Sample records for aromatic rings synthesis

  1. Synthesis and antifungal activity of C-21 steroids with an aromatic D ring. (United States)

    Sonego, Juan M; Cirigliano, Adriana M; Cabrera, Gabriela M; Burton, Gerardo; Veleiro, Adriana S


    Six analogues of salpichrolides with a simplified side chain (6-11) were synthesized using a new methodology to obtain steroids with an aromatic D-ring. The key step was the elimination of HBr in a vicinal dibromo D-homosteroid by treatment with 1,4-diazabicyclo[2.2.2]octane (DABCO). All new compounds were completely characterized by 2D NMR techniques and tested on two fungal pathogenic species, Fusarium virguliforme and Fusarium solani.

  2. Synthesis of a New Aromatic Dianhydride Containing Pyridine Ring and Related Polyimide

    Institute of Scientific and Technical Information of China (English)


    A new aromatic dianhydride monomer containing pyridine moiety, 2,6-bis[4'-(3",4"dicarboxyphenoxy)benzoyl]-pyridine dianhydride (Md), was synthesized in four steps, starting from 2,6-pyridinedicarboxyl chloride. A novel pyridine-containing polyimide was prepared via polycondensation of Md with ODA by two-step method. The resulting polyimide exhibits excellent solubility, film-forming capability and high thermal resistance.

  3. Electronic Aromaticity Index for Large Rings

    CERN Document Server

    Matito, Eduard


    We introduce a new electronic aromaticity index, AV1245, consisting in the average of the 4-center MCI values along the ring that keep a positional relationship of 1,2,4,5. AV1245 measures the extent of transferability of the delocalized electrons between bonds 1-2 and 4-5, which is expected to be large in conjugated circuits and, therefore, in aromatic molecules. A new algorithm for the calculation of MCI for large rings is also introduced and used to produce the data for the calibration of the new aromaticity index. AV1245 does not rely on reference values, does not suffer from large numerical precision errors, and it does not present any limitation on the nature of atoms, the molecular geometry or the level of calculation. It is a size-extensive measure with a small computational cost that grows linearly with the number of ring members. Therefore, it is specially suitable to study the aromaticity of large molecular rings as those occurring in belt-shaped M\\"obius structures or porphyrins.

  4. Optimization of low ring polycylic aromatic biodegradation (United States)

    Othman, N.; Abdul-Talib, S.; Tay, C. C.


    Polycyclic aromatic hydrocarbons (PAHs) are recalcitrance and persistence that finally turn into problematic environmental contaminants. Microbial degradation is considered to be the primary mechanism of PAHs removal from the environment due to its organic criteria. This study is carried out to optimize degradation process of low ring PAHs. Bacteria used in this study was isolated from sludge collected from Kolej Mawar, Universiti Teknologi MARA, Shah Alam, Selangor. Working condition namely, substrate concentration, bacteria concentration, pH and temperature were optimized. PAHs in the liquid sample was extracted by using solid phase microextractio equipped with a 7 µm polydimethylsiloxane (PDMS) SPME fibr. Removal of PAHs were assessed by measuring PAHs concentration using GC-FID. Results from the optimization study of biodegradation indicated that maximum rate of PAHs removal occurred at 100 mgL-1 of PAHs, 10% bacteria concentration, pH 7.0 and 30°C. These working condition had proved the effectiveness of using bacteria in biodegradation process of PAHs.

  5. [Laser Induced Fluorescence Spectroscopic Analysis of Aromatics from One Ring to Four Rings]. (United States)

