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At least 469 records · Page 26Linked to original sources
PubMed2005

Synthesis and supramolecular properties of molecular clips with anthracene sidewalls.

Novel molecular clips with anthracene sidewalls (1 a-c) were synthesized; they form stable host-guest complexes with a variety of electron-deficient aromatic and quinoid molecules. According to single-crystal structure analyses of clip 1 c and 1,2,4,5-tetracyanobenzene (TCNB) complex 14@1 b, the clips' anthracene sidewalls have to be compressed substantially during the complex formation to provide attractive pi-pi interactions between the aromatic guest molecule and the two anthracene sidewalls in the complex. The compression and expansion of aromatic sidewalls are calculated by molecular mechanics to be low-energy processes, so the energy required for compression of the anthracene sidewalls during complex formation is apparently overcompensated by the gain in energy resulting from the attractive pi-pi interactions. The finding that complexes of the clips 1 a-c are more stable than those of the corresponding clips 2 a-c can be explained in terms of the larger van der Waals contact surfaces of the anthracene sidewalls in 1 a-c (relative to the naphthalene sidewalls in 2 a-c). Color changes resulting from charge-transfer (CT) bands are observed in complex formation by 1 a-c: from colorless to red or purple with TCNB (14), and from yellow to green with 2,4,7-trinitro-9-fluorenone TNF (17). Independently, the host 1 b and guest 14 fluoresce from their respective excited singlet states, whilst in the complex 14@1 b the charge-transfer state quenches the higher-energy singlet states of the two components, and as a result luminescence is only observed from this new CT state. To the best of our knowledge, complex 14@1 b is the first example of CT luminescence from a host-guest complex. The binding constant determined for the formation of the TCNB complex 14@1 b from a UV/Vis titration experiment (Ka = 12 400 m(-1)) agrees well with the value (K(a) = 12 800 m(-1)) obtained by 1H NMR titration.

Anthracenes↗
PubMed2005

Structure and IR spectrum of phenylalanyl-glycyl-glycine tripetide in the gas-phase: IR/UV experiments, ab initio quantum chemical calculations, and molecular dynamic simulations.

We investigated the potential-energy surface (PES) of the phenylalanyl-glycyl-glycine tripeptide in the gas phase by means of IR/UV double-resonance spectroscopy, and quantum chemical and statistical thermodynamic calculations. Experimentally, we observed four conformational structures and we recorded their IR spectra in the spectral region of 3000-4000 cm(-1). Computationally, we investigated the PES by a combination of molecular dynamics/quenching procedures with high-level correlated ab initio calculations. We found that neither empirical potentials nor various DFT functionals provide satisfactory results. On the other hand, the approximative DFT method covering the dispersion energy yields a reliable set of the most stable structures, which we subsequently investigated with an accurate, correlated ab initio treatment. The global minimum contains three moderately strong intramolecular hydrogen bonds and is mainly stabilized by London dispersion forces between the phenyl ring, the carboxylic acid group, and various peptide bonds. A proper description of the last type of interaction requires accurate correlated ab initio calculations, including the complete basis set limit of the MP2 method and CCSD(T) correction terms. Since in our beam experiments the conformations are frozen by cooling from a higher temperature, it is necessary to localize the most stable structures on the free-energy surface rather than on the PES. We used two different procedures (rigid rotor/harmonic oscillator/ideal gas approximation based on ab initio characteristics and evaluation of relative populations from the molecular dynamic simulations using the AMBER potential) and both yield four structures, the global minimum and three local minima. These four structures were among the 15 most energetically stable structures obtained from accurate ab initio optimization. The calculated IR spectra for these four structures agree well with the experimental frequencies, which validates the localization procedure.

