WorldWideScience

Sample records for azulene

  1. Comparative study of electron conduction in azulene and naphthalene

    Indian Academy of Sciences (India)

    Sudipta Dutta; S Lakshmi; Swapan K Pati

    2008-06-01

    We have studied the feasibility of electron conduction in azulene molecule and compared with that in its isomer naphthalene. We have used non-equilibrium Green’s function formalism to measure the current in our systems as a response of the external electric field. Parallely we have performed the Gaussian calculations with electric field in the same bias window to observe the impact of external bias on the wave functions of the systems. We have found that the conduction of azulene is higher than that of naphthalene inspite of its intrinsic donor–acceptor property, which leads a system to more insulating state. Due to stabilization through charge transfer the azulene system can be fabricated as a very effective molecular wire. Our calculations show the possibility of huge device application of azulene in nano-scale instruments.

  2. Energy-dependent collisional deactivation of vibrationally excited azulene

    International Nuclear Information System (INIS)

    Collisional energy transfer parameters for highly vibrationally excited azulene have been deduced from new infrared fluorescence (IRF) emission lifetime data with an improved calibration relating IRF intensity to vibrational energy [J. Shi, D. Bernfeld, and J. R. Barker, J. Chem. Phys. 88, XXXX (1988), preceding paper]. In addition, data from previous experiments [M. J. Rossi, J. R. Pladziewicz, and J. R. Barker, J. Chem. Phys. 78, 6695 (1983)] have been reanalyzed based on the improved calibration. Inversion of the IRF decay curves produced plots of energy decay, which were analyzed to determine , the average energy transferred per collision. Master equation simulations reproduced both the original IRF decays and the deduced energy decays. A third (simple) method of determination agrees well with the other two. The results show to be nearly directly proportional to the vibrational energy of the excited azulene from ∼8000 to 33 000 cm-1. At high energies, there are indications that the energy dependence may be slightly reduced

  3. Energy transfer in aggregates of bacteriochlorophyll c self-assembled with azulene derivatives.

    Science.gov (United States)

    Matěnová, Martina; Lorelei Horhoiu, Viviana; Dang, Florian-Xuan; Pospíšil, Petr; Alster, Jan; Burda, Jaroslav V; Balaban, Teodor Silviu; Pšenčík, Jakub

    2014-08-21

    Bacteriochlorophyll (BChl) c is the main light-harvesting pigment of certain photosynthetic bacteria. It is found in the form of self-assembled aggregates in the so-called chlorosomes. Here we report the results of co-aggregation experiments of BChl c with azulene and its tailored derivatives. We have performed spectroscopic and quantum chemical characterization of the azulenes, followed by self-assembly experiments. The results show that only azulenes with sufficient hydrophobicity are able to induce aggregation of BChl c. Interestingly, only azulene derivatives possessing a conjugated phenyl ring were capable of efficient (∼50%) excitation energy transfer to BChl molecules. These aggregates represent an artificial light-harvesting complex with enhanced absorption between 220 and 350 nm compared to aggregates of pure BChl c. The results provide insight into the principles of self-assembly of BChl aggregates and suggest an important role of the π-π interactions in efficient energy transfer. PMID:24999619

  4. Lowest energy vibrational modes of some naphthalene derivatives: Azulene, quinoline, isoquinoline - Experiment and theory

    Science.gov (United States)

    Martin-Drumel, M. A.; Pirali, O.; Loquais, Y.; Falvo, C.; Bréchignac, Ph.

    2013-02-01

    Far infrared (FIR) gas phase absorption spectra of azulene, quinoline and isoquinoline have been recorded using a Fourier transform Bruker IFS125 interferometer at medium resolution (0.5 cm-1). Assignments of these weak vibrational bands were performed using density-functional theory calculations carried out at the harmonic and anharmonic levels. Agreement between observed and calculated band positions is better than 5% for azulene and 1% for quinoline and isoquinoline. The relative band intensities are also correctly predicted. Molecular structure dependence of the FIR spectra is discussed based on the comparative study of three selected FIR modes.

  5. Toward Singlet-Triplet Bistable Nonalternant Kekulé Hydrocarbons: Azulene-to-Naphthalene Rearrangement.

    Science.gov (United States)

    Das, Soumyajit; Wu, Jishan

    2015-12-01

    Recent developments of open-shell singlet diradicaloids motivated the search for stable singlet-triplet bistable nonalternant polycyclic hydrocarbons. During the synthesis of this type of molecule, such as the dibenzo-cyclohepta[def]fluorene 3, an unexpected azulene-to-naphthalene rearrangement was observed at room temperature, which resulted in new nonalternant hydrocarbons 8a/8b with a closed-shell singlet ground state. These studies provided insight into the unique chemistry of azulene and challenges for the synthesis of singlet-triplet bistable polycyclic hydrocarbons. PMID:26569547

  6. Highly substituted azulene dyes as multifunctional NLO and electron-transfer compounds.

    Science.gov (United States)

    Lambert, Christoph; Nöll, Gilbert; Zabel, Manfred; Hampel, Frank; Schmälzlin, Elmar; Bräuchle, Christoph; Meerholz, Klaus

    2003-09-01

    Two highly substituted azulene derivatives were synthesised by Pd-mediated dimerisation from the corresponding tolan species. One azulene derivative (2) has donor functionalities (dianisylaminophenyl and dianisylamino) in the 1-, 2-, 3- and 6-positions, while the other (1) has donors (dianisylaminophenyl) in the 2- and 6-positions and acceptors (nitrophenyl) in the 1- and 3-positions. Each azulene derivative shows strong bond length alternation in the solid state, determined by X-ray crystal analysis, and an intense CT band around 450-500 nm in its UV/Vis spectrum. The first-order hyperpolarisability of 1 and of 2 was measured by hyper-Rayleigh scattering and is about that of disperse red DR1. Both azulene derivatives show multiple oxidation processes. The intramolecular adiabatic ET behaviour of the mixed valence radical cations of 1 and of 2 was investigated by UV/Vis/NIR spectroelectrochemistry. The intervalence-CT band of 1(+) could be analysed by the Generalised Mulliken-Hush theory, which yields an electronic coupling V=1140 cm(-1) for the optically induced adiabatic hole transfer. PMID:12953208

  7. Crystal structure of 1-iodo-3-{[4-(tert-butylsulfanylphenyl]ethynyl}azulene

    Directory of Open Access Journals (Sweden)

    Sebastian Förster

    2015-08-01

    Full Text Available The title compound, C20H19IS, features a 1,3-disubstituted azulene involving an ethynylene elongated 4-(tert-butylsulfanylphenyl sidearm and an iodine atom as the substituents. The azulene ring system is almost planar (r.m.s. deviation = 0.012 Å and subtends a dihedral angle of 35.7 (1° with the benzene ring. As a result of the inherent dipole character of the azulene core, a supramolecular π–π dimer [separation between the centroids of the five- and seven-membered rings = 3.7632 (10 Å] with antiparallel orientated molecules can be observed in the crystal. The packing is consolidated by an unusual I...π(acetylene contact [I...Cg = 3.34 Å, C—I...Cg = 173.3°], and a very weak C—H...π interaction is also found in the structure, with the azulene five-membered ring as the acceptor.

  8. Large negative hyperpolariza-bilities (b) of the protonated Schiff bases of the azulenic retinal analogues

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The molecular first hyperpolarizabilities (b) and electronic properties of some azulenic retinal analogues and their derivatives have been investigated theoretically by employing semiempirical approaches. The results indicate that the protonated Schiff bases (PSB) of the 2-substituted azulenic retinal analogues possess extremely large negative b values and very good transparency. These can be attributed to the large difference between the ground state dipole moment and the first excited state dipole moment according to the electronic property analysis. The characteristic blue- shifted absorption in polar solvents of the 2-substituted PSB chromophores can be well explained by the negative solvato-chromic effects. The largest calculated |mb | value can reach the magnitude of 10-44 esu, which is close to the highest re-ported values of synthesized chromophores.

  9. Crystal structure of diethyl 2-amino-6-[(thiophen-3-ylethynyl]azulene-1,3-dicarboxylate

    Directory of Open Access Journals (Sweden)

    Sebastian Förster

    2015-03-01

    Full Text Available The title compound, C22H19NO4S, has an almost planar geometry supported by intramolecular N—H...O and C—H...O hydrogen bonds. The thiophene ring is inclined to the azulene ring by 4.85 (16°, while the ethoxycarbonyl groups are inclined to the azulene ring by 7.0 (2 and 5.7 (2°. In the crystal, molecules are linked by pairs of N—H...O hydrogen bonds, forming inversion dimers with an R22(12 ring motif. The dimers are linked via C—H...π interactions, forming sheets parallel to (10-1.

  10. Anti-UV Activity of Newly-synthesized Water-soluble Azulenes

    OpenAIRE

    植木, 淳一; 坂上, 宏; 若林, 英嗣

    2013-01-01

    Background: We have previously reported that azulene-related compounds can protect cells from UV-induced cytotoxicity. However, due to their high water insolubility, their anti-UV activity could not be accurately determined. In the present study, we newly-synthesized a total of nine derivatives with higher water solubility, and re-investigated their anti-UV activity. Materials and Methods: Cytotoxicity of these compounds against three human normal oral and three human oral cells squamous cell...

  11. The photofragmentation of naphthalene and azulene monocations in the energy range 7 22 eV

    Science.gov (United States)

    Jochims, H. W.; Rasekh, H.; Rühl, E.; Baumgärtel, H.; Leach, S.

    1992-12-01

    Photoion mass spectrometry was used to study the fragmentation of naphthalene and azulene monocations over the excitation energy range 7-22 eV. Fifteen fragmentation processes in naphthalene and twelve in azulene have been examined in detail. The photoionization mass spectra at 20.58 eV are quasi-identical for the two isomers. This, and the constant value of the difference between the fragment appearance energies (AE) for naphthalene and azulene, equal to the difference in the heats of formations of the neutral parents, suggest that identical products are formed. The unimolecular dissociations fall mainly into (i) a "low energy" group, (AE 18 eV). The reactions in (i) have in common the bicyclic precursor C 10H +8 ion 18 which decays via rupture of one ring. The group (ii) reactions involve rupture of both rings to give an open chain precursor, the 1,6-bis-ethinyl-hexatriene radical cation 20. Thermodynamic and mechanistic arguments are given to propose specific reaction pathways and product structures. Two general schemes rationalize the low-energy and high-energy ionic decompositions.

  12. Theoretical studies on the one- and two-photon absorption properties of azulenylporphyrins and azulene-fused porphyrins

    Institute of Scientific and Technical Information of China (English)

    Li Wen-Chao; Feng Ji-Kang; Ren Ai-Min; Zhang Xiang-Biao; Sun Jia-Zhong

    2009-01-01

    The electronic structures, one-photon absorption (OPA) and two-photon absorption (TPA) properties of the azulenylporphyrins and azulene-fused porphyrins have been comparatively studied by using DFT/B3LYP/6-31G(d)and the ZINDO/SDCI method. With the number of azulenyl groups increasing, the OPA wavelengths of all molecules are red-shifted in 400-600 nm and the two-photon absorption cross section is gradually enlarged. The azulene-fused structures facilitate an expanding conjugated area and increasing TPA cross section. The origin of TPA properties of studied compounds is studied with a two-level model. In summary, the azulene-fused porphyrins exhibit strong two-photon absorption.

