Xanthate complexes of nickel with nitrogen donor ligands. Part V

Nickel(II) xanthate complexes of general formula, [Ni(Rxa)₂(L)] [R = i-Pr, i-Am, xa = OCS^– ₂, L = 4,7-diphenyl-1,10-phenanthroline(baphen), 4,4-dimethyl-2,2-bipyridyl (me₂bpy), 2-9-dimethyl-1,10-phenanthroline(neo) or trans-1,2-diaminocyclohexane (dch)] and [Ni(Rxa)(cyclam)](Rxa) (= 1,4,8,11-tetraazacyclotetradecane) have been synthesized and characterized by elemental analyses, i.r. and electronic spectroscopy, magnetic and conductivity measurements. The complexes with cyclam were studied by cyclic voltammetry. Values of magnetic moments at room temperature lie within the 3.25–3.51 B.M. range and thus indicate the presence of two unpaired electrons, except for the complexes with cyclam, where the anomalous values of 1.76 and 1.74 B.M. were obtained in respect to the nickel(II) complexes. Magnetic susceptibility data for [Ni(i-Prxa)(cyclam)](i-Prxa) were measured over the 79–298 K range and indicate no exchange interaction between paramagnetic nickel(II) centres.     

The satellite-shaped Co-15 Polyoxotungstate, [Co6(H2O)30{Co9Cl2(OH)3(H2O)9(beta-SiW8O31)3}]5-

The 15-cobalt-substituted polyoxotungstate [Co(6)(H(2)O)(30){Co(9)Cl(2)(OH)(3)(H(2)O)(9)(beta-SiW(8)O(31))(3)}](5-) (1) has been characterized by single-crystal XRD, elemental analysis, IR, electrochemistry, magnetic measurements, and EPR. Single-crystal X-ray analysis was carried out on Na(5)[Co(6)(H(2)O)(30){Co(9)Cl(2)(OH)(3)(H(2)O)(9)(beta-SiW(8)O(31))(3)}].37H(2)O, which crystallizes in the hexagonal system, space group P6(3)/m, with a = 19.8754(17) A, b = 19.8754(17) A, c = 22.344(4) A, alpha= 90 degrees, beta = 90 degrees, gamma = 120 degrees, and Z = 2. The trimeric polyanion 1 has a core of nine Co(II) ions encapsulated by three unprecedented (beta-SiW(8)O(31)) fragments and two Cl(-) ligands. This central assembly {Co(9)Cl(2)(OH)(3)(H(2)O)(9)(beta-SiW(8)O(31))(3)}(17-) is surrounded by six antenna-like Co(II)(H(2)O)(5) groups resulting in the satellite-like structure 1. Synthesis of 1 is accomplished in a simple one-pot procedure by interaction of Co(II) ions with [gamma-SiW(10)O(36)](8-) in aqueous, acidic NaCl medium (pH 5.4). Polyanion 1 was studied by cyclic voltammetry as a function of pH. The current intensity of its Co(II) centers was compared with that of free Co(II) in solution. Our results suggest that 1 keeps its integrity in solution. Magnetic susceptibility results show the presence of both antiferro- and ferromagnetic coupling within the (Co(II))(9) core. A fully anisotropic Ising model has been employed to describe the exchange-coupling and yields g = 2.42 +/- 0.01, J(1) = 17.0 +/- 1.5 cm(-1), and J(2) = -13 +/- 1 cm(-(1). Variable frequency EPR studies reveal an anisotropic Kramer's doublet.     

Local dense structural heterogeneities in liquid water from ambient to 300 MPa pressure: evidence for multiple liquid-liquid transitions.

