformation (protonatin degree α < 0.5), the retention of lymphocyte subpopulations was decreased in the order B cell> null cell> T cell. On the other hand, when polyamine existed in an extended conformation into the aqueous interior from the matrix interface (α > 0.5), T cell retention became greater than null cell retention, resulting in a decreased B cell> T cell> null cell order. These results indicate that the differential retention of spleen lymphocyte subpopulations is attributed to their differential responses to the change in matrix interface accompanied by the protonation of amino groups. Furthermore, spleen lymphocytes were compared with lymph node lymphocytes in terms of resolution efficacy by an HA copolymer column.     

Secondary hypervalent I(III)...O interactions: synthesis and structure of hypervalent complexes of diphenyl-lambda3-iodanes with 18-crown-6

Reported here for the first time are the synthesis and characterization of supramolecular complexes between diaryl-lambda(3)-iodanes and 18-crown-6 (18C6). Slow evaporation of solvents afforded 1:1 and 2:1 complexes between Ph(2)IBF(4) and 18C6 as stable crystals, depending on the conditions. X-ray crystal structures of these complexes indicated that each iodine atom contacts with the three adjacent oxygen atoms of 18C6 through two hypervalent secondary bonding and a weak interaction. (1)H NMR analyses and CSI-MS spectra showed that, in dichloromethane solution, Ph(2)IBF(4) exclusively forms the 1:1 complex with 18C6 (binding constant K(a), 1.02 x 10(3) M(-)(1)). The binding constants decrease with the increased solvent donor ability (Gutmann's DN). Changing the heteroatom ligand from BF(4) to the less nucleophilic PF(6) and AsF(6) increased the binding constant by about six times. Substitution of an electron-withdrawing group onto the para position of Ph(2)IBF(4) tends to increase in the complex stability. A linear Hammett relationship (rho = 0.59) between log K(a) and sigma(p)(+) values of substituents indicates that the diaryl-lambda(3)-iodanes with electropositive iodine(III) interact more efficiently with 18C6. Decreased binding magnitude was measured with 15C5, dibenzo-18C6, dibenzo-21C7, and dibenzo-30C10.     

Synthesis and analgesic activity of novel heterocycles, [1]benzothiopyrano[3,4-b]pyrrole derivatives

In order to develop analgesic compounds possessing a sulfur atom in the alicyclic ring, novel cis-fused heterocycles, [1]benzothiopyrano[3,4-b]pyrrole derivatives (II) were synthesized via a unique cyclization reaction starting from 4-(4-methoxyphenylthio)-2-butanone (1) or 6-methoxy-3,4-dihydro-2H-1-benzothiopyran-4-one (7). The analgesic effects of benzothiopyranopyrroles (16, 18) were measured by means of the writhing test. The phenolic derivative 18 completely inhibited the appearance of writhing at the dose of 50 mg/kg, but the methoxy derivative 16 had no analgesic effect.     

Syntheses and biological activities of renin inhibitors containing statine analogues

Syntheses and biological activities of dipeptide renin inhibitors that contain statine analogues are described. The key steps of the synthetic approach to dipeptide renin inhibitors are the asymmetric synthesis of 2(R)-substituted-3-aminocarbonylpropionic acids and the diastereoselective syntheses of (3S,4S)-statine analogues. These inhibitors (2,14-40) inhibited human renin in the 3-140 nM range. Inhibitor ES 6864 (2) was found to be a highly potent inhibitor of human renin (IC50: 4.6 x 10(-9) M) and showed high enzyme specificity. Oral administration of ES 6864 at 3 mg/kg to conscious, sodium-depleted marmosets inhibited plasma renin activity (PRA) more than 80% after 1 h.     

Studies on polyyne polymers containing transition metals in the main chain. VII. Synthesis and characterization of palladium-polyyne polymers

Metal-polyyne polymers consisting of palladium and conjugated acetylenic systems, where P_D and R represent the —Pd(PBu₃)₂—moiety and alkyl groups, respectively, were prepared by polycondensation between palladium chlorides and α,ω-diethynyl compounds in amines using a catalytic amount of cuprous iodide. The molecular weights of the polymers formed were greatly affected by the basicity of the amines and the addition of free phosphines to the polymerization system. Under the optimum conditions, i.e., in the presence of CuI and PBu₃ (in molar ratio 1/4) in piperidine at room temperature, polymer Ia (R¹ = R² = H) having M?_w = 29,000 was obtained.     