  13. CONVERGENT SYNTHESIS AND EVALUATION OF 18F-LABELED AZULENIC COX2 PROBES FOR CANCER IMAGING

    Directory of Open Access Journals (Sweden)

    Donald D. Nolting

    2013-01-01

    Full Text Available The overall objectives of this research are to (i develop azulene-based PET probes and (ii image COX2 as a potential biomarker of breast cancer. Several lines of research have demonstrated that COX2 is overexpressed in breast cancer and that its presence correlates with poor prognoses. While other studies have reported that COX2 inhibition can be modulated and used beneficially as a chemopreventive strategy in cancer, no viable mechanism for achieving that approach has yet been developed. This shortfall could be circumvented through in vivo imaging of COX2 activity, particularly using sensitive imaging techniques such as PET. Toward that goal, our laboratory focuses on the development of novel 18F-labled COX2 probes. We began the synthesis of the probes by transforming tropolone into a lactone, which was subjected to an [8+2] cycloaddition reaction to yield 2-methylazulene as the core ring of the probe. After exploring numerous synthetic routes, the final target molecule and precursor PET compounds were prepared successfully using convergent synthesis. Conventional 18F labeling methods caused precursor decomposition, which prompted us to hypothesize that the acidic protons of the methylene moiety between the azulene and thiazole rings were readily abstracted by a strong base such as potassium carbonate. Ultimately, this caused the precursors to disintegrate. This observation was supported after successfully using an 18F labeling strategy that employed a much milder phosphate buffer. The 18F-labeled COX2 probe was tested in a breast cancer xenograft mouse model. The data obtained via successive whole-body PET/CT scans indicated probe accumulation and retention in the tumor. Overall, the probe was stable in vivo and no defluorination was observed. A biodistribution study and Western blot analysis corroborate with the imaging data. In conclusion, this novel COX2 PET probe was shown to be a promising agent for cancer imaging and deserves further

  14. Electrosynthesis and characterization of poly(2-[(E)-2-azulen-1-ylvinyl] thiophene) using polyazulene as model compound

    International Nuclear Information System (INIS)

    Electrochemical polymerization of azulene and 2-[(E)-2-azulen-1-ylvinyl] thiophene has been studied in this work. Characterization of the formed films was done by cyclic voltammetry (CV), in situ UV-vis absorption spectroscopy and by scanning electron microscopy (SEM). Polymerization was performed by CV in a three-electrode electrochemical cell in 0.1 M tetrabutylammonium hexafluorophosphate-acetonitrile (TBAPF6-ACN) within two different potential ranges. The redox behavior of the films was studied by CV in monomer-free TBAPF6-ACN electrolyte solution. The electrochemical response from the anodic charging (p-doping) in the different films consisted of symmetric and well-resolved redox peaks. During electrochemical doping changes in the UV-vis spectra can be seen due to transformation of the films from the neutral into the doped form. Poly(2-[(E)-2-azulen-1-ylvinyl] thiophene), in particular shows a very broad absorbance spectrum starting at 300 nm extending to 900 nm. Morphologies of the electrosynthesized films were studied by SEM

  15. The dynamics of azulene in liquids and compressed gases on ultrafast timescales

    Energy Technology Data Exchange (ETDEWEB)

    Schultz, K.E.

    1992-02-01

    The ultrafast dynamics of vibrationally hot ground state azulene molecules have been time resolved by picosecond transient absorption spectroscopy in a variety of solvents including hexane, chloromethanes, methanol, CClF{sub 3}, Xe and Kr. A high pressure optical cell was used to liquify gases for use as solvents and change their density and temperature, independently, over the entire liquid density range. Experimental results indicate the vibrational cooling rate is strongly solvent dependent, with cooling rates of approximately 20 psec in molecular solvents and approximately 150 psec in atomic solvents. Comparison of the rates in Xe and Kr at constant density demonstrates the strong effect of solvent mass on energy transfer. The effect of solvent temperature on vibrational cooling is minimal, as is the effect of solvent density. This latter result is quite surprising in light of earlier experiments on simpler molecular systems, such as I{sub 2} in Xe. This anomalous density effect is examined in light of Isolated Binary Collision (IBC) theory and bulk thermal transport models. Both theories accurately model all experimental results obtained with the exception of the density effort. Possible explanations for the breakdown of the IBC theory in this case are offered along with methods to improve IBC theory for application to complex three dimensional molecular systems.

  16. The dynamics of azulene in liquids and compressed gases on ultrafast time scales

    International Nuclear Information System (INIS)

    The ultrafast dynamics of vibrationally hot ground state azulene molecules have been time resolved by picosecond transient absorption spectroscopy in a variety of solvents including hexane, chloromethanes, methanol, CClF3, Xe and Kr. A high pressure optical cell was used to liquify gases for use as solvents and change their density and temperature, independently, over the entire liquid density range. Experimental results indicate that the vibrational cooling rate is strongly solvent dependent, with cooling rates of approximately 20 psec in molecular solvents and approximately 150 psec in atomic solvents. Comparison of the rates in Xe and Kr at constant density demonstrates the strong effect of solvent mass on energy transfer. The effect of solvent temperature on vibrational cooling is minimal, as is the effect of solvent density. This latter result is quite surprising in light of earlier experiments on simpler molecular systems, such as I2 in Xe. This anomalous density effect is examined in light of Isolated Binary Collision (IBC) theory and bulk thermal transport models. Both theories accurately model all experimental results obtained with the exception of the density effect. Possible explanations for the breakdown of IBC theory in this case are offered along with methods to improve IBC theory for application to complex three dimensional molecular systems

  17. Synthesis of carboranes containing an azulene framework and in vitro evaluation as boron carriers.

    Science.gov (United States)

    Nakamura, H; Sekido, M; Yamamoto, Y

    1997-08-29

    3-(o-Carboranylhydroxymethyl)-7-isopropylazulene sodium carboxylate (1) and 3-(o-carboranylmethyl)-7-isopropylazulene sodium sulfonate (2) were synthesized from the palladium-catalyzed addition reaction of 1-carboranyltributylstannane (4) to azulene aldehydes (3 and 9). Although the water solubility of 1 was of the order of 10(-6) M, that of 2 was of the order of 10(-3) M and was enough for clinical use. The cytotoxicity of 1 (IC50) toward B-16 melanoma cells was of the order of 10(-5) M, whereas that of 2 was of the order of 10(-4) M. This value was close to that of BPA (approximately 9 x 10(-3) M) which is utilized for clinical use. The boron uptake by B-16 cells was 0.17 microgram of B/10(6) cells for 1 and 0.25 microgram of B/10(6) cells for 2. It is clear that compound 2 accumulates in B-16 melanoma cells with a significantly high level although it is highly water soluble and its cytotoxicity is significantly low. PMID:9288164

  18. The far-infrared spectrum of azulene and isoquinoline and supporting anharmonic density functional theory calculations to high resolution spectroscopy of polycyclic aromatic hydrocarbons and derivatives

    Science.gov (United States)

    Goubet, Manuel; Pirali, Olivier

    2014-01-01

    In the laboratory, the acquisition and analysis of the rotationally resolved spectra of large molecular systems remain challenging. We report in this paper the rotational analysis of the ν30-GS band of azulene and the ν41-GS band of isoquinoline recorded with synchrotron-based Fourier transform absorption spectroscopy in the far-IR. As a support to rotational analyses, we employed a method based on standard density functional theory calculations performed at the anharmonic level which accurately reproduced the rotational constants of 28 vibrational states of 16 Polycyclic Aromatic Hydrocarbons (PAHs) and aza-derivatives. This method appears as an invaluable support for the spectral assignment of the very congested rotational structures of the infrared bands of PAH species and should be very helpful in the active search of these molecules in space through their pure rotational or rovibrational spectra.

  19. Benchmark theoretical study of the ionization energies, electron affinities and singlet–triplet energy gaps of azulene, phenanthrene, pyrene, chrysene and perylene

    International Nuclear Information System (INIS)

    Highlights: ► Electronic properties of aromatic hydrocarbons are computed at benchmark levels. ► Electron correlation has a very strong influence on the computed results. ► The role of structural relaxation and zero-point vibrations is highlighted. ► We approach chemical accuracy, using the principles of a focal point analysis. -- Abstract: The vertical and adiabatic singlet–triplet energy gaps, electron affinities and ionization energies of azulene, phenanthrene, pyrene, chrysene, and perylene are computed by applying the principles of a focal point analysis onto a series of single-point calculations at the level of Hartree–Fock theory, second-, third-, and fourth-order Møller–Plesset perturbation theory, as well as coupled cluster theory including single, double and perturbative triple excitations, in conjunction with correlation consistent basis sets of improving quality. Results are supplemented with an extrapolation to the limit of an asymptotically complete basis set. According to our best estimates, azulene, phenanthrene, pyrene, chrysene, and perylene exhibit adiabatic singlet–triplet energy gaps of 1.79, 2.92, 2.22, 2.79 and 1.71 eV, respectively. In the same order, the corresponding adiabatic electron affinities (EAs) amount to 0.71, −0.08, −0.40, 0.24, and 0.87 eV, whereas benchmark values equal to 7.43, 8.01, 7.48, 7.66 and 7.15 eV, are found for the adiabatic ionization energies.

  20. 糖を側鎖に持つAzulene誘導体の合成

    OpenAIRE

    杉本, 佑太; Sugimoto, Yuta

    2007-01-01

    Introduction of sugar side chains to azulene derivatives would raise physiological activities of azulenes. Thus, synthetic approaches to these derivatives were explored. Reaction of 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide(TAGB) with azulene carboxylic acids derived from 3-formylguaiazulene by modified Reformatsky or aldol condensation reactions at room temperature afforded the corresponding azulene glycosyl esters in good yields. Deprotection of the 6-O-trityl group of 1,2,3,4-O-tet...

  1. 13b,13c-Di-2-pyridyl-5,7,12,13b,13c,14-hexahydro-6H,13H-5a,6a,12a,13a-tetraazabenz[5,6]azuleno[2,1,8-ija]benz[f]azulene-6,13-dione methanol hemisolvate

    Directory of Open Access Journals (Sweden)

    Lin Li

    2008-01-01

    Full Text Available The title compound, C30H24N6O2·0.5CH3OH, a glycoluril derivative with two pyridine substituents on the convex face of the glycoluril system, is an important intermediate for the synthesis of more complex glycoluril derivatives. The compound crystallizes with two independent molecules in the asymmetric unit, one of which exhibits disorder of one benzene ring over two orientations with refined site occupancy factors 0.65 (4:0.35 (4. The crystal structure contains several short C—H...O contacts, and the methanol molecule forms an O—H...O hydrogen bond to one of the glycoluril molecules.

