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991.
The kinetics of the oxidation of promazine and chlorpromazine by hexaimidazolcobalt(III) were studied in the presence of a
large excess of cobalt(III) and H+ ions using u.v.–vis. spectroscopy ([CoIII] = (1–6) × 10−3 m, [ptz] = (2.5–10) × 10−5 m, [H+] = 0.05–0.8 m, I = 1.0 m (H+, Na+, Cl−), T = 333–353 K, l = 1 cm). In each case, the reversible reaction leads to formation of cobalt(II) species and a stable cationic radical. A
linear dependence of the pseudo-first-order rate constant (kobs) on [CoIII] with a non-zero intercept was established for both phenothiazine derivatives. A marked difference in the observed reaction
rate for promazine and chlorpromazine is associated with the difference in its ability to undergo oxidation and is consistent
with a trend in the redox potential changes for these reductants. The activation parameters for reactions studied were determined.
Mechanistic consequences of all the results are discussed. 相似文献
992.
Krzysztof Winkler Alan L. Balch Włodzimierz Kutner 《Journal of Solid State Electrochemistry》2006,10(10):761-784
The recent results of investigations involving the electrochemical formation of polymers containing fullerenes and studies of their properties and applications are critically reviewed. From a structural point of view, these polymers can be divided into four main categories including (1) polymers with fullerenes physically incorporated into the foreign polymeric network without forming covalent bonds, (2) fullerene homopolymers formed via [2+2] cycloaddition, (3) “pearl necklace” polymers with fullerenes mutually linked covalently to form polymer chains, and (4) “charm bracelet” polymers containing pendant fullerene substituents. The methods of electrochemical polymerization of these systems are described and assessed. The structural features and properties of the electrochemically prepared polymers and their chemically synthesized analogs are compared. Polymer films containing fullerenes are electroactive in the negative potential range due to electroreduction of the fullerene moieties. Related films made with fullerenes derivatized with electron-donating moieties as building blocks are electroactive in both the negative and positive potential range. These can be regarded as “double cables” as they exhibit both p- and n-doping properties. Fullerene-based polymers may find numerous applications. For instance, they can be used as charge-storage and energy-converting materials for batteries and photoactive units of photovoltaic cell devices, respectively. They can be also used as substrates for electrochemical sensors and biosensors. Films of the C60/Pt and C60/Pd polymers containing metallic nano-particles of platinum and palladium, respectively, effectively catalyze the hydrogenation of olefins and acetylenes. Laser ablation of electrochemically formed C60/M and C70/M polymer films (M=Pt or Ir) results in fragmentation of the fullerenes leading to the formation of hetero-fullerenes, such as [C59M]+ and [C69M]+.Dedicated to Professor Dr. Alan M. Bond on the occasion of his 60th birthday. 相似文献
993.
The
reaction of ilmenite titanium raw material with sulphuric acid was investigated
in ‘hazard’ type calorimetric system. The investigations show
the essential influence of initial temperature, particle size distribution
and concentration of sulphuric acid on rate and heat power of reaction and
determine the limits of safety of the process and also its efficiency. 相似文献
994.
Piotr Król Bożena Król Stanisław Pikus Maciej Kozak 《Colloid and polymer science》2006,285(2):169-175
Small angle X-ray scattering and differential scanning calorimetry methods were employed to characterise the internal order of structural phases present in polyurethane coatings obtained as a result of water evaporation from anionomer dispersions. Those anionomers were produced in the reaction of aromatic, cycloaliphatic and aliphatic diisocyanates with polyoxyethylene glycol, 2,2-bis-(hydroxymethyl)propionic acid and 1,6-hexamethylenediamine. The decisive effects were found from ionic and polar structures within the rigid urethane and urea segments on the ordered arrangement degree of the supermolecular structures in the obtained anionomers. That becomes apparent in differential scanning calorimetry thermograms and contributes to improved thermal stability of the produced polyurethane coatings. 相似文献
995.
P. Staszczuk M. Błachnio E. Kowalska D. Sternik 《Journal of Thermal Analysis and Calorimetry》2006,86(1):51-56
Calculations based on the fractal geometry in the estimation of surface
heterogeneity are superior compared with conventional calculation methods
(e.g. from the data of gas adsorption or X-ray radiation scattering) as they
can be applied without limitation as far as the range of surface sizes of
the studied structures is concerned. This paper presents structural characteristics
of carbon and carbon- free nanomaterials based on the determined surface and
volumetric fractal coefficients. Fractal coefficients were determined from
the data obtained by means of two independent methods: sorptometry and atomic
force microscopy (AFM). Correlation between porosity parameters and fractal
coefficients is presented. 相似文献
996.