Difference and double-difference near-infrared DO-D and HO-H stretching overtone (2nuOD and 2nuOH) spectroscopy and a rigorous (physically substantiated) band deconvolution technique were applied to reveal three different kinds of inherent (interstitial) structures of liquid water, which determine its high density (compared to ice lh under ambient conditions), its compressibility (under hydrostatic pressure, up to 300MPa), and its high fragility (manifested under temperature variation). Our data processing allowed the rigorous discrimination of up to six vibrational components. On the basis of an extensive comparative analysis combined with available structural data (X-ray and neutron scattering) and molecular dynamics (MD) simulations for liquid water, as well as with experimental and computed data for small non-tetrahedrally arranged water clusters, the major four components could be ascribed to: i) The basic lh icelike substructure; ii) the temperature-dependent remote interstitial "defects" due to tetrahedral displacements (primarily responsible for transport properties); iii) the interstitial "defects" most probably arranged in quasiplanar noncyclic tetramers (totally absent in the ice structure); and iv) the interstitial "defects" formed with increasing pressure, probably arranged in cubic water octamers and composed of two pairs of noncyclic and cyclic tetramer fragments. The latter structures include, essentially, bent hydrogen bonds stabilized by resonance effects.     

Synthesis and characterization of new strontium 4-carboxyphenylphosphonates

Several new strontium 4-carboxyphenylphosphonates, i.e., two modifications of Sr(HOOCC₆H₄PO₃H)₂, SrH(OOCC₆H₄PO₃)·H₂O, Sr₃(OOCC₆H₄PO₃)₂·4H₂O and Sr₃(OOCC₆H₄PO₃)₂·5.7H₂O were prepared and characterized by elemental analysis, thermogravimetry, X-ray powder diffraction and infrared spectroscopy. It was found that the compositions of these compounds depend on the acidity of the reaction medium. In addition, the presented compounds are interconvertible in dependence on pH. The position of the acid hydrogen atom in SrH(OOCC₆H₄PO₃)·H₂O was determined from the IR spectra of the studied compounds.The structure of the β modification of Sr(HOOCC₆H₄PO₃H)₂ was solved from its X-ray powder diffraction pattern using an ab initio method (the FOX program) with subsequent Rietveld refinement in the FULLPROF program. The compound is monoclinic, with the space group P2₁/c (No. 14), a=49.88(2), b=7.867(2), c=5.602(3) Å, β=128.68(2)°, and Z=4. It has a one-dimensional structure with an inorganic part built of SrO₈ distorted tetragonal antiprisms.     

C.I. Calculations on the lower transitions in the terphenyl and quaterphenyl di-valent ions

Energies and transition dipole moments for the lower electronic transitions in the terphenyl and quaterphenyl di-valent ions have been calculated starting from the Pople SCF MO's for the ground state ions. The configuration interaction included about one-hundred singly and doubly excited configurations. The results of the calculations for the lower allowed electronic transitions are in very satisfactory agreement with the experimental spectra.     

Photoreactivity of tiaprofenic acid and suprofen using pig skin as an ex vivo model

The skin is repeatedly exposed to solar ultraviolet radiation. Photoreaction of drugs in the body may result in phototoxic or photoallergic side effects. Non-steroidal anti-inflammatory drugs, such as tiaprofenic acid (TPA) and the closely related isomer suprofen (SUP) are frequently associated with photosensitive disorders; they may mediate photosensitised damage to lipids, proteins and nucleic acids. Using ex vivo pig skin as a model, we investigated the photodegradation of TPA and SUP, and photobinding of these drugs to protein by means of HPLC analysis and drug-directed antibodies. Both with keratinocytes, which were first isolated from the pig skin and thereafter exposed to UVA and with keratinocytes which were isolated from pig skin after the skin was UVA exposed, time-dependent photodegradation of TPA and SUP was found, beside photoadduct formation to protein. The results of this work show that: (a) TPA and SUP were photodecomposed with similar efficiency; major photoproducts detected were decarboxytiaprofenic acid (DTPA) and decarboxysuprofen (DSUP), respectively. (b) Both drugs form photoadducts, as concluded from recognition by drug-specific antibodies. Pig skin appears to be a good model for studying the skin photosensitising potential of drugs.     

