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61.
Danuta Slawinska Janusz Slawinski Krzysztof Polewski Wojciech Pukacki 《Photochemistry and photobiology》1979,30(1):71-80
Abstract— Peroxidation of tannins with alkaline H2 O2 is accompanied by weak chemiluminescence in the spectral region 480–800 nm. o-Di and tri-hydroxy groups of polyphenols undergo oxidation by a free-radical mechanism and a green intermediate anion-radical with absorption Δmax = 600 nm is formed. The radical mechanism is supported by the low activation energy 14–20 kJ/mol and the quenching effect of radical scavengers. The reaction of the green intermediate with peroxy anions is the chemiluminescence rate limiting step. In the presence of a-hydroxy-methylperoxide formed from H2 O2 and formaldehyde, the alkaline peroxidation of tannins is accompanied by strong red luminescence (420–800 nm). The base catalyzed decomposition of peroxides gives only a weak red emission (460–800 nm). Light intensity is enhanced in D2 O by a factor 6.5. Quenchers of O2 (1 Δg ) and 1,3-di-phenylisobenzofurane diminish light intensity in non-aqueous solutions. The data suggest 1 O2 participation in the observed chemiluminescence. Thermo-chemical calculations give —ΔH values from 250–1000 kJ/mol for one elementary reaction step which limits the mechanism of chemi-enereization. Chemiexcitation of tannins is relevant to biochemical mechanisms of aerobic degradation of aromatic compounds, energy utilization as well as to defense and resistance processes in plants. 相似文献
62.
Janusz Moskal 《Tetrahedron》1984,40(21):4447-4453
Highly substituted 1,Δ-diazabutadienes react with aroyl isothiocyanates in a 1,3-dipolar cycloaddition node yielding five-membered thiohydantoin-type heterocycles. The cycloaddition is accompanied by 1,4 shift of hydrogen from a methyl group attached to C2 of the 1,C-diazabutadiene moiety. The mechanism of this reaction is discussed in comparison with similar cycloadditions with aryl isocyanates. 相似文献
63.
The Na[Cr(PDA)2] · 2H2O complex (PDA1 = dipicolinic acid anion) and its aquation product, [Cr(PDA)(H2O)3]+, were prepared and characterized. The electronic spectra demonstrate that the bis(dipicolinato) complex undergoes very fast partial dechelation during dissolution. In acidic media, pH controlled, rapid protolytic and ring opening processes lead to coexistence of complexes with one tridentate (PDA) and the other bi- or mono-dentate (PDA). The kinetics of PDA ligand liberation were followed spectrophotometrically within the 0.1–2.0 M HClO4 range at I = 2.0 M. The observed first-order rate constant depends on [H+] according to the equation: k
obs = A[H+]/(1 + B[H+] + C[H+]2). A reaction course via the uncharged [Cr(PDA)(HPDA)(H2O)2]0 complex is proposed. The observed rate increase, followed by rate retardation with [H+] increase, is attributed to the unreactive [Cr(PDA)(H2PDA)(H2O)2]+ complex. In terms of the proposed mechanism, A, B, C parameters have been defined as: A = k
1
Q
1, B = Q
1, C = Q
1
Q
2 where k
1 is the rate constant of the CrIII-carboxylato oxygen bond-breaking in the monodentate HPDA ligand, Q
1 is a composite value describing protolytic and dechelation processes and Q
2 is the protonation constant of the uncharged [Cr(PDA)(HPDA)(H2O)2]0 complex. 相似文献
64.
The enantioselective addition of allylstannanes and allylsilanes to alkyl glyoxylates of type 1, catalyzed by chiral (salen)Cr(III) complexes 3, has been studied. We have found that the reaction proceeded smoothly for low loading (1-2 mol %) of (1R,2R)-(salen)Cr(III)BF43a or (1R,2R)-(salen)Cr(III)ClO43c, and allyltributyltin under simple, undemanding conditions, affording (R)-2-hydroxypent-4-enoic acid esters 2 in good yield (61-90%) and enantioselectivity (58-76% ee). 相似文献
65.
E. Kozlowski E. Siekowska-Zyskowska T. Górecki 《Fresenius' Journal of Analytical Chemistry》1992,342(1-2):20-25
Summary The theoretical basis of the optimization of the TLHS analysis has been further developed. A critical value of the enrichment factor (Fcr, inf) has been defined as the value, at which the relative systematic error and the relative precision error are equal. These errors have been defined with respect to the maximum and the inflexion point of the recovery curve of the volatile analyte in the liquid sorbent. Two methods of volatile organic halogen (VOX) determination in tap water, viz. the conductometric and the indirect potentiometric method, have been compared (with respect to their analytical characteristics) using natural samples. The accuracy of both methods proved to be similar, yet the conductometric method was more precise. The variances of the methods occurred to be homogeneous in the particular measuring series independently of the long time intervals between the particular measuring series and the differentiated VOX levels.Part IV see [4] 相似文献
66.
