RADICAL INTERMEDIATES IN THE FLUORESCEIN-AND EOSIN-PHOTOSENSITIZED AUTOXIDATION OF l-TYROSINE*

Abstract The Primary reactions of the cosin-and fluorescein-photosensitized autoxidation of L-tyrosine were studied in aqueous media (pH = 8.6) by the flash-photolysis technique. The dye molecules were quantitatively converted to their triplet states in a single flash. The triplet dye molecules were found to react with tyrosine or oxygen. Ground state or radical dye molecules were formed in these reactions. Some 40 per cent of the triplet-tyrosine reactions yielded radicals, in triplet dye-oxygen reactions the corresponding yield was less than 10 per cent. The ground state dye was regenerated from the semireduced dye in reactions with oxygen and from the semioxidized dye in reactions with tyrosine. In the absence of oxygen the radicals formed in the photoinduced electron-transfer between the triplet dye and tyrosine recombined to a large extent.     

Liquid-vapor interface of square-well fluids of variable interaction range

Properties of the liquid-vapor interface of square-well fluids with ranges of interaction lambda=1.5, 2.0, and 3.0 are obtained by Monte Carlo simulations and from square-gradient theories that combine the Carnahan-Starling equation of state for hard spheres with the second and third virial coefficients. The predicted surface tensions show good agreement with the simulation results for lambda=2 and for lambda=3 in a temperature range reasonably close to the critical point, 0.8相似文献   

Rhodium(II)‐Catalyzed Inter‐ and Intramolecular Cyclopropanations with Diazo Compounds and Phenyliodonium Ylides: Synthesis and Chiral Analysis

Different classes of cyclopropanes derived from Meldrum's acid (=2,2‐dimethyl‐1,3‐dioxane‐4,6‐dione; 4 ), dimethyl malonate ( 5 ), 2‐diazo‐3‐(silyloxy)but‐3‐enoate 16 , 2‐diazo‐3,3,3‐trifluoropropanoate 18 , diazo(triethylsilyl)acetate 24a , and diazo(dimethylphenylsilyl)acetate 24b were prepared via dirhodium(II)‐catalyzed intermolecular cyclopropanation of a set of olefins 3 (Schemes 1 and 4–6). The reactions proceeded with either diazo‐free phenyliodonium ylides or diazo compounds affording the desired cyclopropane derivatives in either racemic or enantiomer‐enriched forms. The intramolecular cyclopropanation of allyl diazo(triethylsilyl)acetates 28, 30 , and 33 were carried out in the presence of the chiral dirhodium(II) catalyst [Rh₂{(S)‐nttl)₄}] ( 9 ) in toluene to afford the corresponding cyclopropane derivatives 29, 31 and 34 with up to 37% ee (Scheme 7). An efficient enantioselective chiral separation method based on enantioselective GC and HPLC was developed. The method provides information about the chemical yields of the cyclopropane derivatives, enantioselectivity, substrate specifity, and catalytic activity of the chiral catalysts used in the inter‐ and intramolecular cyclopropanation reactions and avoids time‐consuming workup procedures.     

Coordination Chemistry of Acrylamide: 1. Cobalt(II) Chloride Complexes with Acrylamide – Synthesis and Crystal Structures

The molecular structures of blue dichloro‐tetrakis(acrylamide) cobalt(II), [Co{O‐OC(NH₂)CH=CH₂}₄Cl₂] ( 1 ) and pink hexakis(acrylamide)cobalt(II) tetrachlorocobaltate(II), [Co{O‐OC‐(NH₂)CH=CH₂}₆][CoCl₄] ( 2 ), characterized by single X‐ray diffraction, IR spectroscopy and elemental analyses, are described. The coordination of Co^II in 1 involves a tetragonally distorted octahedral structure with four O‐donor atoms of acrylamide in the equatorial positions and two chloride ions in the apical positions. The second complex 2 in ionic form contains Co^II cations surrounded by an octahedral array of O‐coordinated acrylamide ligands, accompanied by a [CoCl₄]^2? anion.     

Synthesis of amino sugars via isoxazolines DL- and D-lividosamine (2-amino-2,3-dideoxy-ribo-hexose) derivatives from 4-vinyl-1,3-dioxolanes and nitroacetaldehyde acetals

1,3-Dipolar cycloaddition of nitrile oxides, generated from nitroethanol and nitroacetaldehyde derivatives 3, 21 and 22, respectively, and of benzonitrile oxide to 4-vinyldioxolanes 1, 2 gave ca 4:1 erythro/threo mixtures of corresponding isoxazolines. LAH reduction of erytho isoxazolines proceeded with similar (ca 4:1) selectivity to furnish protected ribo-amino-polyols 11, 15,19, DL- and D-lividosamines 31 and 33, respectively, as main products. The DL-lividosamine derivative 33 was obtained pure by crystallization. In the D-series, the corresponding ribo/arabino mixture D-31/D-32 was transformed to the known α-methyl D-lividosaminide D-37.     

Multivariate comparison of concentration profiles in materials analysis

Hierarchical cluster analysis (HCA) and principal components analysis (PCA) were applied to find groups between similar depth-profiles in thin-layers investigated by Rutherford backscattering spectrometry (RBS).HCA yields in one run an objective hierarchy of similarity for several profiles. Among the similarity coefficients examined the linear measure, the Euclidean distance and the exponential measure respond with different sensitivity to overall shifts in direction of the concentration axis, whereas the correlation measure relates to parallelism of the profiles.For agglomerative HCA with Euclidean distance, a lowest significant linkage level has been defined by use of Fisher'sF-test. For divisive HCA based also on Euclidean distance, the maximum of a separating function marks the most separating cluster step. The outcomes of both proposals agree for the data set investigated.PCA is useful for verifying the results of HCA and yields additional information about the data structure. In the actual example quite different positions of features (concentrations at definite depths) in the space of the two first principal components hint at peculiarities during the metallurgical coating process.     