    Zhang, Peng; Liu, Hai-feng; Yue, Zong-yu; Chen, Bei-ling; Yao, Ming-fa


    In order to distinguish small aromatics preferably, a Nd : YAG Laser was used to supply an excitation laser, which was adjusted to 0.085 J x cm(-2) at 266 nm. Benzene, toluene, naphthalene, phenanthrene, anthracene, pyrene and chrysene were used as the representative of different rings aromatics. The fluorescence emission spectra were researched for each aromatic hydrocarbon and mixtures by Laser induced fluorescence (LIF). Results showed that the rings number determined the fluorescence emission spectra, and the structure with same rings number did not affect the emission fluorescence spectrum ranges. This was due to the fact that the absorption efficiency difference at 266 nm resulted in that the fluorescence intensities of each aromatic hydrocarbon with same rings number were different and the fluorescence intensities difference were more apparently with aromatic ring number increasing. When the absorption efficiency was similar at 266 nm and the concentrations of each aromatic hydrocarbon were same, the fluorescence intensities were increased with aromatic ring number increasing. With aromatic ring number increasing, the fluorescence spectrum and emission peak wavelength were all red-shifted from ultraviolet to visible and the fluorescence spectrum range was also wider as the absorption efficiency was similar. The fluorescence emission spectra from one to four rings could be discriminated in the following wavelengths, 275 to 320 nm, 320 to 375 nm, 375 to 425 nm, 425 to 556 nm, respectively. It can be used for distinguish the type of the polycyclic aromatic hydrocarbons (PAHs) as it exists in single type. As PAHs are usually exist in a variety of different rings number at the same time, the results for each aromatic hydrocarbon may not apply to the aromatic hydrocarbon mixtures. For the aromatic hydrocarbon mixtures, results showed that the one- or two-ring PAHs in mixtures could not be detected by fluorescence as three- or four-ring PAHs existed in mixture

  6. Six-Membered Aromatic Polyazides: Synthesis and Application

    Directory of Open Access Journals (Sweden)

    Sergei V. Chapyshev


    Full Text Available Aromatic polyazides are widely used as starting materials in organic synthesis and photochemical studies, as well as photoresists in microelectronics and as cross-linking agents in polymer chemistry. Some aromatic polyazides possess high antitumor activity, while many others are of considerable interest as high-energy materials and precursors of high-spin nitrenes and C3N4 carbon nitride nanomaterials. The use of aromatic polyazides in click-reactions may be a new promising direction in the design of various supramolecular systems possessing interesting chemical, physical and biological properties. This review is devoted to the synthesis, properties and applications of six-membered aromatic compounds containing three and more azido groups in the ring.

  7. Six-Membered Aromatic Polyazides: Synthesis and Application. (United States)

    Chapyshev, Sergei V


    Aromatic polyazides are widely used as starting materials in organic synthesis and photochemical studies, as well as photoresists in microelectronics and as cross-linking agents in polymer chemistry. Some aromatic polyazides possess high antitumor activity, while many others are of considerable interest as high-energy materials and precursors of high-spin nitrenes and C₃N₄ carbon nitride nanomaterials. The use of aromatic polyazides in click-reactions may be a new promising direction in the design of various supramolecular systems possessing interesting chemical, physical and biological properties. This review is devoted to the synthesis, properties and applications of six-membered aromatic compounds containing three and more azido groups in the ring.

  8. Aromatic and antiaromatic ring currents in a molecular nanoring (United States)

    Peeks, Martin D.; Claridge, Timothy D. W.; Anderson, Harry L.


    Aromatic and antiaromatic molecules—which have delocalized circuits of [4n + 2] or [4n] electrons, respectively—exhibit ring currents around their perimeters. The direction of the ring current in an aromatic molecule is such as to generate a magnetic field that opposes the external field inside the ring (a ‘diatropic’ current), while the ring current in an antiaromatic molecule flows in the reverse direction (‘paratropic’). Similar persistent currents occur in metal or semiconductor rings, when the phase coherence of the electronic wavefunction is preserved around the ring. Persistent currents in non-molecular rings switch direction as a function of the magnetic flux passing through the ring, so that they can be changed from diatropic (‘aromatic’) to paratropic (‘antiaromatic’) simply by changing the external magnetic field. As in molecular systems, the direction of the persistent current also depends on the number of electrons. The relationship between ring currents in molecular and non-molecular rings is poorly understood, partly because they are studied in different size regimes: the largest aromatic molecules have diameters of about one nanometre, whereas persistent currents are observed in microfabricated rings with diameters of 20-1,000 nanometres. Understanding the connection between aromaticity and quantum-coherence effects in mesoscopic rings provides a motivation for investigating ring currents in molecules of an intermediate size. Here we show, using nuclear magnetic resonance spectroscopy and density functional theory, that a six-porphyrin nanoring template complex, with a diameter of 2.4 nanometres, is antiaromatic in its 4+ oxidation state (80 π electrons) and aromatic in its 6+ oxidation state (78 π electrons). The antiaromatic state has a huge paramagnetic susceptibility, despite having no unpaired electrons. This work demonstrates that a global ring current can be promoted in a macrocycle by adjusting its oxidation state