Gases↗
PubMed2005

Hydrocarbon oxidation by beta-halogenated dioxoruthenium(VI) porphyrin complexes: effect of reduction potential (RuVI/V) and C-H bond-dissociation energy on rate constants.

beta-Halogenated dioxoruthenium(VI) porphyrin complexes [Ru(VI)(F(28)-tpp)O(2)] [F(28)-tpp=2,3,7,8,12,13, 17,18-octafluoro-5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato(2-)] and [Ru(VI)(beta-Br(8)-tmp)O(2)] [beta-Br(8)-tmp=2,3,7,8,12,13,17,18-octabromo-5,10,15,20- tetrakis(2,4,6-trimethylphenyl)porphyrinato(2-)] were prepared from reactions of [Ru(II)(por)(CO)] [por=porphyrinato(2-)] with m-chloroperoxybenzoic acid in CH(2)Cl(2). Reactions of [Ru(VI)(por)O(2)] with excess PPh(3) in CH(2)Cl(2) gave [Ru(II)(F(20)-tpp)(PPh(3))(2)] [F(20)-tpp=5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato(2-)] and [Ru(II)(F(28)-tpp)(PPh(3))(2)]. The structures of [Ru(II)(por)(CO)(H(2)O)] and [Ru(II)(por)(PPh(3))(2)] (por=F(20)-tpp, F(28)-tpp) were determined by X-ray crystallography, revealing the effect of beta-fluorination of the porphyrin ligand on the coordination of axial ligands to ruthenium atom. The X-ray crystal structure of [Ru(VI)(F(20)-tpp)O(2)] shows a Ru=O bond length of 1.718(3) A. Electrochemical reduction of [Ru(VI)(por)O(2)] (Ru(VI) to Ru(V)) is irreversible or quasi-reversible, with the E(p,c)(Ru(VI/V)) spanning -0.31 to -1.15 V versus Cp(2)Fe(+/0). Kinetic studies were performed for the reactions of various [Ru(VI)(por)O(2)], including [Ru(VI)(F(28)-tpp)O(2)] and [Ru(VI)(beta-Br(8)-tmp)O(2)], with para-substituted styrenes p-X-C(6)H(4)CH=CH(2) (X=H, F, Cl, Me, MeO), cis- and trans-beta-methylstyrene, cyclohexene, norbornene, ethylbenzene, cumene, 9,10-dihydroanthracene, xanthene, and fluorene. The second-order rate constants (k(2)) obtained for the hydrocarbon oxidations by [Ru(VI)(F(28)-tpp)O(2)] are up to 28-fold larger than by [Ru(VI)(F(20)-tpp)O(2)]. Dual-parameter Hammett correlation implies that the styrene oxidation by [Ru(VI)(F(28)-tpp)O(2)] should involve rate-limiting generation of a benzylic radical intermediate, and the spin delocalization effect is more important than the polar effect. The k(2) values for the oxidation of styrene and ethylbenzene by [Ru(VI)(por)O(2)] increase with E(p,c)(Ru(VI/V)), and there is a linear correlation between log k(2) and E(p,c)(Ru(VI/V)). The small slope (approximately 2 V(-1)) of the log k(2) versus E(p,c)(Ru(VI/V)) plot suggests that the extent of charge transfer is small in the rate-determining step of the hydrocarbon oxidations. The rate constants correlate well with the C-H bond dissociation energies, in favor of a hydrogen-atom abstraction mechanism.

Crystallography, X-Ray↗
PubMed2006

Macropodumines A-C: novel pentacyclic alkaloids with an unusual skeleton or zwitterion moiety from Daphniphyllum macropodum Miq.

Three novel alkaloids, macropodumines A-C (1-3), were isolated from the stem of Daphniphyllum macropodum Miq. Interestingly, the structure of macropodumine A (1) was characterized as having a fused pentacyclic system including an unusual eleven-membered macrolactone ring, whereas macropodumine B (2) contains a rare cyclopentadienyl carbanion, which is stabilized as a zwitterion by an internal iminium cation. The structures of these new metabolites were established on the basis of their detailed spectroscopic analysis. In particular, the unique structure of zwitterion 2 was further confirmed by using single-crystal X-ray diffraction analysis.

Alkaloids↗
PubMed2006

Host-guest chemistry of copper(II)-histidine complexes encaged in zeolite Y.