1,3-Alternate calix[4]arenes, selectively functionalized by amino groups

General strategies are described to synthesize calix[4]arenes which are fixed in the 1,3-alternate conformation and substituted selectively by amino groups. These derivatives are useful starting materials for the attachment of various groups via amide bonds, as demonstrated by several examples, but may be converted also to ureas, imides or azomethines. Four amino groups may be attached to the narrow rim via(several) methylene groups as spacer by O-alkylation with omega-bromophthalimides or omega-bromonitriles. From the resulting tetraethers the amino functions are obtained by cleavage with hydrazine or by hydrolysis, allowing a selective functionalisation of both sides of the molecule (phenolic units A, C versus B, D). Amino functions at the wide rim are introduced by ipso-nitration of the respective t-butylcalix[4]arene derivatives and subsequent reduction. Selective ipso-nitration of a 1,3-diether, followed by O-alkylation with allylbromide to obtain the tetraether in the 1,3-alternate conformation, hydrogenation of allyl and nitro groups (in one step), protection of the amino functions as phthalimides followed by ipso-nitration of the remaining t-butyl phenol rings, allows again to distinguish both sides of the molecule (units A, C versus B, D). Reaction of a wide rim tetraamine in the 1,3-alternate conformation by Boc-anhydride allows not only to obtain the mono- and tri-Boc derivative, but also in nearly 60% yield the C2-symmetrical di-Boc derivative, in which two adjacent phenolic units are protected (distinction of A, B from C, D). This paves the way for the preparation of chiral derivatives or assemblies. O-Alkylation with omega-bromophthalimides followed by ipso-nitration leads to precursors for octaamines in the 1,3-alternate conformation, in which the potential amino functions on both rims can be selectively "activated" by reduction or hydrazinolysis. The structures of the newly synthesized molecules were mainly confirmed by their 1H NMR spectra, which allow a distinction from isomeric derivatives in the cone and partial cone conformation. Single crystal X-ray analyses were obtained for two analogous derivatives in the 1,3-alternate conformation (27, n = 3,4), an isomeric compound in the cone conformation (27, n = 3,4), and a derivative in the partial cone conformation (11).     

CEPA calculations on open-shell molecules. V. The vibration frequencies of SF and SCl

Ab initio calculations for the ² ground states of SF and SCl have been performed on Hartree-Fock level and with inclusion of valence shell correlation effects by means of the CI and CEPA approaches. The calculated properties are: Equilibrium distances, vibration frequencies, and dipole moment curves in the vicinity of the respective equilibrium geometries. Our best estimates for the 0 1 infrared absorption frequencies _o for SF and SCl are 786 cm^–1 and 520 cm^–1, respectively, both with an uncertainty of about 10 cm^–1. This confirms a recent experimental value obtained by Willner for SF (791 cm^–1), but indicates that for SCl both experimental values reported previously in the literature (617 cm^–1 and 574 cm^–1) are wrong. The S—F and S—Cl bonds in SF and SCl are very similar to the ones in SF₂ and SCl₂, being essentially single p-bonds in either case. In the analogous oxygen-halogen molecules the situation is different, the O—F and O—Cl bonds in the diatomic radicals OF and OCl have partial double bond character and are much stronger than those in OF₂ and OCl₂ or in HOF and HOCl.     

Metal- and ligand-directed one-pot syntheses,crystal structures,and properties of novel oxo-centered tetra- and hexametallic clusters

Starting from closely related metal-ligand combinations, completely different oligomeric metal clusters are synthesized. Whereas, picoline-tetrazolylamide HL(1) (1) and zinc or nickel acetate afforded [2x2] grids [M(4)(L(1))(8)] (2), slightly different N-(2-methylthiazole-5-yl)-thiazole-2-carboxamide HL(2) (5 a) and nickel acetate yielded the monometallic complex [Ni(L(2))(2)(OH(2))(2)] (6). In contrast, reaction of 5 a with zinc acetate produced the tetrametallic zinc cluster [Zn(4)O(L(2))(4)(OAc)(2)] (7). Even more surprising, when 3-methyl-substituted HL(3) (5 b) instead of 2-methyl-substituted HL(2) (5 a) was allowed to react under identical conditions with zinc acetate, the cluster [Zn(4)O(L(3))(4)Cl(2)] (8) crystallized from dichloromethane. Clusters 7 and 8 are isostructural. As for 7, in 8 two of the edges of the tetrahedron of zinc ions are doubly bridged, two are singly bridged, and the other two are nonbridged. On the other hand, when iron(II) acetate under aerobic conditions was allowed to react with 5 a, the unprecedented complex [[Fe(3)O(L(2))(2)(OAc)(4)](2)O] (9) was isolated. Cluster 9 is composed of two trimetallic, triangular mu(3)-O(2-)-centered [Fe(3)O(L(2))(2)(OAc)(4)](+) modules, linked by an almost linear mu(2)-O(2-) bridge. The M?ssbauer spectrum together with cyclic voltammetric and square-wave voltammetric measurements of 9 are reported, and 6-9 were characterized unequivocally by single-crystal X-ray structure analyses.