Biosynthesis of anthecotuloide,an irregular sesquiterpene lactone from Anthemis cotula L. (Asteraceae) via a non-farnesyl diphosphate route

Retrobiosynthetic analysis of the allergenic sesquiterpene lactone, anthecotuloide, suggested that this natural product could be formed either by head to head condensation of geranyl diphosphate with dimethylallyl diphosphate, or from farnesyl diphosphate (FPP), the accepted regular sesquiterpene precursor via the rearrangement of a germacranolide precursor. Isotopic labelling of anthecotuloide has now been achieved by feeding [1-(13)C]-glucose, [U-13C6]-glucose and [6,6-(2)H2]-glucose to aseptically grown plantlets of Anthemis cotula(family Asteraceae). Analysis of labelling patterns and absolute 13C abundances using quantitative 13C NMR spectroscopy showed that the isoprene building blocks of this sesquiterpene are formed exclusively via the MEP terpene biosynthetic pathway. This was supported by results from an experiment using [U-13C6]-glucose. A deuterium labelling experiment using [6,6-(2)H2]-glucose supported the original proposal and showed that anthecotuloide is formed from a non FPP precursor. Isotope ratio mass spectrometry suggested that there were two pathways for sesquiterpene biosynthesis in A. cotula.     

Synthesis and conformational evaluation of p-tert-butylthiacalix[4]arene-crowns

Bridging of p-tert-butylthiacalix[4]arene afforded 1,3-dihydroxythiacalix[4]arene-monocrown-5 (3b), 1,2-alternate thiacalix[4]arene-biscrown-4 and -5 (4a,b), and 1,3-alternate thiacalix[4]arene-biscrown-5 and -6 (5a,b), depending on the metal carbonates and oligoethylene glycol ditosylates used. Starting from 1,3-dialkylated thiacalix[4]arenes, the corresponding bridging reaction gave 1,3-alternate, partial-cone, and cone conformers 10-19, depending on the substituents present. Temperature-dependent studies revealed that the conformationally flexible 1,3-dimethoxythiacalix[4]arene-crowns 10a-c exclusively occupy the 1,3-alternate conformation. Demethylation exclusively gave the cone 1,3-dihydroxythiacalix[4]arene-crowns (3a,c), which could not be obtained by direct bridging of thiacalix[4]arene. The different structures were assigned on the basis of several X-ray crystal structures and extensive 2-D (1)H NMR studies.     

Sequential isomerization and ring-closing metathesis: masked styryl and vinyloxyaryl groups for the synthesis of benzo-fused heterocycles

The use of an aryl allyl ether and an arylallyl group as masked vinyl ether and 1-propenylphenyl groups for ring-closing metathesis (RCM) leading to the synthesis of benzo-fused heterocycles was demonstrated by using a ruthenium-mediated isomerization followed by a ruthenium-mediated RCM reaction. This resulted in the syntheses of a variety of products including two substituted benzo[1,4]dioxins, a naphtho[2,3-b][1,4]dioxin, a 2H-chromene and a benzo[b]furan.     

End-evaporation dynamics revisited

We present analytical results on the so-called end-evaporation kinetics in equilibrium polymeric systems following a temperature jump (T jump). A T jump prepares the system with a nonequilibrium length distribution, after which it relaxes back to its equilibrium state. Starting from a master equation, we develop a mean-field analytical theory based on a generating function approach, which allows explicit approximate expressions for the monomer and dimer concentrations to be derived in a discrete setting; the concentrations of the other chains as well as the average chain length were shown to be entirely expressible in terms of the monomer and dimer concentrations. We find that the calculated monomer and dimer concentrations as well as the average chain length are in good agreement with numerical simulation results and do not suffer from some of the defects of earlier continuum theories. Furthermore, the relaxation was shown to take place in three different stages. The first stage comprises the very fast relaxation of the monomers to almost their equilibrium concentration; the other polymer chains have hardly relaxed. During the second stage, which is highly nonlinear, a redistribution of material at practically constant monomer density takes place. Only in the final stage of the relaxation process the chain concentrations approach their true equilibrium values. In this stage there are only very small shifts in the concentrations of chains, which are governed by extremely slow "indirect" monomer-mediated processes.