  9. Development of highly potent phosphodiesterase 4 inhibitors with anti-neuroinflammation potential: Design, synthesis, and structure-activity relationship study of catecholamides bearing aromatic rings. (United States)

    Zhou, Zhong-Zhen; Ge, Bing-Chen; Zhong, Qiu-Ping; Huang, Chang; Cheng, Yu-Fang; Yang, Xue-Mei; Wang, Hai-Tao; Xu, Jiang-Ping


    In this study, catecholamides (7a-l) bearing different aromatic rings (such as pyridine-2-yl, pyridine-3-yl, phenyl, and 2-chlorophenyl groups) were synthesized as potent phosphodiesterase (PDE) 4 inhibitors. The inhibitory activities of these compounds were evaluated against the core catalytic domains of human PDE4 (PDE4CAT), full-length PDE4A4, PDE4B1, PDE4C1, and PDE4D7 enzymes, and other PDE family members. Eight of the synthesized compounds were identified as having submicromolar IC50 values in the mid-to low-nanomolar range. Careful analysis on the structure-activity relationship of compounds 7a-l revealed that the replacement of the 4-methoxy group with the difluoromethoxy group improved inhibitory activities. More interesting, 4-difluoromethoxybenzamides 7i and 7j exhibited preference for PDE4 with higher selectivities of about 3333 and 1111-fold over other PDEs, respectively. In addition, compound 7j with wonderful PDE4D7 inhibitory activities inhibited LPS-induced TNF-α production in microglia.

  10. Aromaticity in Polyacene Analogues of Inorganic Ring Compounds

    CERN Document Server

    Chattaraj, P K; Chattaraj, Pratim Kumar; Roy, Debesh Ranjan


    The aromaticity in the polyacene analogues of several inorganic ring compounds (BN-acenes, CN-acenes, BO-acenes and Na6-acenes) is reported here for the first time. Conceptual density functional theory based reactivity descriptors and the nucleus independent chemical shift (NICS) values are used in this analysis.

  11. Molecular recognition of aromatic rings by flavin: electrostatics and dispersion determine ring positioning above isoalloxazine. (United States)

    Koziol, Lucas; Kumar, Neeraj; Wong, Sergio E; Lightstone, Felice C


    Aromatic stacking interactions between isoalloxazine (ISA) of flavin and three prototypical aromatics (benzene, pyridine, chlorobenzene) were investigated using electronic structure calculations with Monte Carlo simulated annealing. The Effective Fragment Potential (EFP) method was used to locate the low-energy equilibrium configurations for the three dimer systems. These structures were further characterized through DFT (M06-2X) and MP2 calculations. One equilibrium configuration exists for ISA-benzene; characterizing the stacked dimer surface revealed a steep, single-welled potential that funnels benzene directly between rings II and III, positioning a substituent hydrogen adjacent to the redox-active N5. ISA-pyridine and ISA-chlorobenzene minimum-energy structures contain the aromatic ring in very similar position to that in ISA-benzene. However, the added rotational degree of freedom leads to two distinct binding motifs, having approximately antiparallel or parallel dipole moment alignment with ISA. The existence of the latter binding configuration was unexpected but is explained by the shape of the ISA electrostatic potential. Dispersion is the primary noncovalent interaction driving the positioning of aromatic rings above ISA, while electrostatics determine the orientation in dipole-containing substituted benzenes. The interplay of these interactions can be used to tune molecular recognition properties of synthetic redox cofactors, including positioning desired functional groups adjacent to the redox-active N5.