  2. Activation energies of photoinduced unimolecular, bimolecular and termolecular processes on silica gel surfaces.

    Science.gov (United States)

    Williams, Siân L; Worrall, David R; Kirkpatrick, Iain; Vancea, Anisoara; Pan, Jiawei

    2011-01-01

    Activation energies for energy and electron transfer have been measured in various systems on silica gel. In the case of ion-electron recombination, a facile technique involving fluorescence recovery is described which complements diffuse reflectance spectroscopy in the study of these systems. In bimolecular anthracene/azulene systems, activation energies have been shown to be independent of pre-treatment temperature in the range 25-210 °C, demonstrating that physisorbed water plays little role in determining diffusion rates on silica gel. In a ternary anthracene/azulene/perylene system, we have for the first time presented comparative activation energies for the diffusion of azulene and its radical cation, and have shown a greater activation energy for diffusion of the latter species. PMID:20978659

  3. New Synthetic Method of Azuleno[1,2-c]thiophenes

    Institute of Scientific and Technical Information of China (English)

    WANG,Bing; WANG,Dao-Lin; IMAFUKU,Kimiakic

    2004-01-01

    @@ On the viewpoints of physical and chemical properties and biological activities, syntheses of a variety of heterocycle-fused azulenes have been repoted.[1] Of them, thiophene-fused azulenes were prepared by using different types of stating materials as follows. Azuleno[2,1-b] thiophenes are readily obtained from the reactions of 2-chloroazulene derivatives with ethyl mercaptoacetate in a few steps in good yield by Matsui[2] and Yamane.[3] On the other hand, the first synthesis of azuleno[1,2-c]thiophenes was accomplished by the reaction of 3-methoxycarbonyl-2H-cyclohepta[b]furan2-one with morpholino enamine of 3-oxotetrahydro-thiophene followed by dehydrogenation in poor yield by Fujimori.

  4. Absolute Configuration Determination of Azulenyl Diols Isolated From Asymmetric Pinacol Coupling.

    Science.gov (United States)

    Dragu, Eugenia Andreea; Naubron, Jean-Valere; Hanganu, Anamaria; Razus, Alexandru C; Nica, Simona

    2015-11-01

    A convenient enantioselective approach for the pinacol coupling of 1-acetylazulene involving easily accessible (R)- or (S)-BINOLs as chiral additive is reported. This supposes the preformation of the chiral titanium-BINOL complex in 1:2 ratio and subsequent reduction with zinc when, 2,3-di(azulen-1-yl)butane-2,3-diol can be isolated in around 60% enantiomeric excess. The absolute configuration of the isolated enantiomers was assigned by comparison of the experimental and Boltzmann-weighted calculated VCD and ECD spectra and assigned as (+)-(2S;3S)-di(azulen-1-yl)butane-2,3-diol. Chirality 27:826-834, 2015. © 2015 Wiley Periodicals, Inc. PMID:26364568

  5. New bioactive hydrogenated linderazulene-derivatives from the gorgonian Echinogorgia complexa

    Digital Repository Service at National Institute of Oceanography (India)

    Manzo, E.; Ciavatta, M.L.; Gresa, M.P.L.; Gavagnin, M.; Villani, G.; Naik, C.G.; Cimino, G.

    -1 New Bioactive Hydrogenated Linderazulene-Derivatives from the Gorgonian Echinogorgia complexa Emiliano Manzo,a* Maria Letizia Ciavatta,a Maria Pilar Lopez Gresa,b Margherita Gavagnin,a Guido Villani,a Chandrakant Govind Naikc and Guido Ciminoa...; E-mail: emanzo@icmib.na.cnr.it Azulene sesquiterpenes are typical secondary metabolites of marine octocorals of the order Gorgonacea.1-11 Most of them are responsible of the brilliant colors of gorgonians and in addition various bioactivities...

  6. A facile synthesis of sodium 3-[1-[sup 14]C]-ethyl-7-isopropyl-1-azulenesulfonate

    Energy Technology Data Exchange (ETDEWEB)

    Shimada, Takeshi; Yanagisawa, Takashi; Tomiyama, Tsuyoshi (Kotobuki Pharmaceutical Co. Ltd., Nagano (Japan). Research Labs.); Okazaki, Mitsuo (Shinshu Univ., Nagano (Japan). Dept. of Applied Biology)

    1994-01-01

    Sodium 3-ethyl-7-isopropyl-1-azulenesulfonate 1, a new therapeutic agent for stomatitis, pharyngitis and ophthalmia was labelled with carbon-14 in the ethyl group attached to the azulene ring for use in metabolic studies. [sup 14]C-labelled 1 with a specific activity of 1.98 GBq/mmol was prepared in four steps in 39.3% overall chemical yield from [1-[sup 14]C]acetic acid sodium salt. (Author).

  7. 無溶媒Ugi反応によるアズレンアミド類の合成

    OpenAIRE

    熊倉, 健太; KUMAKURA, Kenta

    2014-01-01

    A simple and eco-friendly synthesis of azulene amide derivatives has achieved via solvent-free Ugireaction. We found that efficient solvent-free reactions required the formation of a liquid phase throughoutthe course of the reactions. In this context, we developed effective Ugi reaction utilizing previously preparedimines. Furthermore, we also found that under the optimized condition the reaction proceeded selectivelyjust mixing four-components (aldehydes, amines, carboxylic acids, and 3-isoc...

  8. Pharmacological Potential of Matricaria recutita-A Review

    OpenAIRE

    Vikas Gupta; Payal Mittal; Parveen Bansal; SUKHBIR L. KHOKRA; Dhirender Kaushik

    2010-01-01

    Matricaria recutita, once it has been called as Marticaria chamomilla, Chamomilla recutita, and Chamomilum nobile family Asteraceae. The main constituents of this plant include the terpenoids α-bisabolol and its oxides and azulenes, including chamazulene. Matricaria recutita shows different pharmacological activities like anti-inflammatory, anti- cancer, treatment of stress and depression, anti-allergic etc. This review focuses on the detailed chemical constituents, pharmacological activities...

  9. Pharmacological Potential of Matricaria recutita-A Review

    Directory of Open Access Journals (Sweden)

    Vikas Gupta

    2010-01-01

    Full Text Available Matricaria recutita, once it has been called as Marticaria chamomilla, Chamomilla recutita, and Chamomilum nobile family Asteraceae. The main constituents of this plant include the terpenoids α-bisabolol and its oxides and azulenes, including chamazulene. Matricaria recutita shows different pharmacological activities like anti-inflammatory, anti- cancer, treatment of stress and depression, anti-allergic etc. This review focuses on the detailed chemical constituents, pharmacological activities of different parts of this plant.

  10. Physico-chemical investigation of some areas of fundamental significance to biophysics. Annual report, 1978-1979

    International Nuclear Information System (INIS)

    Work in progress includes: analyzing the lowest-energy Rydberg transitions of the alkyl halides; decomposition of a spectroscopic signal S into a system of bands; luminescence of aqueous systems; a study of the effects of small molecules on hydrogen bonding via glass transitions in ethanol; Rydberg/intravalence mixing in the S2 state of azulene; ultraviolet photoelectron spectroscopy of carbonyls; and multi-photon processes

  11. Detecting CO, NO and NO2 gases by Boron-doped graphene nanoribbon molecular devices

    Science.gov (United States)

    Xie, Zhen; Zuo, Xi; Zhang, Guang-Ping; Li, Zong-Liang; Wang, Chuan-Kui

    2016-07-01

    Combining nonequilibrium Green's function method and density functional theory, an azulene-like dipole molecule sandwiched between two graphene nanoribbon (GNR) electrodes are explored to gas sensors. Both the pristine zigzag edged GNR and Boron-doped armchair-edged GNR are considered in this study. It shows that certain specific toxic molecules CO, NO and NO2 would adsorb on the doped Boron atoms of the GNR, resulting in a dramatic change in the current-voltage profile. Changes in the subbands of electrodes, induced by gas adsorption, are responsible for the variation of current. The devices are thus demonstrated to be sensitive nanosensors for these toxic gases.

  12. Study of reduction methods for irradiation on oral mucositis. The examination of reduction methods for mucosal failure

    International Nuclear Information System (INIS)

    Reduction methods for irradiation on oral mucosa examined concerning in acute phase of the carbon ion radiotherapy for head and neck malignancies. We enforced a mechanical teeth and gingival cleaning as an Oral hearth care and gargled a polaprezinc with sodium alginate, and azulene- lidocaine with glycerin sodium as a oral linces before radiation. The response of the mucosal failure was reduced compare with no care group. In this Result, we considered that oral hearth care for prevention of infection, and mucosa protection by the drug was important factor. (author)

  13. Analgesic and anti-inflammatory activities of the sesquiterpene fraction from Annona reticulata L. bark.

    Science.gov (United States)

    Chavan, Machindra J; Wakte, Pravin S; Shinde, Devanand B

    2012-01-01

    The sesquiterpene fraction of Annona reticulata bark was studied by GC/MS. Three major components were identified: copaene (35.40%), patchoulane (13.49%) and 1H-cycloprop(e)azulene (22.77%). The fraction was also screened for its analgesic and anti-inflammatory activities. The sesquiterpene fraction at doses 12.5 and 25 mg kg⁻¹ and the unsaponified petroleum ether extract at a dose of 50 mg kg⁻¹ exhibited significant central as well as peripheral analgesic and anti-inflammatory activities. These activities were comparable with the standard drugs used in the respective experiments. PMID:22007723

  14. Searching the Hearts of Graphene-like Molecules for Simplicity, Sensitivity, and Logic.

    Science.gov (United States)

    Sangtarash, Sara; Huang, Cancan; Sadeghi, Hatef; Sorohhov, Gleb; Hauser, Jürg; Wandlowski, Thomas; Hong, Wenjing; Decurtins, Silvio; Liu, Shi-Xia; Lambert, Colin J

    2015-09-01

    If quantum interference patterns in the hearts of polycyclic aromatic hydrocarbons could be isolated and manipulated, then a significant step toward realizing the potential of single-molecule electronics would be achieved. Here we demonstrate experimentally and theoretically that a simple, parameter-free, analytic theory of interference patterns evaluated at the mid-point of the HOMO-LUMO gap (referred to as M-functions) correctly predicts conductance ratios of molecules with pyrene, naphthalene, anthracene, anthanthrene, or azulene hearts. M-functions provide new design strategies for identifying molecules with phase-coherent logic functions and enhancing the sensitivity of molecular-scale interferometers. PMID:26288219

  15. Silicon-Initiated Carbonylative Carbotricyclization and [2+2+2+1] Cycloaddition of Enediynes Catalyzed by Rhodium Complexes

    OpenAIRE

    Bennacer, Bibia; Fujiwara, Masaki; Lee, Seung-Yub; Ojima, Iwao

    2005-01-01

    The reaction of dodec-11-ene-1,6-diynes or their heteroatom congeners with a hydrosilane catalyzed by Rh(acac)(CO)2 at ambient temperature and pressure of CO gives the corresponding fused 5-7-5 tricylclic products, 5-oxo-1,3a,4,5,7,9-hexahydro-3H-cyclopenta[e]azulenes or their heteroatom congeners, in excellent yields through a unique silicon-initiated cascade carbonylative carbotricyclization (CO-SiCaT) process. It has also been found that the 5-7-5 fused tricyclic products can be obtained f...

  16. Hydrocarbon structure in primary tar of Kansk-Achinsk brown coal

    Energy Technology Data Exchange (ETDEWEB)

    Platonov, V.V.; Klyavina, O.A.; Kasimtseva, T.V.; Ivleva, L.N.; Tabolenko, N.V.; Mazurov, V.V.