Construction of a liquid-membrane type periodate ion-selective electrode and its application to the potentiometric titration of alpha-diols and alpha-amino-alcohols

The construction of a liquid-membrane type periodate ion-selective electrode and its application to the potentiometric titration of alpha-diols and alpha-amino-alcohols are described. The ion-pair of periodate anion with Capriquat (tri-n-octylmethylammonium chloride), is easily extracted into nitrobenzene, and this extract is employed as a liquid ion-exchange membrane. The calibration curve shows Nernstian response towards periodate ion over the concentration range from 10(-1)M to 10(-7)M with a slope of 60 mV/pIO(-)(4). Selectivity coefficients with respect to various ions were evaluated. The electrode potential was independent of pH in the range 2.5-7.5. Some alpha-diols and monoethanolamine were successfully titrated potentiometrically with the aid of the present electrode.     

Dependence of selective enclathration on types of cholic acid crystals

Competitive recrystallizations of cholic acid (CA) from 1:1 binary mixtures of seven mono-substituted benzenes are demonstrated. The order of preference for guests to be incorporated into the cholic acid crystals are as follows: benzene, toluene > n-amylbenzene, n-hexylbenzene > ethylbenzene, n-propylbenzene, n-butylbenzene. These seven compounds afford bilayer type inclusion crystals that are classified into four types based on the host frameworks and host-guest stoichiometries. The order of selective enclathration corresponds to the four types as follows: 1:1 alpha G > 2:1 alpha G > 1:1 beta T or 2:1 alpha T. The preference for the alpha G type was also confirmed by investigating the host frameworks of the crystals obtained from binary mixtures. The dependence of the selectivity on the different types of CA crystals can be understood in terms of the fit of the guest molecule in the host cavity.     

Determination of daidzein and genistein in soybean foods by automated on-line in-tube solid-phase microextraction coupled to high-performance liquid chromatography

An automated on-line method for the determination of the isoflavones, daidzein and genistein, was developed using in-tube solid-phase microextraction coupled to high-performance liquid chromatography (in-tube SPME-HPLC). In-tube SPME is a new extraction technique for organic compounds in aqueous samples, in which analytes are extracted from the sample directly into an open tubular capillary by repeated draw/eject cycles of sample solution. Daidzein, genistein and their glucosides tested in this study were clearly separated within 8 min by HPLC using an XDB-C8 column with diode array detection. In order to optimize the extraction of these compounds, several in-tube SPME parameters were examined. The glucosides daidzin and genistin were analyzed as aglycones after hydrolysis because the glucosides were not concentrated by in-tube SPME. The optimum extraction conditions for daidzein and genistein were obtained with 20 draw/eject cycles of 40 microl of sample using a Supel-Q porous layer open tubular capillary column. The extracted compounds were easily desorbed from the capillary by mobile phase flow, and carryover was not observed. Using the in-tube SPME-HPLC method, the calibration curves of these compounds were linear in the range 5-200 ng/ml, with a correlation coefficient above 0.9999 (n = 18), and the detection limits (S/N = 3) were 0.4-0.5 ng/ml. This method was successfully applied to the analysis of soybean foods without interference peaks. The recoveries of aglycones and glucosides spiked into food samples were above 97%.     

Benzoyl(acetylacetonato)nickel(II) complexes containing tertiary phosphine ligands. Their synthesis,dynamic behavior in solution,and decarbonylation

Carbon monoxide is readily inserted into the phenyl—nickel bond of PhNi(acac)(PR₃)_n to give benzoylnickel complexes, PhCONi(acac)PR₃ (R = Ph, Et, cyclo-C₆H₁₁), which were characterized by elemental analysis, IR and NMR spectroscopy, as well as chemical reactions. The reactions of the benzoylnickel complexes with methyl iodide and alcohols give acetophenone and corresponding benzoates, respectively, accompanied by some decomposition reactions. The solid benzoylnickel complexes when heated at elevated temperatures are decarbonylated and biphenyl, benzophenone and carbon monoxide are liberated. The dynamic behavior of the acac ligand in acetone solution was studied and the activation parameters for the acac exchange reactions were obtained. The decarbonylation reaction of the benzoyl complex PhCONi(acac)PPh₃ in acetone was studied by NMR, and found to be first order in the benzoylnickel complex.     

Isolation, characterization, and theoretical study of La2@C78

A new metallofullerene, La2@C78, has been synthesized by DC arc discharge method, isolated by high-performance liquid chromatography, and characterized by laser desorption time-of-flight mass spectrometry, UV-vis-NIR absorption, differential pulse voltammetry, 13C NMR spectroscopy, and theoretical calculations. The La2@C78/CS2 solution is dark violet and presents several characteristic absorption features at 647, 561, 533, and 386 nm, with an onset around 1000 nm. With respect to empty D3-C78, the capability of La2@C78 as an electron acceptor or donor is stronger. Addition of 1,1,2,2-tetrakis(2,4,6-trimethylphenyl)-1,2-disirane to La2@C78 photochemically, as well as thermally, affords bis- and mono-adducts. Theoretical studies and 13C NMR spectroscopic analysis of La2@C78 indicate that it possesses a D3h-C78 cage (78:5).