Structural analysis has been carried out on copper(II)-histidine (Cu(2+)/His) complexes after immobilization in the pore system of the zeolites NaY and de-aluminated NaY (DAY). The aim of this study was to determine the geometrical structure of Cu(2+)/His complexes after encaging, to obtain insight into both the effect of the zeolite matrix on the molecular structure and redox properties of the immobilized complexes. In addition to N(2) physisorption and X-ray fluorescence (XRF) analyses, a combination of UV/Vis/NIR, ESR, X-ray absorption (EXAFS and XANES), IR, and Raman spectroscopy was used to obtain complementary information on both the first coordination shell of the copper ion and the orientation of the coordinating His ligands. It was demonstrated that two complexes (A and B) are formed, of which the absolute and relative abundance depends on the Cu(2+)/His concentration in the ion-exchange solution and on the Si/Al ratio of the zeolite material. In complex A, one His ligand coordinates in a tridentate facial-like manner through N(am), N(im), and O(c), a fourth position being occupied by an oxygen atom from a zeolite Brønsted site. In complex B, two His ligands coordinate as bidentate ligands; one histamine-like (N(am), N(im)) and the other one glycine-like (N(am), O(c)). In particular the geometrical structure of complex A differs from the preferred structure of Cu(2+)/His complexes in aqueous solutions; this fact implies that the zeolite host material actively participates in the coordination and orientation of the guest molecules. The tendency for complex A to undergo reduction in inert atmosphere to Cu(1+) (as revealed by dynamic XANES studies) suggests activation of complex A by the interaction with the zeolite material. EXAFS analysis confirms the formation of a distorted four coordinate geometry of complex A, suggesting that the combination of zeolite and one His ligand force the Cu(2+) complex into an activated, entactic state.

Copper↗
PubMed2006

Electron transfer in nonpolar solvents in fullerodendrimers with peripheral ferrocene units.

Two new fullerodendrimers, with two and four ferrocene units on their periphery, have been synthesized by 1,3-dipolar cycloaddition reactions between the corresponding azomethine ylides and C(60). These new compounds have been studied by using cyclic voltammetry and UV/Vis spectroscopy. Weak intramolecular interactions between the fullerene cage and the ferrocene groups have been found. The photochemical events of both fullerene-ferrocene dendrimers have been probed by means of steady-state and time-resolved techniques. The steady-state emission intensities of the fulleropyrrolidine-ferrocene dendrimers 1 and 2 were found to be quenched relative to the N-methylfulleropyrrolidine without substituents that was used as a model. The nanosecond transient absorption spectral studies revealed efficient charge separation in both systems, even in toluene. The lifetimes of the (C(60))(*-)-(dendron)(*+) are higher for the second-generation fullerodendrimer (with four ferrocene units) and they are of the order of tens of nanoseconds in toluene and hundreds of nanoseconds in polar solvents.

Cyclization↗
PubMed1980

Synthesis and pharmacological activity of three new 9-aryl-8-azaadenine derivatives.

This paper describes the synthesis of three new 9-aryl-8-azaadenine derivatives (Ic, d, e) and of some related compounds, using the appropriate 1-substituted-5-amino triazoles (IV) as starting material. The new azaadenines were subjected to pharmacological screening and the carboxylic compound (I c) showed an interesting antiallergic activity, depending on the presence of the free acid function.

Adenine↗
PubMed1980

Synthesis and pharmacological activity of some 9-aryl-8-azapurine derivatives.

Because of the biological interest of 8-azaanologous of purine bases, the preparation of some 8-azapurines (IV) and (V), substituted in 9 position with aryl groups, is described. Compounds were obtained by closure of a pyrimidine nucleus on performed 5-amino-1,2,3-triazole derivatives. Some substances, subjected to pharmacological screening, showed an interesting antiallergic activity.

Animals↗
PubMed2000

Phenolic compounds from Eucalyptus maculata.

From the chloroformic extract of the resinous exudate of the stems of Eucalyptus maculata, four phenolic constituents have been isolated. A new di-cinnamic acid glucose ester was isolated, in addition to cinnamic acid, 7-methyl aromadendrin and sakuranetin. The isolated compounds were elucidated using UV, IR, 1D and 2D NMR and MS.

Chromatography, Thin Layer↗
PubMed2004

Analgesic, antiinflammatory and CNS depressant activities of sesquiterpenes and a flavonoid glycoside from Polygonum viscosum.