    1987-07-01

    Develops method for separating primary hydrocarbons from low temperature carbonization tar of Berezovsk brown coal in conditions which exclude high-temperature pyrolysis of vapor-gas products, and makes it possible to isolate concentrates of triterpanes, steranes, azulenes, flavonoids and terpenes. Compounds obtained were analyzed using infrared and ultraviolet spectroscopy, chromoto-mass-spectrometry, spectral, emissive and functional analysis, cryoscopy, thin-layer and capillary chromatography. Characteristics of eluates obtained are given. Assumes that cellular polyamantine structure together with long polymethylene and isoprene bonds play an important role in maintaining bituminous-waxy complex in brown coal. 15 refs.

  17. Palladium(II), Ruthenium(II), and Ruthenium(III) Complexes of 23-Thiaazuliporphyrin: The Case of Coordination-Induced Contraction.

    Science.gov (United States)

    Białek, Michał J; Latos-Grażyński, Lechosław

    2016-02-15

    5,10,15,20-Tetraaryl-23-thiaazuliporphyrin (SAz) was synthesized starting from nonfunctionalized azulene using a "1 + 3" method to be applied as a monoanionic macrocyclic ligand that provides a peculiar [CNSN] coordination cavity. An insertion of palladium(II) afforded the cationic [Pd(II)(SAz)](+), which readily undergoes the seven-membered ring contraction to form palladium(II) 23-thiabenzocarbaporphyrin [Pd(SBzC)] providing the first example of metal azuliporphyrinoid contraction. A reaction of SAz and a ruthenium source ([RuCl2(CO)3]2, [RuCl2(p-cymene)]2, or [RuCl2(cod)]) yielded ruthenium(II) 23-thiaazuliporphyrin [Ru(II)(SAz)Cl(CO)]. As shown by X-ray crystallography the thiophene ring in [Ru(SAz)Cl(CO)] is sharply tilted out of the plane of the two pyrrole nitrogen and carbon atoms being bound to the ruthenium through the pyramidal sulfur in the η(1) fashion. In solution, as demonstrated by variable-temperature (1)H NMR investigations, [Ru(SAz)Cl(CO)] exists as an equilibrium mixture of two isomers that are differentiated by the direction of thiophene folding (toward or outward of the axial chloride ligand). Apart of [Ru(II)(SAz)Cl(CO)], ruthenium(III) 23-thiaazuliporphyrin [Ru(III)(SAz)Cl2] was obtained when [RuCl2(p-cymene)]2 or [RuCl2(cod)]n were used for insertion. The most characteristic (1)H NMR features of paramagnetic [Ru(SAz)Cl2] are negative isotropic shifts of resonances assigned to meso-aryl, azulene, and pyrrolic hydrogen atoms. The analysis of contact shifts and the parallel density functional theory calculations of spin density distribution documented that in [Ru(SAz)Cl2] the metal ion acquires the dxy(2)(dxzdyz)(3) ground electronic state. This Cs symmetry complex has singly occupied dxz or dyz orbitals that are symmetrically unequivalent. The resulting two different spin density distributions, when merged, reflect the spectroscopic image with the very specific π-spin delocalization, also including the azulene moiety. PMID:26808147

  18. Low-intensity laser coupled with photosensitizer to reduce bacteria in root canals compared to chemical control; Laser em baixa intensidade associado a fotosensibilizador para reducao bacteriana intracanal comparado ao controle quimico

    Energy Technology Data Exchange (ETDEWEB)

    Garcez Segundo, Aguinaldo Silva

    2002-07-01

    The photodynamic therapy is a process in which a dye is associate with an appropriate wavelength of light and this dye goes to an excited state. The excited reacts with oxygen to form the highly reactive compound singlet oxygen, and this compound can kill bacteria and tumor cells. The purpose of this study was to evaluate the bactericidal reduction in root canal contaminated with E. Faecalis. Thirty teeth with their root canals prepared were contaminated with E. faecalis. The teeth have received the chemical substance sodium hypochlorite for 30 minutes; ten teeth have received the azulene dye paste for 5 minutes and have been irradiated with a diode laser, output power 10 mW and {lambda}= 685 nm for 3 minutes. Ten teeth have not received treatment (control group). The bacterial reduction was significantly higher for laser group when compared to chemical and control groups. These results indicate photodynamic therapy as an effective method to kill bacteria. (author)

  19. On-line database of the spectral properties of polycyclic aromatic hydrocarbons

    CERN Document Server

    Malloci, G; Mulas, G; 10.1016/j.chemphys.2007.01.001

    2009-01-01

    We present an on-line database of computed molecular properties for a large sample of polycyclic aromatic hydrocarbons (PAHs) in four charge states: -1, 0, +1, and +2. At present our database includes 40 molecules ranging in size from naphthalene and azulene (C10H8) up to circumovalene (C66H20). We performed our calculations in the framework of the density functional theory (DFT) and the time-dependent DFT to obtain the most relevant molecular parameters needed for astrophysical applications. For each molecule in the sample, our database presents in a uniform way the energetic, rotational, vibrational, and electronic properties. It is freely accessible on the web at http://astrochemistry.ca.astro.it/database/ and http://www.cesr.fr/~joblin/database/.

  20. Palladium-mediated strategies for functionalizing the dihydroazulene photoswitch: paving the way for its exploitation in molecular electronics.

    Science.gov (United States)

    Jevric, Martyn; Broman, Søren Lindbæk; Nielsen, Mogens Brøndsted

    2013-05-01

    The dihydroazulene (DHA)/vinylheptafulvene (VHF) photo/thermoswitch has attracted interest as a molecular switch for advanced materials and molecular electronics. We report here two synthetic approaches using palladium catalysis for synthesizing dihydroazulene (DHA) photoswitches with thioacetate anchoring groups intended for molecular electronics applications. The first methodology involves a Suzuki coupling using tert-butyl thioether protecting groups. Conversion to the thioacetate using boron tribromide/acetyl chloride results in the formation of the product as a mixture of regioisomers mediated by a ring-opening reaction. The second approach circumvents isomerization by the synthesis of stannanes as intermediates and their use in a Stille coupling. Although fully unsaturated azulenes are formed as byproducts during the synthesis of the DHA stannanes, this approach allowed the regioselective incorporation of the thioacetate anchoring group in either one of the two ends (positions 2 or 7) or at both. PMID:23586425

  1. Low-intensity laser coupled with photosensitizer to reduce bacteria in root canals compared to chemical control

    International Nuclear Information System (INIS)

    The photodynamic therapy is a process in which a dye is associate with an appropriate wavelength of light and this dye goes to an excited state. The excited reacts with oxygen to form the highly reactive compound singlet oxygen, and this compound can kill bacteria and tumor cells. The purpose of this study was to evaluate the bactericidal reduction in root canal contaminated with E. Faecalis. Thirty teeth with their root canals prepared were contaminated with E. faecalis. The teeth have received the chemical substance sodium hypochlorite for 30 minutes; ten teeth have received the azulene dye paste for 5 minutes and have been irradiated with a diode laser, output power 10 mW and λ= 685 nm for 3 minutes. Ten teeth have not received treatment (control group). The bacterial reduction was significantly higher for laser group when compared to chemical and control groups. These results indicate photodynamic therapy as an effective method to kill bacteria. (author)

  2. Ab-initio and DFT methodologies for computing hyperpolarizabilities and susceptibilities of highly conjugated organic compounds for nonlinear optical applications

    Science.gov (United States)

    Karakas, A.; Karakaya, M.; Ceylan, Y.; El Kouari, Y.; Taboukhat, S.; Boughaleb, Y.; Sofiani, Z.

    2016-06-01

    In this talk, after a short introduction on the methodologies used for computing dipole polarizability (α), second and third-order hyperpolarizability and susceptibility; the results of theoretical studies performed on density functional theory (DFT) and ab-initio quantum mechanical calculations of nonlinear optical (NLO) properties for a few selected organic compounds and polymers will be explained. The electric dipole moments (μ) and dispersion-free first hyperpolarizabilities (β) for a family of azo-azulenes and a styrylquinolinium dye have been determined by DFT at B3LYP level. To reveal the frequency-dependent NLO behavior, the dynamic α, second hyperpolarizabilities (γ), second (χ(2)) and third-order (χ(3)) susceptibilites have been evaluated using time-dependent HartreeFock (TDHF) procedure. To provide an insight into the third-order NLO phenomena of a series of pyrrolo-tetrathiafulvalene-based molecules and pushpull azobenzene polymers, two-photon absorption (TPA) characterizations have been also investigated by means of TDHF. All computed results of the examined compounds are compared with their previous experimental findings and the measured data for similar structures in the literature. The one-photon absorption (OPA) characterizations of the title molecules have been theoretically obtained by configuration interaction (CI) method. The highest occupied molecular orbitals (HOMO), the lowest unoccupied molecular orbitals (LUMO) and the HOMO-LUMO band gaps have been revealed by DFT at B3LYP level for azo-azulenes, styrylquinolinium dye, push-pull azobenzene polymers and by parametrization method 6 (PM6) for pyrrolo-tetrathiafulvalene-based molecules.

  3. The amino acid-rich elemental diet Elental® preserves lean body mass during chemo- or chemoradiotherapy for esophageal cancer.

    Science.gov (United States)

    Ishikawa, Takeshi; Yasuda, Tomoyo; Doi, Toshifumi; Okayama, Tetsuya; Sakamoto, Naoyuki; Gen, Yasuyuki; Dohi, Osamu; Yoshida, Naohisa; Kamada, Kazuhiro; Uchiyama, Kazuhiko; Handa, Osamu; Takagi, Tomohisa; Konishi, Hideyuki; Yagi, Nobuaki; Kokura, Satoshi; Naito, Yuji; Itoh, Yoshito

    2016-08-01

    Chemo (chemoradio) therapy can induce oral mucositis and change body composition in patients with esophageal cancer. The impact of the amino acid-rich elemental diet Elental® on oral mucositis and changes in body composition during chemo (chemoradio) therapy is unclear. Thus, the purpose of the present study was to examine the preventive effects of Elental on oral mucositis and sarcopenia progression during chemo (chemoradio) therapy for esophageal cancer. Patients were randomized to receive either azulene oral rinse (Arm 1) or Elental (Arm 2) during the treatment cycle (4 weeks). The incidence of oral mucositis and other adverse events was evaluated weekly. Body composition pre- and post-treatment cycle was measured by bioelectric impedance analysis. Thirty‑three patients (17 azulene and 16 Elental) completed the study, and the groups were well matched. Elental tended to reduce the incidence of oral mucositis (Arm 1, 23.5% and Arm 2, 12.5%), but there was no statistically significant difference between the groups. The average body mass index (BMI) and body fat mass decreased significantly in both groups after the treatments. Lean body mass (LBM) was reduced in Arm 1, but was increased in Arm 2 after the treatment; the relative change of LBM after the treatment was significant between Arm 1 and Arm 2 (P=0.007). This study revealed that Elental nutrition could counteract sarcopenia development during chemoradiotherapy for esophageal cancer. These properties may lead to improvement of the quality of life and clinical outcome of esophageal cancer patients treated with chemo (chemoradio) therapy (Clinical Trial Registry ID: UMIN 000007960). PMID:27374272

  4. A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface

    Science.gov (United States)

    Solano, Eduardo A.; Mayer, Paul M.