Janusz Matkowski 《Aequationes Mathematicae》1992,43(2-3):219-224
Summary In the present note we prove that every functionf: (0, ) [0, ) satisfying the inequalityaf(s) + bf(t) f(as + bt), s, t > 0, for somea andb such that 0 <a < 1 <a + b must be of the formf(t) = f(1)t, (t > 0). This improves our recent result in [2], where the inequality is assumed to hold for alls, t 0, and gives a positive answer to the question raised there.An analogue for functions of several real variables of the above result characterizes concave functions. Conjugate functions and some relations to Hölder's and Minkowski's inequalities are mentioned. 相似文献
67.
Krzysztof Ejsmont Magorzata Broda Andrzej Domaski Janusz B. Kyzio Jacek Zaleski 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(9):o545-o548
The two isomeric compounds 4‐amino‐ONN‐azoxybenzene [or 1‐(4‐aminophenyl)‐2‐phenyldiazene 2‐oxide], i.e. the α isomer, and 4‐amino‐NNO‐azoxybenzene [or 2‐(4‐aminophenyl)‐1‐phenyldiazene 2‐oxide], i.e. the β isomer, both C12H11N3O, crystallized from a polar solvent in orthorhombic space groups, and their crystal and molecular structures have been determined using X‐ray diffraction. There are no significant differences in the bond lengths and valence angles in the two isomers, in comparison with their monoclinic polymorphs. However, the conformations of the molecules are different due to rotation along the Ar—N bonds. In the α isomer, the benzene rings are twisted by 31.5 (2) and 14.4 (2)° towards the plane of the azoxy group; the torsion angles along the Ar—N bond in the β isomer are 24.3 (3) and 23.5 (3)°. Quantum‐mechanical calculations indicate that planar conformations are energetically favourable for both isomers. The N—H?O hydrogen bonds observed in both networks may be responsible for the deformation of these flexible molecules. 相似文献
68.
The full configuration interaction method in the space of fractionally occupied unrestricted natural orbitals (UNO-CAS method)
is extended to excited states as well as to strongly correlated and reactive systems with large active spaces. This is accomplished
by␣using restricted active space (RAS) wave functions introduced by Olsen et al. [(1988) J Chem Phys 89: 2185] and using the
UNOs without the expensive orbital optimization step. In RAS, the space of active orbitals is subdivided into three groups:
a group with essentially doubly occupied orbitals (RAS1), the usual CAS space (RAS2), and a space with weakly occupied active
orbitals (RAS3). We select these spaces on the basis of the occupation numbers of the UNOs. All possible electron distributions
are allowed in the usual CAS space, but the number of vacancies is limited in RAS1 and the number of electrons is limited
in RAS3. We discuss an efficient algorithm for generating a RAS wave function. This is based on the Handy-Knowles determinantal
expansion with an addressing scheme adopted for the restricted expansion. Results for both ground and excited states of azulene
and free base porphyrin are presented.
Received: 16 July 1998 / Accepted: 7 August 1998 / Published online: 19 October 1998 相似文献
69.
Mieczysław Jaroniec Jarosław Ościk Anna Deryło Ryszard Kusak Janusz Czarniecki 《Monatshefte für Chemie / Chemical Monthly》1982,113(1):29-35
An equation for multilayer adsorption from multicomponent liquid mixtures on solid surfaces1 has been examined. For this purpose experimental adsorption data for four alcohols from benzene/n-heptane mixture on silica gel have been measured. Average number of the adsorbed layers, heterogeneity parameter and capacity of the surface phase have been evaluated by using the equation mentioned above.
Mehrschichten-Adsorption von Alkoholen aus Benzol/n-Heptan-Mischung an Silica Gel
Zusammenfassung Eine Gleichung für Mehrschichten-Adsorption an festen Oberflächen1 aus Mehrkomponentenlösungen wurde getestet. Zu diesem Zweck wurden experimentelle Daten für die Adsorption von vier Alkoholen aus Benzol/n-Heptan-Mischung an Silica Gel herangezogen. Der Mittelwert für die Anzahl der Adsorptionsschichten, der Heterogenitätsparameter und die Kapazität der Oberflächenphase wurde aus dieser Gleichung berechnet.相似文献
70.
Valensin D Luczkowski M Mancini FM Legowska A Gaggelli E Valensin G Rolka K Kozlowski H 《Dalton transactions (Cambridge, England : 2003)》2004,(9):1284-1293
Potentiometric and spectroscopic data have shown that octarepeat dimer and tetramer are much more effective ligands for Cu(II) ions than simple octapeptide. Thus, the whole N-terminal segment of prion protein due to cooperative effects, could be more effective in binding of Cu(II) than simple peptides containing a His residue. The gain of the Cu(II) binding by longer octarepeat peptides derives from the involvement of up to four imidazoles in the coordination of the first Cu(II) ion. This type of binding increases the order of the peptide structure, which allows successive metal ions for easier coordination. 相似文献