  12. Literature Survey and Further Studies on the 3-Alkylation of N-Unprotected 3-Monosubstituted Oxindoles. Practical Synthesis of N-Unprotected 3,3-Disubstituted Oxindoles and Subsequent Transformations on the Aromatic Ring

    Directory of Open Access Journals (Sweden)

    Eszter Kókai


    Full Text Available The paper provides a comprehensive review of the base-catalysed C3-alkylation of N-unprotected-3-monosubstituted oxindoles. Based on a few, non-systematic studies described in the literature using butyllithium as the deprotonating agent, an optimized method has now been elaborated, via the corresponding lithium salt, for the selective C3-alkylation of this family of compounds. The optimal excess of butyllithium and alkylating agent, and the role of the halogen atom in the latter (alkyl bromides vs. iodides were also studied. The alkylation protocol has also been extended to some derivatives substituted at the aromatic ring. Finally, various substituents were introduced into the aromatic ring of the N-unprotected 3,3-dialkyloxindoles obtained by this optimized method.

  13. Coulomb pairing resonances in multiple-ring aromatic molecules

    CERN Document Server

    Huber, D L


    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 ...

  14. Synthesis of azaphenanthridines via anionic ring closure

    DEFF Research Database (Denmark)

    Hansen, Henriette Møller; Lysén, M.; Begtrup, M.;


    A new and convergent synthesis of azaphenanthridines via an anionic ring closure is reported. Ortho-lithiation/in situ borylation of cyanopyridines produces the corresponding cyanopyridylboronic esters, which undergo a Suzuki-Miyaura cross-coupling to give the key intermediates. Addition of lithium...

  15. Linkage of Aromatic Ring Structures in Saturates, Aromatics, Resins and Asphaltenes Fractions of Vacuum Residues Determined by Collision-Induced Dissociation Technology

    Institute of Scientific and Technical Information of China (English)

    Wang Wei; Liu Yingrong; Liu Zelong; Hou Huandi; Tian Songbai


    The linkage of aromatic ring structures in vacuum residues was important for the reifning process. The Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) combined with collision-induced dissociation (CID) is a powerful method to characterize the molecular structure of petroleum fractions. In this work, model compounds with differ-ent aromatic ring structures were measured by CID FT-ICR MS. The cracking of the parent ions and the generated fragment ions were able to distinguish different linkage of the model compounds. Then, vacuum residues were separated into saturates, aromat-ics, resins and asphaltenes fractions (SARA), and each fraction was characterized by CID technology. According to the experi-mental results, the aromatic rings in saturates and aromatics fractions were mainly of the island-type structures, while the aromatic rings in resins and asphaltenes fractions had a signiifcant amount of archipelago-type structures.

  16. Synthesis and characterization of methacryloyl monomers containing short perfluorocarbon side chains and aromatic rings%含短氟碳侧链及芳香环的甲基丙烯酰类单体的合成与表征

    Institute of Scientific and Technical Information of China (English)

    冯泽峰; 谭业邦; 邢卫国; 袁培林; 王明刚


    以全氟己基碘烷为原料通过一锅法制备了3-(全氟正已基)环氧丙烷,总收率达79.6%.从该环氧丙烷出发合成分离出了5种含短氟碳侧链及芳香环侧基的甲基丙烯酰类单体,并探讨了中间体含氟醇的最佳合成条件;通过1 HNMR、13CNMR、19FNMR对合成单体进行了表征.%Perfluorohexyl iodide has been used as a raw material in preparing 3-perfluorohexyl-l, 2-epoxypropane ( PFOP) by one-pot reaction. The total yield reached 79. 6% . Starting from 3-perfluorohexyl-l ,2-epoxypropane,five novel methacryloyl monomers containing aromatic rings and short perfluorocarbon side chains were obtained;and the optimal conditions of the intermediates were discussed. The monomers were confirmed by 1HNMR,13CNMR and 19FNMR.

  17. Condensation reactions of glucose and aromatic ring; Glucose to hokokan tono shukugo hanno

    Energy Technology Data Exchange (ETDEWEB)

    Komano, T.; Mashimo, K.; Wainai, T.; Tanaka, C.; Yoshioka, T. [Nihon University, Tokyo (Japan). College of Science and Technology; Sugimoto, Y.; Miki, Y. [National Institute of Materials and Chemical Research, Tsukuba (Japan)