Pryjomska I Bartosz-Bechowski H Ciunik Z Trzeciak AM Ziółkowski JJ 《Dalton transactions (Cambridge, England : 2003)》2006,(1):213-220
The new phosphinite and phosphonite complexes (1-8) are very efficient catalysts for the methoxycarbonylation of iodobenzene and Heck cross-coupling of bromobenzene with butyl acrylate. High catalytic activity of these complexes can be explained by their in situ transformations during the reaction, stimulated by the presence of water, acid (HCl) or base (NEt(3)). Hydrolysis of phosphinite palladium complexes of the form trans-PdCl(2)[PPh(2)(OR)](2) (R = C(6)F(5), 2, (t)Bu 3, or O-menthyl 4) results in the formation of the dimeric complex [mu-ClPd(PPh(2)OH)(PPh(2)O)](2) 5, which is deprotonated by NEt(3), producing a polymeric complex of formula [Pd(P(O)PPh(2))(2)](n) 8. The reverse reaction, protonolysis of 8 with HCl, leads back to 5 and the monomeric complex 5a. The phosphinite complex PdCl(2)[PPh(2)(OBu)](2)1 with a more lipophilic ligand, PPh(2)(OBu), does not undergo hydrolysis under the same conditions. In the reaction of PdCl(2)(cod) with P(OPh)(2)(OH), the new dimer [mu-ClPd(P(OPh)(2)OH)(P(OPh)(2)O)](2) 6 was obtained, whereas reaction of Pd(OAc)(2) with P(OPh)(2)(OH) leads to the polymeric complex [Pd[P(O)(OPh)(2)](2)](n) 7. Protonolysis of 7 with HCl results in the formation of 6. 相似文献
997.
We consider a model for adsorption of a simple fluid in disordered polydisperse adsorbents. The fluid consists of hard sphere particles. On the other hand, the adsorbents of this study are modeled as a collection of hard spheres with their diameter obeying a certain distribution function. Our focus is in the evaluation of the chemical potential of the fluid immersed in such a polydisperse material. It permits us to obtain porosity and pore size distribution for the adsorbent, as well as a set of adsorption isotherms. The latter have been calculated theoretically and by grand canonical Monte Carlo simulations. We observe that the width of assumed polydispersity distribution affects all the properties of the system. Nevertheless, the effect of matrix packing is dominant in determining adsorption for this class of models. We are convinced that the matrix structures generated via more sophisticated algorithms would exhibit stronger effects of polydispersity on the entire set of properties of adsorbed simple fluids. 相似文献
998.
The enantiomers of some amino acids have been separated on commercial chiral TLC plates in reversed-phase mode. The effect
of the pH* of the aqueous-organic mobile phase on the retention and mobility of the enantiomers and on selectivity was investigated.
It was shown that for most of the amino acids investigated the highest enantioselectivity was obtained at pH* 3–4 or 6–7.
The drift and disturbance of the baseline on the chromatograms were also much smaller at pH* 3–4 and 6–7. 相似文献
999.
Małgorzata Pazderska-Szabłowicz Agnieszka Białkowska Ewa Kita 《Transition Metal Chemistry》2006,31(3):413-420
New chromium(III) complexes, [Cr(C2O4)2(2-hnic)]2− and [Cr(C2O4)2(3-hpic)]2− (where 2-hnic = O,O′-bonded 2-hydroxynicotinic acid and 3-hpic = N,O-bonded 3-hydroxypicolinic acid), were obtained and characterized
in solution. The acid-catalyzed aquation of the both complexes leads to liberation of the appropriate pyridinecarboxylic acid
and formation of cis-[Cr(C2O4)2(H2O)2]−. Kinetics of these reactions were studied spectrophotometrically in the 0.1–1.0 M HClO4 range, at I = 1.0 M. In the case of [Cr(C2O4)2(2-hnic)]2−, a slow chelate-ring opening at the Cr–O (phenolate) bond is followed by a fast Cr–O (carboxylate) bond breaking. The rate
law: kobs = kHQH[H+] was established, where kH is the acid-catalyzed rate constant and QH is the protonation constant of the coordinated phenolate oxygen atom. In the case of [Cr(C2O4)2(3-hpic)]2−, the reversible chelate-ring opening at Cr–N bond is followed by the rate determining step – the one-end bonded ligand liberation.
The rate law for the first step was determined: kobs = k1+k−1/Q1[H+], where k1 and k−1 are the rate constants of the chelate-ring opening and closure and Q1 is the protonation constant of the pyridine nitrogen atom. The aquation mechanisms are proposed and the effect of ligand
coordination mode on complex reactivity is discussed. 相似文献
1000.
Marek Daszkiewicz Zbigniew Staszak Adam Pietraszko Wiesława Bronowska Maria Cieślak-Golonka 《Structural chemistry》2006,17(6):599-608
Two polymeric complexes: catena(μ-CrO4-O,O′)[Co(HIm)3H2O] (1) and catena(μ-CrO4-O,O′)[Co0.43Ni0.57(HIm)3H2O] (2) (where HIm=imidazole) with a cis-bridging coordination mode of the CrO4
2− anion have been synthesized and characterized by X-ray and spectroscopic methods. These crystals were isolated from nine
systems of varying reagent molar ratios and three excluding anions: Cl−, NO3
− and SO4
2− exclusively as mer [M(HIm)3O3]-type isomers. The unit cell of these isostructural complexes (monoclinic crystal system P21
/n) contains two independent helixes, left- and right handed, stabilized by intrahelical and interhelical hydrogen bonding and
π–π interaction between pairs of the imidazole rings from neighbouring helixes. The Raman spectra at 77 K of 1 and 2 deconvoluted into lorentzian components revealed the block-type polymeric structure of the complexes. Moreover, the solution
studies at millimolar concentrations of 1 and 2 indicated their complete decomposition in water. Four K electronic spectral analysis of the crystals (band deconvolution
into gaussian components) enhanced with the data obtained in the polarized light allowed for assignment of the bands to the
respective d–d transition (D4h symmetry). It was found that the metallic centres are independently absorbing species, which supports the suggestion of a
block-type structure of the polymers. The respective crystal field parameters for Co and Ni were calculated. 相似文献