Functional polymers. III. Asymmetric Michael reactions catalyzed by cinchona alkaloid–acrylonitrile copolymers

The enantio-differentiating abilities of cinchona alkaloid–acrylonitrile copolymers (AN–CA) in the Michael reactions were studied. The reaction of methyl indan-1-one-2-carboxylate (I) with methyl vinyl ketone in toluene at room temperature yielded product (II) in 24–42% optical yield, depending on the type and frequency of the alkaloid units on the polymeric skeleton. The catalysts were recovered from the reaction mixture by filtration and with retention of their stereoselectivities. Modification of the amino or hydroxyl group of the alkaloid moiety greatly reduced the reaction rate and optical yield. The asymmetric reactions of other donors (III–VII) with methyl vinyl ketone were also studied.     

Cobalt(III), copper(II), and nickel(II) complexes of 1-thia-4,7-diazacyclononane-S-oxide

Summary The title complexes [ML₂]ⁿ⁺=Co^III, Cu^II, Ni^II; L=1-thia-4,7-diazacyclononane-S-oxide) have been prepared and characterized spectroscopically. The sulphoxide group is coordinated through the oxygen atom and the complexes have atrans-O,O geometry. The nickel(II) complex of bis(2-amino-ethyl)sulphoxide has also been studied.     

Use of the vanadium(V)-xylenol orange mixture as an improved reagent for the spectrophotometric determination of traces of hydrogen peroxide

The reaction in V(V)-xylenol orange (XO)-H₂O₂ system was studied by spectrometry. On the addition of hydrogen peroxide to the mixture of vanadium(V) and XO (V-XO reagent), the absorption peak of V(V)-XO complex (λ_max = 582 nm) decreased significantly. The decrease in the absorbance (denoted as ΔA) was proportional to the concentration of hydrogen peroxide. The constant values of ΔA were obtained under the condition of [XO]/[V(V)] = 0.5 ~ 1.2 and in the pH 3.5 ~ 4.5 region. Based on these results, the conditions for the use of the V-XO reagent in the colorimetric determination of hydrogen peroxide were examined in detail. The V-XO reagent was found to be useful for the trace analysis of hydrogen peroxide with high sensitivity, and the data were little affected by the presence of some inorganic and organic substances. The lower limit of the determination is about 1 × 10^?6M.     

Iron twin-coronet porphyrins as models of myoglobin and hemoglobin: amphibious electrostatic effects of overhanging hydroxyl groups for successful CO/O2 discrimination

Inspired by the observation of polar interactions between CO and O(2) ligands and the peptide residues at the active site of hemoglobin and myoglobin, we synthesized two kinds of superstructured porphyrins: TCP-IM, which contains a linked imidazole ligand, and TCP-PY, which contains a linked pyridine ligand, and examined the thermodynamic, kinetic, and spectroscopic (UV/Vis, IR, NMR, and resonance Raman) properties of their CO and O(2) complexes. On both sides of each porphyrin plane, bulky binaphthyl bridges form hydrophobic cavities that are suitable for the binding of small molecules. In the proximal site, an imidazole or pyridine residue is covalently fixed and coordinates axially to the central iron atom. In the distal site, two naphtholic hydroxyl groups overhang toward the center above the heme. The CO affinities of TCPs are significantly lower than those of other heme models. In contrast, TCPs have moderate O(2) binding ability. Compared with reported model hemes, the binding selectivity of O(2) over CO in TCP-IM and TCP-PY complexes is greatly improved. The high O(2) selectivity of the TCPs is mainly attributable to a low CO affinity. The comparison of k(on)(CO) values of TCPs with those of unhindered hemes indicates the absence of steric hindrance to the intrinsically linear CO coordination to Fe(II) in TCP-IM and TCP-PY. The abnormally large k(off)(CO) values are responsible for the low CO affinities. In contrast, k(off)(O(2)) of TCP-PY is smaller than those of other pyridine-coordinated model hemes. For the CO adducts of TCPs, unusually low nu(Fe-CO) and unusually high nu(C-O) frequencies are observed. These results can be ascribed to decreased back-bonding from the iron atom to the bound CO. The lone pairs of the oxygen atoms of the hydroxyl groups prevent back-bonding by exertion of a strong negative electrostatic interaction. On the other hand, high nu(Fe-O(2)) frequencies are observed for the O(2) adducts of TCPs. In the resonance Raman (RR) spectrum of oxy-TCP-IM, we observed simultaneous enhancement of the Fe-O(2) and O-O stretching modes. Furthermore, direct evidence for hydrogen bonding between the hydroxyl groups and bound dioxygen was obtained by RR and IR spectroscopy. These spectroscopic data strongly suggest that O(2) and CO binding to TCPs is controlled mainly by the two different electrostatic effects exerted by the overhanging OH groups: destabilization of CO binding by decreasing back-bonding and stabilization of O(2) binding by hydrogen bonding.     

Reaction specificity of a titanium(IV)-porphyrin complex to hydrogen peroxide in view of an Ab initio study.

A Ti-TPyP reagent, i.e. an acidic aqueous solution of oxo[5,10,15,20-tetra(4-pyridyl)porphyrinato]titanium(IV) complex, TiO(tpyp), was previously developed as a highly sensitive and specific reagent for determining hydrogen peroxide. In the present work, the reaction specificity of the TiO(tpyp) complex to hydrogen peroxide was clarified based on ab initio calculations. The results provide a well-grounded argument for determining hydrogen peroxide using the Ti-TPyP reagent experimentally.     

Analyticity of nonlinear semigroups

The Cauchy problemdu/dt =Au(t),u(0) =u ₀∈D(A) has analytic solutions whenA has first and second Gateaux derivatives along the solution curve in a certain weak sense. HereA is a maximal monotone operator in a complex Hilbert space.     

Adsorption study of acetylcholine and cholinergic and anticholinergic drugs onto an electrode surface

As a type of interaction of acetylcholine and cholinergic and anticholinergic drugs with a charged surface, their adsorption onto a gold electrode has been examined by measuring the specular reflectivity and differential capacity of the electrode-solution interface.Based on the adsorption potential profiles, the drugs have been divided into three groups: (I) carbamylcholine and methacholine; (II) tetraethylammonium ion and hexamethonium; (III) nicotine, atropine, scopolamine and pilocarpine. Group I includes cholinergic drugs. Group II and III include antichilinergic drugs whose adsorptivity is stronger than that of acetylcholine. The results of the adsorption of acetylcholine and drugs onto a charged electrode surface should provide information about the competitive inhibitory effects on the attachement of acetylcholine to receptor sites.