    For artificial coalification, condensation reactions of aromatic ring and activated compounds produced by dehydrating reaction of glucose were studied experimentally. In heat treatment experiment in water, three reaction specimens such as glucose, glucose and phenol, and glucose and benzaldehyde were fed into an autoclave together with distilled water, and subjected to reaction at 180{degree}C under spontaneous pressure for 50 hours. In hydrogenation experiment, the specimens were fed into an autoclave together with tetradecane and sulfurization catalyst, and subjected to reaction at 350{degree}C under initial pressure of 9.8MPa for 2 hours for gas chromatography (GC) analysis of products. As the experimental result, the reaction between glucose and aromatic ring in heat treatment in water occurred between aromatic ring and active fragment with a mean carbon number of 4-5 produced by decomposition of glucose. The reactivity was higher in benzaldehyde addition than phenol addition. 3 refs., 4 figs., 1 tab.

  18. Electron correlation in C (4N+2) carbon rings aromatic vs. dimerized structures

    CERN Document Server

    Torelli, T; Torelli, Tommaso; Mitas, Lubos


    The electronic structure of C_(4N+2) carbon rings exhibits competing many-body effects of Huckel aromaticity, second-order Jahn-Teller and Peierls instability at large sizes. This leads to possible ground state structures with aromatic, bond angle or bond length alternated geometry. Highly accurate quantum Monte Carlo results indicate the existence of a crossover between C_10 and C_14 from bond angle to bond length alternation. The aromatic isomer is always a transition state. The driving mechanism is the second-order Jahn-Teller effect which keeps the gap open at all sizes.

  19. Synthesis, structure, and fullerene-complexing property of azacalix[6]aromatics. (United States)

    Fa, Shi-Xin; Wang, Li-Xia; Wang, De-Xian; Zhao, Liang; Wang, Mei-Xiang


    Synthesis, structure, and fullerene-binding property of azacalix[6]aromatics were systematically studied. By means of [3 + 3] and [2 + 2 + 2] fragment coupling protocols, a number of azacalix[6]aromatics containing different combinations of benzene, pyridine, and pyrimidine rings and various substituents on the bridging nitrogen atoms were synthesized conveniently in moderate to good yields. The resulting macrocycles adopt in the solid state symmetric and heavily distorted 1,3,5-alternate conformations depending on the aromatic building units, whereas, in solution, they exist as a mixture of conformers that undergo rapid interchanges relative to the NMR time scale. All macrocycles were able to form 1:1 complexes with C60 and C70 in toluene with the association constants up to 7.28 × 10(4) M(-1). In the crystalline state, azacalix[6]aromatics form complexes with C60 and C70 with 2:1, 1:1, and 1:2 stoichiometric ratios between host and guest. Azacalix[6]aromatics interact with fullerene by forming mainly the sandwich structure in which C60 or C70 is sandwiched by two macrocycles. X-ray molecular structures revealed that multiple π-π and CH-π interactions between concave azacalix[6]aromatics and convex fullerenes C60 and C70 contribute a joint driving force to the formation of host-guest complexes.

  20. Microwave-assisted synthesis of α-hydroxy aromatic ketones from α-bromo aromatic ketones in water

    Institute of Scientific and Technical Information of China (English)

    Xiang Liu; Hai Bo Chen; Zheng Guang Pan; Jian He Xu; He Xing Li


    A reaction of α-bromo aromatic ketones in water with microwave irradiation gave the corresponding α-hydroxy aromatic ketones in good yields.The use of microwaves was found to significantly improve yields and shorten the reaction time.This reaction afforded a very clean,convenient method for the synthesis of α-hydroxy aromatic ketones.

  1. Influence of chemical structure on skin reactions induced by antiepileptic drugs--the role of the aromatic ring. (United States)

    Wang, Xiang-Qing; Shi, Xiao-Bing; Au, Ran; Chen, Fu-Shun; Wang, Fang; Lang, Sen-Yang


    Here we assessed whether the presence of an aromatic ring as a commonality in chemical structures of AEDs can explain skin reaction. We found that 164 cases of skin reactions associated with the use of AEDs were reported. Aromatic AEDs were suspected in 88.41% (145/164) of patients with skin reactions versus 59.80% (2316/3873) of patients without skin reactions. The presence of an aromatic ring in the chemical structure was associated with a significant increased risk of skin reactions (adjusted ROR 3.50; 95% CI 2.29, 5.35). Among the aromatic AEDs, skin reactions were significantly associated with carbamazepine, lamotrigine, and oxarbazepine. These results confirm that the presence of an aromatic ring as a common feature in chemical structures of AEDs partly explains AED-skin reactions. Skin reactions were reported triple as frequently with aromatic AEDs than with non-aromatic AEDs.