    2015-09-01

    The fragmentation mechanisms of the naphthalene molecular ion to [M-C4H2]+•, [M-C2H2]+•, [M-H2]+•, and [M-H•]+ were obtained at the UB3LYP/6-311+G(3df,2p)//UB3LYP/6-31G(d) level of theory and were subsequently used to calculate the microcanonical rate constants, k(E)'s, for all the steps by the Rice-Ramsperger-Kassel-Marcus formalism. The pre-equilibrium and steady state approximations were applied on different regions of the potential energy profiles to obtain the fragmentation k(E)'s and calculate the relative abundances of the ions as a function of energy. These results reproduce acceptably well the imaging photoelectron-photoion coincidence spectra of naphthalene, in the photon-energy range 14.0-18.8 eV that was previously reported by our group. Prior to dissociation, the molecular ion rapidly equilibrates with a set of isomers that includes the Z- and E-phenylvinylacetylene (PVA) radical cations. The naphthalene ion is the predominant isomer below 10 eV internal energy, with the other isomers remaining at steady state concentrations. Later on, new steady-state intermediates are formed, such as the azulene and 1-phenyl-butatriene radical cations. The naphthalene ion does not eject an H atom directly but eliminates an H2 molecule in a two-step fragmentation. H• loss occurs instead from the 1-phenyl-butatriene ion. The PVA ions initiate the ejection of diacetylene (C4H2) to yield the benzene radical cation. Acetylene elimination yields the pentalene cation at low energies (where it can account for 45.9%-100.0% of the rate constant of this channel), in a three-step mechanism starting from the azulene ion. However, above 7.6 eV, the major [M-C2H2]+• structure is the phenylacetylene cation.

  5. Can model Hamiltonians describe the electron–electron interaction in π-conjugated systems?: PAH and graphene

    International Nuclear Information System (INIS)

    performance of CI will be checked on small molecules. The electronic structure of azulene and fused azulene will be used to illustrate several aspects of the method. As regards graphene, several questions will be considered: (i) paramagnetic versus antiferromagnetic solutions, (ii) forbidden gap versus dot size, (iii) graphene nano-ribbons, and (iv) optical properties. (topical review)

  6. 吸附-热解吸法与气相色谱-质谱法联用测定蚊香烟雾中的有机化合物%Determination of Organic Compounds in the Smog of Mosquito-Repellent Incense by Adsorption-Thermal Desorption-GC/MS

    Institute of Scientific and Technical Information of China (English)

    刘秀华; 钟志京; 孟丹; 丁兰岚; 田军华

    2012-01-01

    利用吸附-热解吸法与气相色谱-质谱法联用,对两种固体蚊香烟气中的有机成分进行定性和半定量分析.在两种固体蚊香烟气中共检测出52种挥发性成分,包括酚类、醇类、醛类以及脂肪烃和芳香烃等多种化合物,其中的部分化合物对人体有毒害作用.蚊香A烟气中含量较多的成分为右旋烯丙菊酯(30.06%)、1,6-脱水-β-D-吡喃葡萄糖(19.4%)和甘菊环(13.9%)等;蚊香B烟气中含量较多的成分为1,6-脱水-β-D-吡喃葡萄糖(24.4%)、甘菊环(14.4%)和正十四烷(5.91%)等.%The organic components in the smog of mosquito-repellent incense were analyzed qualitatively and semi-quantitatively by adsorption-thermal desorption with gas chromatog-raphy-mass spectrometry. 52 kinds of compounds are identified in two kinds of solid mosquito-repellent incenses, including phenolic compounds, alcohols, aldehydes, aliphatic hydrocarbons, aromatic hydrocarbons and so on. Some compounds are poisonous to people's health. The principal components in the smog of mosquito-repellent incense A are allethrin (30.06%), l,6-Anhydro-β-D-glucopyranose(19. 4%), azulene(13. 9%) , while the principal components are 1,6-Anhydro-β-D-glucopyranose(24. 4%), azulene(14. 4%), tetrade-cane(5. 91%) for the mosquito-repellent incense B.

  7. A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface

    International Nuclear Information System (INIS)

    The fragmentation mechanisms of the naphthalene molecular ion to [M–C4H2]+•, [M–C2H2]+•, [M–H2]+•, and [M–H•]+ were obtained at the UB3LYP/6-311+G(3df,2p)//UB3LYP/6-31G(d) level of theory and were subsequently used to calculate the microcanonical rate constants, k(E)’s, for all the steps by the Rice-Ramsperger-Kassel-Marcus formalism. The pre-equilibrium and steady state approximations were applied on different regions of the potential energy profiles to obtain the fragmentation k(E)’s and calculate the relative abundances of the ions as a function of energy. These results reproduce acceptably well the imaging photoelectron-photoion coincidence spectra of naphthalene, in the photon-energy range 14.0–18.8 eV that was previously reported by our group. Prior to dissociation, the molecular ion rapidly equilibrates with a set of isomers that includes the Z- and E-phenylvinylacetylene (PVA) radical cations. The naphthalene ion is the predominant isomer below 10 eV internal energy, with the other isomers remaining at steady state concentrations. Later on, new steady-state intermediates are formed, such as the azulene and 1-phenyl-butatriene radical cations. The naphthalene ion does not eject an H atom directly but eliminates an H2 molecule in a two-step fragmentation. H• loss occurs instead from the 1-phenyl-butatriene ion. The PVA ions initiate the ejection of diacetylene (C4H2) to yield the benzene radical cation. Acetylene elimination yields the pentalene cation at low energies (where it can account for 45.9%–100.0% of the rate constant of this channel), in a three-step mechanism starting from the azulene ion. However, above 7.6 eV, the major [M–C2H2]+• structure is the phenylacetylene cation

  8. A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface

    Energy Technology Data Exchange (ETDEWEB)

    Solano, Eduardo A.; Mayer, Paul M., E-mail: pmmayer@uottawa.ca [Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 6N5 (Canada)

    2015-09-14

    The fragmentation mechanisms of the naphthalene molecular ion to [M–C{sub 4}H{sub 2}]{sup +•}, [M–C{sub 2}H{sub 2}]{sup +•}, [M–H{sub 2}]{sup +•}, and [M–H{sup •}]{sup +} were obtained at the UB3LYP/6-311+G(3df,2p)//UB3LYP/6-31G(d) level of theory and were subsequently used to calculate the microcanonical rate constants, k(E)’s, for all the steps by the Rice-Ramsperger-Kassel-Marcus formalism. The pre-equilibrium and steady state approximations were applied on different regions of the potential energy profiles to obtain the fragmentation k(E)’s and calculate the relative abundances of the ions as a function of energy. These results reproduce acceptably well the imaging photoelectron-photoion coincidence spectra of naphthalene, in the photon-energy range 14.0–18.8 eV that was previously reported by our group. Prior to dissociation, the molecular ion rapidly equilibrates with a set of isomers that includes the Z- and E-phenylvinylacetylene (PVA) radical cations. The naphthalene ion is the predominant isomer below 10 eV internal energy, with the other isomers remaining at steady state concentrations. Later on, new steady-state intermediates are formed, such as the azulene and 1-phenyl-butatriene radical cations. The naphthalene ion does not eject an H atom directly but eliminates an H{sub 2} molecule in a two-step fragmentation. H{sup •} loss occurs instead from the 1-phenyl-butatriene ion. The PVA ions initiate the ejection of diacetylene (C{sub 4}H{sub 2}) to yield the benzene radical cation. Acetylene elimination yields the pentalene cation at low energies (where it can account for 45.9%–100.0% of the rate constant of this channel), in a three-step mechanism starting from the azulene ion. However, above 7.6 eV, the major [M–C{sub 2}H{sub 2}]{sup +•} structure is the phenylacetylene cation.

  9. Molecular Design of Doped Polymers for Thermoelectric Systems-Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Chabinyc, Michael L. [University of California, Santa Barbara; Hawker, Craig J. [University of California, Santa Barbara

    2013-10-09

    The self-assembly of organic semiconducting molecules and polymers is critical for their electrical properties. This project addressed the design of organic semiconductors with novel synthetic building blocks for proton-dopable conducting materials and the molecular order and microstructure of high performance semiconducting polymers blended with charge transfer dopants. Novel azulene donor-acceptor materials were designed and synthesized with unique electronic effects upon protonation to generate charged species in solution. The microstructure and optical properties of these derivatives were examined to develop structure-property relationships. Studies of the microstructure of blends of charge transfer doped semiconducting polymers revealed highly ordered conductive phases in blends. The molecular packing of one blend was studied in detail using a combination of solid-state NMR and x-ray scattering revealing that dopant incorporation is unlikely to be random as assumed in transport models. Studies of the electrical properties of these highly ordered blends revealed a universal trend between the thermopower and electrical conductivity of semiconducting polymers that is independent of the doping mechanism.

  10. Polaprezinc prevents oral mucositis associated with radiochemotherapy in patients with head and neck cancer.

    Science.gov (United States)

    Watanabe, Tomoko; Ishihara, Masashi; Matsuura, Katsuhiko; Mizuta, Keisuke; Itoh, Yoshinori

    2010-10-15

    Oral mucositis is frequent but serious adverse event associated with radiotherapy or radiochemotherapy in head and neck cancer severely impairs health-related quality of life, leading to poor prognosis due to discontinuation of the therapy. Although a number of compounds have been tested for prophylaxis of oral mucositis, few of them are satisfactory. We investigated the effect of polaprezinc (zinc L-carnosine), a gastric mucosal protective drug, on radiochemotherapy-induced oral mucositis, pain, xerostomia and taste disturbance in patients with head and neck cancer. Patients were randomly assigned to receive polaprezinc (n = 16) or azulene oral rinse as the control (n = 15). The incidence rates of mucositis, pain, xerostomia and taste disturbance were all markedly lower in polaprezinc group than in control. Moreover, the use of analgesics was significantly (p = 0.003) less frequent and the amount of food intake was significantly (p = 0.002) higher in polaprezinc group than in control. On the other hand, tumor response rate in patients with neoadjuvant radiochemotherapy was not significantly affected by polaprezinc, in which the response rate (complete plus partial response) was 88% for polaprezinc and 92% for control (p = 1.000). Therefore, it is highly assumable that polaprezinc is potentially useful for prevention of oral mucositis and improvement of quality of life without reducing the tumor response. PMID:20104529

  11. Comparative study of the effects of photodynamic therapy and conventional therapy on ligature induced peri-implantitis in dogs; Estudo comparativo dos efeitos do laser de baixa potencia associado a fotossensibilizador e terapia convencional em periimplantes induzidas em mandibulas de caes

    Energy Technology Data Exchange (ETDEWEB)

    Hayek, Ricardo Rada Ahmad

    2004-07-01

    Progressive peri-implanter bone losses, which are accompanied by inflammatory process in the soft tissues is referred to as peri-implantitis. The aim of this study was to compare the effects of lethal photosensitisation with the conventional technique on bacterial reduction in ligature induced peri-implantitis in dogs. Seventeen third pre-molars of Labrador dogs were extracted and, immediately after, the implants were submerged. After osteointegration, peri-implantitis was induced. After 4 months, ligature were removed and the same period was waited for natural induction of bacterial plaque. The dogs were randomly divided into two groups. In the conventional group, they were treated with the conventional techniques of mucoperiosteal flaps for scaling the implant surface and irrigate it. In the laser group, only mucoperiosteal scaling was carried out before photodynamic therapy. On the peri-implanter pocket an azulene paste was injected and a GaAlAs low-power laser ({lambda}= 660 nm, P= 30 mW, E= 5,4 J and {delta}t= 3 min.). Microbiological samples were obtained before and immediately after treatment. One implant was removed to be analyzed by scan electron microscopy to verify contamination on the implant surface. The results of this study showed that Prevotella sp., Fusobacterium e S. Beta-haemolyticus were significantly reduced for the conventional and laser groups. (author)

