Ab initio DFT computations reveal that the essential structural and photophysical features of the conjugated π‐electron system of retinal and carotenoids are dictated by “innocent” methyl substituents. These methyl groups shape the conformation and symmetry of the isoprenoid chromophores by causing a sigmoidal distortion of the polyene skeleton and increasing its flexibility, which facilitates fitting to their binding pockets in proteins. Comparison of in vacuo conformations of the chromophores with their native (protein‐bound) conformations showed, surprisingly, that the peripheral groups and interactions with the protein environment are much less significant than the methyl side groups in tuning their structural features. The methyl side groups also contribute to a loss of symmetry elements specific to linear polyenes. In effect, the symmetry‐imposed restrictions on the chromophore electronic properties are disabled, which is of tremendous relevance to their photophysics. This is evidenced by their non‐negligible permanent dipole moments and by the simulated and experimentally measured circular dichroism spectra, which necessarily reflect the chirality of the conjugated π‐electron system. 相似文献
Bacteriochlorophyll (BChl) derivatives (with central Mg replaced by metal "M") ([M]-BChl with M = 2H, Mg, Zn, Pd, Cu) have been investigated for their photodynamic capacity and stability toward photodegradation in organic solvents and aqueous micellar solution. A protocol has been developed for screening new sensitizers. BChl and [Zn]-BChl are efficient sensitizers, but they are also quickly degraded by the reactive oxygen species (ROS) produced by autosensitization, as well as by hetero-sensitization with 17(4)-methyl-13(2)-demethoxycarbonyl-pheophorbide a (MPP). Photostable [Cu]-BChl is a poor sensitizer, whereas [Pd]-BChl and bacteriopheophytin a are not only very efficient sensitizers but are also very stable toward ROS. beta-Carotene is no efficient physical quencher of ROS in the system; rather, it acts as a photochemical quencher that competes with [M]-BChl and undergoes photooxygenation at high rates. Photolability seems to depend on the pigment oxidation potential and, in parallel, on the presence of central metals preferring coordination numbers higher than 4, whereas photodynamic capacity depends on long excited state life-times of the pigment or efficient intersystem crossing (or both). 相似文献
The asymptotic behaviour of entropy numbers of TrudingerStrichartzembeddings of radial Besov spaces on Rn into exponential Orliczspaces is calculated. Estimates of the entropy numbers as wellas estimates of entropy numbers of Sobolev embeddings of radialBesov spaces are applied to spectral theory of certain pseudo-differentialoperators. 相似文献
Summary. Several compounds may exist in LnCl3–MCl mixtures. Those corresponding to the M2LnCl5 and MLn2Cl7 stoichiometries are formed in a few systems only, with diverse stability strongly dependent on both the corresponding lanthanide
and alkali metal. On the other hand, M3LnCl6 that occur in most systems have a far larger stability range and melt congruently. These latter compounds were investigated
in the present work by differential scanning calorimetry and electrical conductivity measurements. The thermodynamic and transport
properties were correlated to structural features and related to the mechanism of compound formation.
Corresponding author. E-mail: Marcelle.Gaune-Escard@polytech.univ-mrs.fr
Received October 2, 2002; accepted November 6, 2002
Published online April 24, 2003
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ID="a" This paper is dedicated to Professor H. Gamsj?ger on the occasion of his birthday 相似文献
Summary The composition and stability of the following biogenic amine complexes have been investigated: 1,4-diaminobutane(Put), 4-azaoctane-1,8-diamine(Spd), 4,9-diazadodecan-1, 12-diamine(Spm) as well as homologues such as 1,3-diaminopropane(Put3), 4-azaheptane-1, 7-diamine(Spd3,3) and 4,8-diazaundecan-1,11-diamine(Spm3,3,3) with H+, Cu(II), Zn(II), Pb(II) and Mg(II). A potentiometric method was used. The VIS technique enabled the determination of coordination mode in copper/amine systems. It was found that Mg(II) does not form coordination compounds with any of the studied polyamines in solution. An increase in the concentration of ligand and metal was found to result in a stronger tendency towards the formation of protonated compounds accompanied by a decrease in the concentration of hydroxocomplexes. At physiologicalpH (7.4) an increase in the concentration of protonated compounds by approximately 15% was observed within the ligand concentration range from 0.001 mol dm–3 to 0.0001 mol dm–3 at a Cu(II) concentration of 0.000177 mol dm–3.