  2. Aromaticity in benzene-like rings - An experimental electron density investigation

    Indian Academy of Sciences (India)

    Anupama Ranganathan; G U Kulkarni


    An experimental charge density study has been carried out on perylene based on X-ray diffraction measurements at 130 K. The electron density and its associated properties have been evaluated at the bond and the ring critical points for the naphthalene residues as well as for the central ring. The variation of the Laplacian along the axis, above and below the ring plane, is found to be symmetric for the central ring while for the naphthalene rings, the Laplacian values are enhanced under the bow-shaped region. A plot of the Laplacian versus density evaluated at various points along the axis above the ring plane, shows a steep variation in the case of the central ring implying that the -density is smeared out compared to that over the naphthalene rings. Similar data extracted from a quinoid ring and a regular phenyl ring (both based on earlier reports from this laboratory) exhibit increasingly shallower trends and indicate, by contrast, that the central ring of perylene is much less aromatic.

  3. Silica Chloride Nano Particle Catalyzed Ring Opening of Epoxides by Aromatic Amines

    Institute of Scientific and Technical Information of China (English)

    Karimian Ramin; Piri Farideh; Karimi Babak; Moghimi Abolghasem


    Silica chloride nano particle (nano SiO2-Cl), has been found to be heterogeneous catalyst for facile, simple and mild ring opening of epoxides with aromatic amines to afford β-amino alcohols in dry CH2Cl2 at room temperature.

  4. Aromatic A-ring analogues of orobanchol, new germination stimulants for seeds of parasitic weeds

    NARCIS (Netherlands)

    Malik, H.; Kohlen, W.; Jamil, M.; Rutjes, F.P.J.T.; Zwanenburg, B.


    Strigolactones are signaling compounds in plants of increasing importance. In this paper the focus is on their activity as germinating agents for seeds of parasitic weeds. The syntheses of aromatic A-ring analogues of the germination stimulant orobanchol have been described. Starting substrate is th

  5. Argentation chromatography for the separation of polycyclic aromatic compounds according to ring number. (United States)

    Nocun, Margarete; Andersson, Jan T


    Crude oils are the most complex mixtures known and every speciation method relies on a simplification of their complexity. Argentation chromatography is shown to be superior to traditional liquid chromatographic ways of separating aromatic compounds based on the number of aromatic carbon atoms. A silver(I) mercaptopropano silica gel allows an efficient group separation of polycyclic aromatic compounds to be achieved. The usefulness of this phase is demonstrated for SRM 1582 Wilmington crude oil and a diesel fuel. Furthermore, the phase can also be used for semi-preparative purposes to collect fractions for further analysis with high resolution mass spectrometry. Orbitrap mass spectra are obtained here for the polycyclic aromatic sulfur heterocycles and it is demonstrated that they can contain one to five naphtheno rings.

  6. [Asymmetric synthesis of aromatic L-amino acids catalyzed by transaminase]. (United States)