Analgesic, antiinflammatory and CNS depressant activities of four sesquiterpenes, viscosumic acid, viscozulenic acid, viscoazucine and viscoazulone, and a flavonoid glycoside, quercetin-3-O-(6''-feruloyl)-beta-D-galactopyranoside isolated form the aerial parts of Polygonum viscosum (Polygonaceae) have been assessed. All test compounds exhibited CNS depressant activity in open field test, all but viscoazulone showed analgesic activity in Eddy's hot plate test, all sesquiterpenes inhibited acetic acid induced abdominal writhing in mice, and all but viscoazucine and the flavonoid glycoside exhibited mild to moderate antiinflammatory effect on carrageenan induced rat paw edema.

Acetic Acid↗
PubMed2006

Synthesis of a new series of 4-aryl-1,4-dihydropyridines with calcium channel blocking and vasodilatory activity.

Synthesis of a new series of 4-aryl-1,4-dihydropyridines possessing potential calcium channel blocking activity along with good vasodilatory profile is reported. The compounds were synthesized using modified Hantzsch condensation of various aldehydes with methyl 3-aminocrotonate in the presence of a catalytic amount of trifluoroacetic acid and subsequent alkylation with various hydrochlorides of dialkylaminoalkyl chlorides. In vitro calcium channel blocking activity has been evaluated in cultures of neonatal rat cortical neurons by measuring the inhibitory response at L-type calcium channels activated by veratridine. Many compounds exhibited moderate to significant calcium channel blockade around 1 microM. The vasodilatory activity was assessed on isolated rat thoracic aortic rings precontracted by phenylephrine/KCl (30 mM). Most of the compounds produced a concentration-dependent inhibition of the contractile response.

Animals↗
PubMed2006

New compounds from Commiphora myrrha (Nees) Engl.

Phytochemical investigation of Commiphora myrrha (Nees) Engl. has afforded six new compounds identified as cadina-3-en-15-ol (myrracadinol A) (1), 7, 8-seco-2, 5-dihydroxy-12-acetoxycalam-8-ene (myrracalamene A) (2), 7, 8-seco-2, 3, 5-hydroxy-12-acetoxycalame-8-ene (myrracalamene B) (3), 7, 8-seco-cadin-3, 8-dien-2beta, 12-diol (myrracadinol B) (4), 7, 8-seco-12-hydroxycalam-8-ene (myrracalamene C) (6), 7, 8-seco-cadin-3,7(12)-dien-5alpha,10alpha-diol (myrracadinol C) (7) along with a known compound tria-cont-1-ene (5). Their structures were elucidated on the basis of spectral and chemical analyses.

Acetylation↗
PubMed1995

Folding of aminosuccinyl peptides: thermodynamic data from temperature dependent circular dichroism measurements.

The conformational equilibrium of aminosuccinyl peptides between extended conformations and an intramolecularly hydrogen bonded type II' beta-turn conformation has been studied on the peptide Boc-L-Asu-Gly-L-Ala-OMe (Asu = aminosuccinyl residue) by means of temperature dependence of circular dichroism spectra. Owing to the peculiar chiroptical and conformational properties of the Asu residue, this technique proved to be very useful for deriving thermodynamic data for the above folding process. The value of delta H0 (-6.6 kJ mol-1), obtained for the peptide studied in a chloroformacetonitrile mixture, shows that the lower energy of the folded conformer is primarily due to the characteristic intramolecular hydrogen bond of the beta turns.

Amino Acid Sequence↗
PubMed1976

Lipid oxidation. Part 3. Oxidation of egg phosphatidylethanolamine.

Phosphatidylamine isolated from egg yolk phospholipids was autoxidized at 60 degrees C. Oxidation products were separated by thin layer chromatography on silica gel and by column chromatography of DEAE-cellulose. The fractions were characterized by UV and IR spectra and by chemical analysis. Polyunsaturated fatty acids were destroyed during the oxidation, the content of primary amino groups decreased and imine derivatives appeared.

Chromatography, DEAE-Cellulose↗