Untersuchungen zur Komplexbildung von Polyaminen mit H+, Cu(II), Zn(II), Pb(II) und Mg(II) in wäßriger Lösung
Zusammenfassung Anhand einer Analyse von potentiometrischen Daten wurden Zusammensetzung und Beständigkeit folgender biogener Aminkomplexe untersucht: 1,4-Diaminobutan(Put), 4-Azaoktan-1,8-diamin(Spd), 4,9-Diazadodekan-1,12-diamin(Spm), sowie auch deren Homologen 1,3-Diaminopropan(Put3), 4-Azaheptan-1,7-diamin(Spd3,3) und 4,8-Diazaundekan-1,11-diamin(Spm3,3,3) mit H+, Cu(II), Zn(II), Pb(II) und Mg(II). Mit Hilfe der VIS-Technik wurde die Koordinationsweise in Kupfer/Amin-Systemen bestimmt. Es wurde festgestellt, daß Mg(II) keine Koordinationsverbindungen mit den untersuchten Polyaminen bildet. Eine höhere Konzentration von Ligand und Metall führte zu stärkerer Tendenz der Bildung protonierter Verbindungen, wobei die Konzentration von Hydroxokomplexen kleiner wurde. Bei physiologischempH (7.4) wurde im Bereich der Ligand-Konzentration von 0.001 mol dm–3 bis 0.0001 mol dm–3 bei einer Cu(II)-Konzentration von 0.000177 mol dm–3 ein Anstieg der Konzentration protonierter Verbindungen um etwa 15% beobachtet.
The Quantitative Property-Retention Relation (QPRR) approach was applied to analyze the correlations between the retention parameters of ampholytic, biologically active substances and their physicochemical (predicted/spectral) characteristics. The retention parameters were obtained for polar and semipolar HPLC columns at various compositions of mobile phases and pH conditions. These values are a unique collection of chromatographic parameters that are a measure of lipophilicity and, consequently, can be very helpful in assessing pharmacological potency of the compounds investigated. Three QPRR models that meet the predictive capability criteria were developed. The relationships can be used to gain pharmacologically interesting information on the biologically active ampholytic substances.
Theoretical models of the interfacial tension coefficient in polymer blends, v12, were evaluated. A new working relation was derived that makes it possible to compute v12 from the chemical structure of two polymers. The calculations involve determination of the dispersive, polar and hydrogen-bonding parts of the solubility parameter from the tabulated group and bond contributions. The computed values of v12 for 46 blends were found to follow the experimental ones with a reasonable scatter of ± 36%. Next, the experimental methods of v12-measurements were critically examined. Although many have been developed for low viscosity Newtonian fluids, most are irrelevant to industrial polymeric systems. For the present studies two were selected. Values of v12 were measured using the so-called “capillary breakup method,” and a newly developed method based on the retraction rate of deformed drop. 相似文献
Normal modes of s-triazine and cyanuric acid were calculated at the DFT(B3LYP)/6-311++G(d,p) level. These modes were analyzed in terms of potential energy distribution (PED), computed using a specially designed set of symmetry coordinates. The normal-mode analysis was described in detail and the PED matrix definition used in the calculations was provided. Particular attention has been devoted to the degenerate vibrations. The experimental infrared spectra of s-triazine and cyanuric acid isolated in low-temperature Ar matrices have been recorded and interpreted by comparison with the theoretically predicted normal modes. In the spectrum of matrix-isolated s-triazine, the IR bands originating from 13C and 15N isotopologues with one of the ring atoms substituted by a rare isotope were detected. These bands were identified thanks to the excellent agreement between the experimentally observed and theoretically predicted isotope shifts. 相似文献