  12. Kinetics of the Self Reaction of Cyclopentadienyl Radicals.

    Science.gov (United States)

    Knyazev, Vadim D; Popov, Konstantin V

    2015-07-16

    The kinetics of the self-reaction of cyclopentadienyl radicals (c-C5H5) was studied by laser photolysis/photoionization mass spectroscopy. Overall rate constants were obtained in direct real-time experiments in the temperature region 304-600 K and at bath gas densities of (3.00-12.0) × 10(16) molecules cm(-3). The room-temperature value of the rate constant, (3.98 ± 0.41) × 10(-10) cm(3) molecule(-1) s(-1), is significantly higher than the rate constants for most hydrocarbon radical-radical reactions and coincides with the estimated collision rate. The observed overall c-C5H5 + c-C5H5 rate constant demonstrates an unprecedented strong negative temperature dependence: k1 = 2.9 × 10(-12) exp(+1489 K/T) cm(3) molecule(-1) s(-1), with estimated uncertainty increasing with temperature, from 13% at 304 to 32% at 600 K. Formation of C10H10 as the primary product of cyclopentadienyl self-reaction was observed. In additional experiments performed at the temperature of 800 K, formation of C10H10, C10H9, and C10H8 was observed. Final product analysis by gas chromatography/mass spectrometry detected two isomers of C10H8 at 800 K: naphthalene (major) and azulene (minor). PMID:25760686

  13. Artemisia arborescens L essential oil loaded beads: preparation and characterization.

    Science.gov (United States)

    Lai, Francesco; Loy, Giuseppe; Manconi, Maria; Manca, Maria Letizia; Fadda, Anna Maria

    2007-01-01

    The purpose of this work was to prepare sodium alginate beads as a device for the controlled release of essential oil for oral administration as an antiviral agent. Different formulations were prepared with sodium alginate as a natural polymer and calcium chloride or glutaraldehyde as a cross-linking agent. Loading capacities of between 86% and 100% were obtained in freshly prepared beads by changing exposure time to the cross-linking agent. Drying of the calcium alginate beads caused only a slight decrease in the loading efficiency. The surface morphology of the different bead formulations were studied using scanning electron microscopy (SEM). Stability studies over a 3-month period showed that glutaraldehyde reacted with some components of Artemisia arborescens L essential oil, changing its composition. Calcium alginate beads showed an in vitro controlled release of the essential oil for the investigated 24 hours, while the use of glutaraldehyde as a cross-linking agent was found not appropriate because of the interactions with azulene derivatives and the low degree of matrix cross-linkage. PMID:17915817

  14. Coulomb pairing resonances in multiple-ring aromatic molecules

    CERN Document Server

    Huber, D L

    2015-01-01

    We present an analysis of the Coulomb pairing resonances observed in photo-double-ionization studies of CnHm aromatic molecules with multiple benzene-like rings. It is applied to naphthalene, anthracene, phenanthrene, pyrene and coronene, all of which have six-member rings, and azulene which is comprised of a five-member and a seven-member ring. There is a high energy resonance at ~ 40 eV that is found in all of the molecules cited and is associated with paired electrons localized on carbon sites on the perimeter of the molecule, each of which having two carbon sites as nearest neighbors. The low energy resonance at 10 eV, which is found only in pyrene and coronene, is attributed to the formation of paired electrons localized on arrays of interior carbon atoms that have the point symmetry of the molecule with each carbon atom having three nearest neighbors. The origin of the anomalous increase in the doubly charged to singly charged parent-ion ratio that is found above the 40 eV resonance in all of the cited ...

  15. Selection of active spaces for multiconfigurational wavefunctions

    International Nuclear Information System (INIS)

    The efficient and accurate description of the electronic structure of strongly correlated systems is still a largely unsolved problem. The usual procedures start with a multiconfigurational (usually a Complete Active Space, CAS) wavefunction which accounts for static correlation and add dynamical correlation by perturbation theory, configuration interaction, or coupled cluster expansion. This procedure requires the correct selection of the active space. Intuitive methods are unreliable for complex systems. The inexpensive black-box unrestricted natural orbital (UNO) criterion postulates that the Unrestricted Hartree-Fock (UHF) charge natural orbitals with fractional occupancy (e.g., between 0.02 and 1.98) constitute the active space. UNOs generally approximate the CAS orbitals so well that the orbital optimization in CAS Self-Consistent Field (CASSCF) may be omitted, resulting in the inexpensive UNO-CAS method. A rigorous testing of the UNO criterion requires comparison with approximate full configuration interaction wavefunctions. This became feasible with the advent of Density Matrix Renormalization Group (DMRG) methods which can approximate highly correlated wavefunctions at affordable cost. We have compared active orbital occupancies in UNO-CAS and CASSCF calculations with DMRG in a number of strongly correlated molecules: compounds of electronegative atoms (F2, ozone, and NO2), polyenes, aromatic molecules (naphthalene, azulene, anthracene, and nitrobenzene), radicals (phenoxy and benzyl), diradicals (o-, m-, and p-benzyne), and transition metal compounds (nickel-acetylene and Cr2). The UNO criterion works well in these cases. Other symmetry breaking solutions, with the possible exception of spatial symmetry, do not appear to be essential to generate the correct active space. In the case of multiple UHF solutions, the natural orbitals of the average UHF density should be used. The problems of the UNO criterion and their potential solutions are discussed

  16. Muscodor albus E-6, an endophyte of Guazuma ulmifolia making volatile antibiotics: isolation, characterization and experimental establishment in the host plant.

    Science.gov (United States)

    Strobel, Gary A; Kluck, Katreena; Hess, Wilford M; Sears, Joe; Ezra, David; Vargas, Percy N

    2007-08-01

    Muscodor albus is an endophytic fungus, represented by a number of isolates from tropical tree and vine species in several of the world's rainforests, that produces volatile organic compounds (VOCs) with antibiotic activity. A new isolate, E-6, of this organism, with unusual biochemical and biological properties, has been obtained from the branches of a mature Guazuma ulmifolia (Sterculiaceae) tree growing in a dry tropical forest in SW Ecuador. This unique organism produces many VOCs not previously observed in other M. albus isolates, including butanoic acid, 2-methyl-; butanoic acid, 3-methyl-; 2-butenal, 2-methyl-; butanoic acid, 3-methylbutyl ester; 3-buten-1-ol, 3-methyl; guaiol; 1-octene, 3-ethyl-; formamide, N-(1-methylpropyl); and certain azulene and naphthalene derivatives. Some compounds usually seen in other M. albus isolates also appeared in the VOCs of isolate E-6, including caryophyllene; phenylethyl alcohol; acetic acid, 2-phenylethyl ester; bulnesene; and various propanoic acid, 2-methyl- derivatives. The biological activity of the VOCs of E-6 appears different from the original isolate of this fungus, CZ-620, since a Gram-positive bacterium was killed, and Sclerotinia sclerotiorum and Rhizoctonia solani were not. Scanning electron micrographs of the mycelium of isolate E-6 showed substantial intertwining of the hyphal strands. These strands seemed to be held together by an extracellular matrix accounting for the strong mat-like nature of the mycelium, which easily lifts off the agar surface upon transfer, unlike any other isolate of this fungus. The ITS-5.8S rDNA partial sequence data showed 99 % similarity to the original M. albus strain CZ-620. For the first time, successful establishment of M. albus into its natural host, followed by recovery of the fungus, was accomplished in seedlings of G. ulmifolia. Overall, isolates of M. albus, including E-6, have chemical, biological and structural characteristics that make them potentially useful in

  17. Selection of active spaces for multiconfigurational wavefunctions

    Energy Technology Data Exchange (ETDEWEB)

    Keller, Sebastian; Boguslawski, Katharina; Reiher, Markus, E-mail: markus.reiher@phys.chem.ethz.ch [Laboratorium für Physikalische Chemie, ETH Zürich, Vladimir-Prelog-Weg 2, CH-8093 Zürich (Switzerland); Janowski, Tomasz; Pulay, Peter, E-mail: pulay@uark.edu [Department of Chemistry and Biochemistry, Fulbright College of Arts and Sciences, University of Arkansas, Fayetteville, Arkansas 72701 (United States)

    2015-06-28

    The efficient and accurate description of the electronic structure of strongly correlated systems is still a largely unsolved problem. The usual procedures start with a multiconfigurational (usually a Complete Active Space, CAS) wavefunction which accounts for static correlation and add dynamical correlation by perturbation theory, configuration interaction, or coupled cluster expansion. This procedure requires the correct selection of the active space. Intuitive methods are unreliable for complex systems. The inexpensive black-box unrestricted natural orbital (UNO) criterion postulates that the Unrestricted Hartree-Fock (UHF) charge natural orbitals with fractional occupancy (e.g., between 0.02 and 1.98) constitute the active space. UNOs generally approximate the CAS orbitals so well that the orbital optimization in CAS Self-Consistent Field (CASSCF) may be omitted, resulting in the inexpensive UNO-CAS method. A rigorous testing of the UNO criterion requires comparison with approximate full configuration interaction wavefunctions. This became feasible with the advent of Density Matrix Renormalization Group (DMRG) methods which can approximate highly correlated wavefunctions at affordable cost. We have compared active orbital occupancies in UNO-CAS and CASSCF calculations with DMRG in a number of strongly correlated molecules: compounds of electronegative atoms (F{sub 2}, ozone, and NO{sub 2}), polyenes, aromatic molecules (naphthalene, azulene, anthracene, and nitrobenzene), radicals (phenoxy and benzyl), diradicals (o-, m-, and p-benzyne), and transition metal compounds (nickel-acetylene and Cr{sub 2}). The UNO criterion works well in these cases. Other symmetry breaking solutions, with the possible exception of spatial symmetry, do not appear to be essential to generate the correct active space. In the case of multiple UHF solutions, the natural orbitals of the average UHF density should be used. The problems of the UNO criterion and their potential solutions

  18. Selection of active spaces for multiconfigurational wavefunctions

    Science.gov (United States)

    Keller, Sebastian; Boguslawski, Katharina; Janowski, Tomasz; Reiher, Markus; Pulay, Peter

    2015-06-01

    The efficient and accurate description of the electronic structure of strongly correlated systems is still a largely unsolved problem. The usual procedures start with a multiconfigurational (usually a Complete Active Space, CAS) wavefunction which accounts for static correlation and add dynamical correlation by perturbation theory, configuration interaction, or coupled cluster expansion. This procedure requires the correct selection of the active space. Intuitive methods are unreliable for complex systems. The inexpensive black-box unrestricted natural orbital (UNO) criterion postulates that the Unrestricted Hartree-Fock (UHF) charge natural orbitals with fractional occupancy (e.g., between 0.02 and 1.98) constitute the active space. UNOs generally approximate the CAS orbitals so well that the orbital optimization in CAS Self-Consistent Field (CASSCF) may be omitted, resulting in the inexpensive UNO-CAS method. A rigorous testing of the UNO criterion requires comparison with approximate full configuration interaction wavefunctions. This became feasible with the advent of Density Matrix Renormalization Group (DMRG) methods which can approximate highly correlated wavefunctions at affordable cost. We have compared active orbital occupancies in UNO-CAS and CASSCF calculations with DMRG in a number of strongly correlated molecules: compounds of electronegative atoms (F2, ozone, and NO2), polyenes, aromatic molecules (naphthalene, azulene, anthracene, and nitrobenzene), radicals (phenoxy and benzyl), diradicals (o-, m-, and p-benzyne), and transition metal compounds (nickel-acetylene and Cr2). The UNO criterion works well in these cases. Other symmetry breaking solutions, with the possible exception of spatial symmetry, do not appear to be essential to generate the correct active space. In the case of multiple UHF solutions, the natural orbitals of the average UHF density should be used. The problems of the UNO criterion and their potential solutions are discussed

  19. 2,3,7,8-TCDD-mediated toxicity in peripheral blood mononuclear cells is alleviated by the antioxidants present in Gelidiella acerosa: an in vitro study.

    Science.gov (United States)

    Kalaiselvan, Ilavarasi; Senthamarai, Muthumanikandan; Kasi, Pandima Devi

    2016-03-01

    Seaweeds have been used as a source of traditional medicine worldwide for the treatment of various ailments, mainly due to their ability to quench the free radicals. The present study aims at evaluating the protective effect of methanolic extract of Gelidiella acerosa, an edible red seaweed against 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)-induced toxicity in peripheral blood mononuclear cells (PBMC). For evaluating the protective effect of G. acerosa, PBMC were divided into four groups: vehicle control, TCDD (10 nM), TCDD + G. acerosa (300 μg/ml), and G. acerosa alone treated. Scavenging of intracellular reactive oxygen species (ROS) induced by TCDD was assessed by the dichloro-dihydro-fluorescein diacetate (DCFH-DA) method. Alterations at macromolecular level were quantified through lipid peroxidation (LPO) level, protein carbonyl content (PCC) level, and comet assay. The cellular morphology upon TCDD toxicity and G. acerosa treatment was obtained by light microscopy and histopathological studies. The chemical composition present in the methanolic extract of G. acerosa was determined by gas chromatography-mass spectrometry (GC-MS) analysis. The results reveal that 10 nM TCDD caused significant (P 114 ± 0.09), and PCC (15.13 ± 1.53) compared to the control, whereas co-treatment with G. acerosa significantly (P acid (retention time (RT) 13.15), cholesterol (RT 28.80), α-D-glucopyranose, 4-O-α-D-galactopyranosyl (RT 20.01), and azulene (RT 4.20). The findings suggest that G. acerosa has a strong protective ability against TCDD-induced cytotoxicity, oxidative stress, and DNA damage. PMID:25388558

  20. Selection of active spaces for multiconfigurational wavefunctions.

    Science.gov (United States)

    Keller, Sebastian; Boguslawski, Katharina; Janowski, Tomasz; Reiher, Markus; Pulay, Peter

    2015-06-28

    The efficient and accurate description of the electronic structure of strongly correlated systems is still a largely unsolved problem. The usual procedures start with a multiconfigurational (usually a Complete Active Space, CAS) wavefunction which accounts for static correlation and add dynamical correlation by perturbation theory, configuration interaction, or coupled cluster expansion. This procedure requires the correct selection of the active space. Intuitive methods are unreliable for complex systems. The inexpensive black-box unrestricted natural orbital (UNO) criterion postulates that the Unrestricted Hartree-Fock (UHF) charge natural orbitals with fractional occupancy (e.g., between 0.02 and 1.98) constitute the active space. UNOs generally approximate the CAS orbitals so well that the orbital optimization in CAS Self-Consistent Field (CASSCF) may be omitted, resulting in the inexpensive UNO-CAS method. A rigorous testing of the UNO criterion requires comparison with approximate full configuration interaction wavefunctions. This became feasible with the advent of Density Matrix Renormalization Group (DMRG) methods which can approximate highly correlated wavefunctions at affordable cost. We have compared active orbital occupancies in UNO-CAS and CASSCF calculations with DMRG in a number of strongly correlated molecules: compounds of electronegative atoms (F2, ozone, and NO2), polyenes, aromatic molecules (naphthalene, azulene, anthracene, and nitrobenzene), radicals (phenoxy and benzyl), diradicals (o-, m-, and p-benzyne), and transition metal compounds (nickel-acetylene and Cr2). The UNO criterion works well in these cases. Other symmetry breaking solutions, with the possible exception of spatial symmetry, do not appear to be essential to generate the correct active space. In the case of multiple UHF solutions, the natural orbitals of the average UHF density should be used. The problems of the UNO criterion and their potential solutions are discussed

  1. Search for compounds for prevention and treatment of oral mucositis induced by radiotherapy

    International Nuclear Information System (INIS)

    In the clinical setting, the frequency of adverse effects is directly linked to the results of treatment. However, in the case of head and neck radiotherapy for cancer, adverse effects are unavoidable and among them, oral mucositis is considered to be the most significant and debilitating acute complication associated with such radiation therapy. In patients receiving head and neck radiotherapy, the prevalence of mucositis is 85-100% and mucositis-associated pain is the main type of cancer treatment-related pain. A mouthwash or iceball containing sodium alginate, sodium azulene sulfonate and fibrinolysin deoxyribonuclease is widely used for the prevention and treatment of mucositis. In the USA, many strategies for the prevention of oral mucositis have been evaluated, but conflicting data has made the results inconclusive. Keratinocyte Growth Factor 1 (KGF1) has achieved promising results in therapy and is the only medication currently approved by the Food and Drug Administration (FDA), though in Japan, it is not covered by the National Health Insurance scheme. Therefore, we feel it is important to establish useful strategies for the prevention and treatment of radiotherapy-induced mucositis based on significant scientific evidence. As oxidative stress is associated with radiation-induced mucositis, in this study, we used 60Co-γray-induced HO-1-N-1 cell injury to studying the characteristics of mucositis in this regard and found that two well-known antioxidants, N-Acetyl-L-cysteine and catechins, had preventive effects against γray-induced cytotoxicity. N-Acetyl-L-cysteine and catechins would therefore be good materials for the prevention of mucositis in patients undergoing cancer radiotherapy. (author)

  2. Regiospecific protonation of organic chromophores.

    Science.gov (United States)

    Tang, Tao; Lin, Tingting; Wang, FuKe; He, Chaobin

    2016-07-28

    Highly conductive, acid doped polymers such as PEDOT/PSS and polyaniline (PANI) have attracted much attention due to their potential applications in flexible electronics. However, the understanding of the mechanism behind the doping process is still lacking. In this paper, we conduct a systematic and detailed investigation on the acid doping behaviors of four model compounds which were synthesized by combining different protonatable units such as pyridal[2,1,3]thiadiazole (PT), benzo[2,1,3]thiadiazole (BT), cyclopentadithiophene (CPDT), and azulene. DFT simulation and UV-vis-NIR spectral studies show that while the site of first protonation was mainly determined by proton affinity, the subsequent site of protonation and doping density were determined by the nature of the first protonation and influenced by the following two factors: (1) electrostatic charge repulsion and (2) the possible delocalization of protonated charge in the conjugated structure. If the first protonation occurs at heteroatoms and results in a coplanar structure, the subsequent sites of protonation are mainly determined by the distance from the positive charge center to lower the effect of static repulsion and charge delocalization. On the other hand, if the first protonation occurs on the main chain carbon atoms which induce a large torsional angle (non-coplanar) as the carbon hybridization changes from sp(2) to sp(3), the conformation and the possible charge delocalization in the protonated molecules will play an important role in determining the subsequent protonation. Our study provides new insight into the acid-doping mechanism of conductive polymers, which could be used as a guide to design new acid doped highly conductive polymers. PMID:27346384

  3. 顶空萃取-气相色谱-质谱法测定一种儿童专用防痱止痒水的挥发性成分%Analysis of Volatile Flavor Components in One Type of Remove Philippine and Itching Water by Headspace Extraction-GC/MS

    Institute of Scientific and Technical Information of China (English)

    李红; 熊爽; 田福林; 赵海波

    2011-01-01

    采用顶空萃取-气相色谱/质谱法分析鉴定防痱止痒水的挥发性成分。结果表明:共检测出35种挥发性成分,主要成分为乙醇和酞酸二乙酯,其它成分主要包括醇、烯、酯、甘菊环等。检出的物质中,α-蒎烯、β-蒎烯、莰烯、桉叶醇、樟脑、α-萜品醇、龙脑、醋酸异龙脑酯、石竹烯为野菊花挥发油的有效成分;苯甲酸甲酯、苯甲酸苄酯、丁香酚为金银花挥发油的有效成分;广藿香醇为广藿香提取物的主要成分。α-蒎烯、β-月桂烯、β-蒎烯、莰烯、薄荷醇、丁香酚等成分都具有较强的驱避蚊虫的作用。%The volatile components in one type of remove philippine and itching water were analyzed by headspace extraction-gas chromatography-mass spectrometry(HS-GC/MS).The results showed that HS-GC/MS is effective in the analysis of remove philippine and itching water.35 components are separated and identified.The main components are ethyl alcohol and diethyl phthalate acid,the others are alcohols,terpenes,esters and azulenes.alpha.-Pinene,beta.-pinene,camphene,eucalyptol,camphor,p-menth-1-en-8-ol,borneol,isobornyl acetate,caryophyllene are the effective components of the volatile oil in chrysanthemum indicum L.Benzoic acid methyl ester,benzyl benzoate,eugenol are the effective components of the volatile oil in flos lonicerae.Patchouli alcohol is the effective components of the volatile oil in pogostemon cablin(blanco) benth.alpha.-Pinene,beta.-myrcene,beta.-pinene,camphene,menthol,eugenol are all effictive repellent.

  4. 中国名优红茶香气成分的比较研究%Study on the Aroma Components in Chinese Famous Black Tea

    Institute of Scientific and Technical Information of China (English)

    王秋霜; 陈栋; 许勇泉; 尹军峰

    2013-01-01

    为了研究中国名优红茶挥发性香气物质并确定主要呈香特征,采用顶空固相微萃取方法(HS-SPME)提取红茶样品中的挥发性物质,用气相色谱/质谱联用技术(GC-MS)结合挥发性物质的保留指数(RI)鉴定红茶样品中香气物质种类及其对总体香气的贡献.结果表明,鉴定出约60种香气化合物,主要包含醇类、酯类、醛类、酮类和烯类、烷烃类等,其中醇类是国内名优红茶香气中最主要的物质,其次是酯类和醛类.香气化合物中芳樟醇、橙花醇、水杨酸甲酯、氧化芳樟醇是最主要的呈香物质,平均含量分别占总香气的39.48%、17.5%、8.21%、4.74%.所体现的花香、甜香、果香是中国红茶的香气特征.%With the aim to study the volatile aroma component of native black tea and determine the main aroma characters, the headspace solid-phase micro-extraction (HS-SPME) method was adopted to extract the volatiles and gas chromatography-mass spectrometry(GC-MS) coupled with retention index(RI) of the volatiles were used to determine the volatiles variety in black tea samples and their contribution to the total aroma. The result showed that more than fifty aroma compounds were determined including alcohol, ester, aldehyde, azulene ketones and terpenes, hydrocarbon and etc., among which the alcohol was the most important compounds and ester and aldehyde were next to it. Li nalool, ger-ariol, methl salcylate, linalool oxide were the most important compounds, representing 39.48%, 17.5%, 8.21% and 4.74% of the total aroma respectively. Flower-like, fruit-like, refreshing fragrance and sweet aroma were the main character of native black tea.

  5. Investigation of how to prevent mucositis induced by chemoradiotherapy

    International Nuclear Information System (INIS)

    Chemoradiotherapy for head and neck cancer is associated with a high incidence of severe oral mucositis; an adverse, painful event. Oral mucositis also causes nutritional deficiency by making oral feeding difficult. This may lead to prolongation of hospitalization due to complications caused by malnutrition. However, an effective way to prevent oral mucositis completely, remains to be found. In this study, we evaluated the occurrence of oral mucositis, and nutritional conditions such as hypoalbuminemia, reduction of body weight, and length of hospital stay (days) when the mouth was rinsed using rebamipide solution (R solution), or Poraprezinc-alginate sodium solution (P-A solution) (both considered to be effective for oral mucositis). A mouth rinsed with sodium azulene sulfonate (S solution) was used as a control. The mouth was rinsed out six times per day continuously during chemoradiotherapy. In the study, 31 patients were assigned to rinse their mouths using R solution, 11 patients using P-A solution, and 15 patients using S solution (reduction rate of body weight in 14 patients). For the evaluation, the criteria for adverse drug reactions CTCAE (v3.0) were used. Grade 1 and over, oral mucositis occurred in 48% of the R solution group, 36% of the P-A solution group, and 80% of the S solution group, indicating that the P-A solution group significantly prevented the occurrence of oral mucositis as opposed to the S solution group. A reduction in body weight was observed in 81% of the R solution group, 82% of the P-A solution group, and 79% of the S solution group, indicating a similar weight reduction rate among individual solution groups. Hypoalbuminemia equal to grade 2 or higher occurred in 3% of the R solution group, 18% of the P-A solution group, and 29% of the S solution group, indicating that the R group significantly prevented the occurrence of hypoalbuminemia compared to the S solution group. In addition, the length of hospital stays were 44±8.0 days for

  6. Identificação de espécies da família Asteraceae, revisão sobre usos e triagem fitoquímica do gênero Eremanthus da Reserva Boqueirão, Ingaí-MG Asteraceae species identification, use revision and phytochemical screening of Eremanthus genus in Boqueirão Ecological Reserve, Ingaí - Minas Gerais State, Brazil

    Directory of Open Access Journals (Sweden)

    A.O. Ribeiro

    2010-12-01

    humans. The phytochemical screening of the hydroalcoholic extracts indicated the presence of reducing sugars, carbohydrates, amino acids, tannins, flavonoids, glycosides cardiotonics, carotenoids, steroids and triterpenoids, depsides and depsidones, coumarin derivatives, soapy saponins, alkaloids, purines, polysaccharides and anthraquinones. On the other hand, organic acids, catechins, sesquiterpene lactones and azulenes were not detected.

  7. Diverse Natural Products from Dichlorocyclobutanones: An Evolutionary Tale.

    Science.gov (United States)

    Deprés, Jean-Pierre; Delair, Philippe; Poisson, Jean-François; Kanazawa, Alice; Greene, Andrew E

    2016-02-16

    11-Nor PGE2 was prepared in our laboratory several years ago and used to obtain the corresponding ring-expanded γ-butyrolactam, γ-butyrolactone, and cyclopentanone derivatives. The conversion of a cyclobutanone into a cyclopentanone had relatively little precedent and merited further study. It was soon found that the presence of a single chlorine adjacent to the carbonyl not only greatly accelerated the reaction with ethereal diazomethane, but also substantially enhanced its regioselectivity; not surprisingly, a second chlorine further increased both. The confluence of this finding and the discovery by Krepski and Hassner that the presence of phosphorus oxychloride significantly improved the Zn-mediated dehalogenation procedure for the preparation of α,α-dichlorocyclobutanones from olefins provided the starting point for decades' worth of exciting adventures in natural product synthesis. A wide variety of naturally occurring 5-membered carbocycles (e.g., hirsutanes, cuparenones, bakkanes, guaianolides, azulenes) could thus be prepared by using dichloroketene-olefin cycloaddition, followed by regioselective one-carbon ring expansion with diazomethane. Importantly, it was also found that natural γ-butyrolactones (e.g., β-oxygenated γ-butyrolactones, lactone fatty acids) could be secured through regioselective Baeyer-Villiger oxidation of cycloadducts with m-CPBA and that naturally occurring γ-butyrolactam derivatives (e.g., amino acids, pyrrolidines, pyrrolizidines, indolizidines) could be efficiently obtained by regioselective Beckmann ring expansion of the adducts with O-(mesitylenesulfonyl)hydroxylamine (Tamura's reagent). These 5-membered carbocycles, γ-butyrolactones, and γ-butyrolactam derivatives were generally secured in enantiopure form through the use of either intrinsically chiral olefins or olefins bearing Stericol, a highly effective chiral auxiliary developed specifically for this "three-atom olefin annelation" approach. In addition

  8. Analysis of volatile compounds in oleoresin obtained from wind-dried and baked chilli (Capsicum annuum L.) using solid-phase micro-extraction coupled with gas chromatography-mass%固相微萃取-气相色谱质谱联用分析辣椒油树脂挥发性成分

    Institute of Scientific and Technical Information of China (English)

    曹雁平; 张东

    2011-01-01

    Volatile components emitted from oleoresin of wind-dried and baked Capsicum annuum L. with cultivation place of Wangdu of Hebei were analyzed by using solid- phase micro- extraction coupled with gas chromatography-mass. 28 Volatile components were identified in oleoresin from wind-dried chilli. Acetic acid ( 14.43 % ) ,2 ,4a,5,6 ,7 ,8,9,9a- octahydro-3,5,5 - trimethyl-9- methylene- 1H- benzocycloheptene ( 5.74% ), 1 -methoxy-4- (1-propenyl) - benzene ( 5.67% ) and 10s, 11 s- himachala-3 ( 12 ) ,4- diene (41.14%) were the primary volatile components. On the other hand,32 volatile components were identified in oleoresin from baked chilli, beta-Myrcene(3.14% ) ,2,6- dimethyl-2,6-octadiene(5.54% ) ,2-isopropyl-5-methyl-3-cyclohexen-1-one( 10.15% ),1 a,2,3,4,4a,5,6, 7 b- octahydro- 1,1, 4,7- tetramethyl- 1H- cycloprop [ e ] azulene ( 3.51% ) ,4- ( 1 - methylethyl ) -benzaldehyde ( 6.54% ), phenyl ethyl tiglate( 8.12% ), 1 - methoxy-4- ( 1 - propenyl ) - benzene ( 23.45 % ) and 1, 6-dimethyl-4 - ( 1 - methylethyl ) - naphthalene ( 3.69% ) were the primary volatile components. The composition of volatile components clearly differed between wind-dried and baked chilli.%以河北望都产朝天椒为原料,利用固相微萃取-气相色谱质谱联用技术分析风干辣椒和焙烤辣椒油树脂挥发性成分.从风干辣椒中共鉴定出28种挥发性成分,其中主要挥发性成分为:乙酸(14.43%),2,4a,5,6,7,8,9,9a-八氢-3,5,5-三甲基-9-亚甲基1H-苯(并)环庚烯(5.74%),1-甲氧基-4-(1-丙烯基)-笨(5.67%),10s,11s-Himachala-3(12),4-diene(41.14%).从焙烤辣椒中共鉴定出32种挥发性成分,其中主要挥发性成分为:β-月桂烯(3.14%),2,6-二甲基-2,6-辛二烯(5.54%),2-异丙基-5-甲基-3-环己烯-1-酮(10.15%),1a,2,3,4,4a,5,6,7b-八氢-1,1,4,7-四甲基-环丙苷菊(3.51%),4-(1-甲乙基)-苯甲醛(6.54%),苯基乙酸酯(8.12%),1-甲氧基-4-(1-丙烯基)-苯(23.45%),1,6-二甲基-4-(1-甲乙基)-萘(3.69%).风干

  9. Antibacterial effect of ginger (Zingiber officinale roscoe and bioactive chemical analysis using Gas chromatography mass spectrum

    Directory of Open Access Journals (Sweden)

    Hasanain Khaleel Shareef

    2016-05-01

    Full Text Available The objectives of this research was to determine the chemical composition of roscoe extract from methanol and evaluation of antibacterial activity. The phytochemical compound screened by GC-MS method. Forty eight bioactive phytochemical compounds were identified in the methanolic extract of Zingiber officinale. The identification of phytochemical compounds is based on the peak area, retention time molecular weight, molecular formula, MS Fragment-ions and pharmacological actions. GC-MS analysis of Zingiber officinale revealed the existence of the Octanal, 2-Naphthalenamine,1,2,4a,5,6,7,8,8a-octahydro-4a-methyl, 1-(Cyclopropyl-nitro-methyl-cyclopentanol, Endo-Borneol, Decanal, 1,2-15,16-Diepoxyhexadecane, Propanal,2-methyl-3-phenyl, Benzeneacetic acid ,4-(1H-1,2,3,4-tetrazol-1-yl, Ascaridole epoxide, 2-Methoxy-4-vinylphenol, 6-epi-shyobunol, Phenol,2-methoxy-5-(1-propenyl-,E, Alfa.-Copaene, 8-Isopropenyl-1,5-dimethyl-cyclodeca-1,5-diene, Bicyclo[3.1.0]hexane-6-methanol,2-hydroxy-1,4,4-trimethyl, 7-epi-cis-sesquisabinene hydrate, Alloaromadendrene, Benzene,1-(1,5-dimethyl-4-hexenyl-4-methyl, 1,3-Cyclohexadiene ,5-(1,5-dimethyl-4-hexenyl-2methyl-,[S-(R*,S*], Aromadendrene oxide, 1,6,10-Dodecatrien-3-ol,3,7,11-trimethyl-,(E, 4-((1H-3-Hydroxy-1-propenyl-2-methoxyphenol, Butan-2-one,4-(3-hydroxy-2-methoxyphenyl, Longipinocarveol,trans, Cholestan-3-ol,2-methylene-,(3ß,5α-, Bicyclo[4.4.0]dec-2-ene-4-ol,2-methyl-9-(prop-1-en-3-ol-2-yl-, Corymbolone, Estra-1,3,5(10-trien-17ß-ol, 1-Heptatriacotanol, Fenretinide, Folic acid, Spiro[4.5]decan-7-one,1,8-dimethyl-8,9-epoxy-4-isopropyl-, 7H-6,9a-Methano-4H-cyclopenta[9,10] cyclopropa[5,6]cyclodeca[1, Gingerol, 1b,4a-Epoxy-2H-cyclopenta[3,4]cyclopropa [8,9]cycloundec[1,2-b]o, Cyclopropa[5,6]-A-nor-5α-androstane-3,7-dione,3´,6ß-dihydro-17ß-h, Olean-12-ene-3,15,16,21,22,28-hexol,(3ß,15α,16α,21ß,22α-, Benz[e]azulen-3(3aH-one,4,6a,7,8,9,10,10a,10b-octahydro-3a,8,1, Naphthalene, decahydro-1-pentadecyl-, 13