    Xia, Wenna; Sun, Yu; Min, Cong; Han, Wei; Wu, Sheng


    Aromatic L-Amino acids are important chiral building blocks for the synthesis of many drugs, pesticides, fine chemicals and food additives. Due to the high activity and steroselectivity, enzymatic synthesis of chiral building blocks has become the main research direction in asymmetric synthesis field. Guided by the phylogenetic analysis of transaminases from different sources, two representative aromatic transaminases TyrB and Aro8 in type I subfamily, from the prokaryote Escherichia coli and eukaryote Saccharomyces cerevisia, respectively, were applied for the comparative study of asymmetric transamination reaction process and catalytic efficiency of reversely converting keto acids to the corresponding aromatic L-amino acid. Both TyrB and Aro8 could efficiently synthesize the natural aromatic amino acids phenylalanine and tyrosine as well as non-natural amino acid phenylglycine. The chiral HPLC analysis showed the produced amino acids were L-configuration and the e.e value was 100%. L-alanine was the optimal amino donor, and the transaminase TyrB and Aro8 could not use D-amino acids as amino donor. The optimal molar ratio of amino donor (L-alanine) and amino acceptor (aromatic alpha-keto acids) was 4:1. Both of the substituted group on the aromatic ring and the length of fatty acid carbon chain part in the molecular structure of aromatic substrate alpha-keto acid have the significant impact on the enzyme-catalyzed transamination efficiency. In the experiments of preparative-scale transamination synthesis of L-phenylglycine, L-phenylalanine and L-tyrosine, the specific production rate catalyzed by TryB were 0.28 g/(g x h), 0.31 g/(g x h) and 0.60 g/(g x h) and the specific production rate catalyzed by Aro8 were 0.61 g/(g x h), 0.48 g/(g x h) and 0.59 g/(g x h). The results obtained here were useful for applying the transaminases to asymmetric synthesis of L-amino acids by reversing the reaction balance in industry.

  7. Methanogenic biodegradation of two-ringed polycyclic aromatic hydrocarbons. (United States)

    Berdugo-Clavijo, Carolina; Dong, Xiaoli; Soh, Jung; Sensen, Christoph W; Gieg, Lisa M


    Polycyclic aromatic hydrocarbons (PAH) are widespread in methane-rich subsurface environments, such as oil reservoirs and fuel-contaminated aquifers; however, little is known about the biodegradation of these compounds under methanogenic conditions. To assess the metabolism of PAH in the absence of electron acceptors, a crude oil-degrading methanogenic enrichment culture was tested for the ability to biodegrade naphthalene, 1-methylnaphthalene (1-MN), 2-methylnaphthalene (2-MN), and 2, 6-dimethylnaphthalene (2, 6-diMN). When methane was measured as an indicator of metabolism, nearly 400 μmol of methane was produced in the 2-MN- and 2, 6-diMN-amended cultures relative to substrate-unamended controls, which is close to the amount of methane stoichiometrically predicted based on the amount of substrate added (51-56 μmol). In contrast, no substantial methane was produced in the naphthalene- and 1-MN-amended enrichments. In time course experiments, metabolite analysis of enrichments containing 2-MN and 2, 6-diMN revealed the formation of 2-naphthoic acid and 6-methyl-2-naphthoic acid, respectively. Microbial community analysis by 454 pyrosequencing revealed that these PAH-utilizing enrichments were dominated by archaeal members most closely affiliated with Methanosaeta and Methanoculleus species and bacterial members most closely related to the Clostridiaceae, suggesting that these organisms play an important role in the methanogenic metabolism of the substituted naphthalenes in these cultures.

  8. Facile synthesis of (S)-beta-hydroxy-beta-trichloromethylated aromatic ketones by the regioselective ring cleavage of chiral beta-trichloromethyl-beta-propiolactone under the Friedel-Crafts conditions

    NARCIS (Netherlands)

    Fujisawa, T; Ito, T; Fujimoto, K; Shimizu, M; Wynberg, H; Staring, EGJ


    The reaction of enantiomerically pure beta-trichloromethyl-beta-propiolactone (1) as a chiral building block with an aromatic compound in the presence of Lewis acid provided an acylated product with a chiral trichloromethyl carbinol moiety. The acylated product was used as an effective chiral syntho

  9. Structural variations in aromatic 2-electron three-membered rings of the main group elements

    Indian Academy of Sciences (India)

    Dibyendu Mallick; Eluvathingal D Jemmis


    Structural variations of different 2-aromatic three-membered ring systems of main group elements, especially group 14 and 13 elements as compared to the classical description of cyclopropenyl cation has been reviewed in this article. The structures of heavier analogues as well as group 13 analogues of cyclopropenyl cation showed an emergence of dramatic structural patterns which do not conform to the generalnorms of carbon chemistry. Isolobal analogies between the main group fragments have been efficiently used to explain the peculiarities observed in these three-membered ring systems.

  10. Microwave-induced nucleophilic [18F]fluorination on aromatic rings: synthesis and effect of halogen on [18F]fluoride substitution of meta-halo (F, Cl, Br, I)-benzonitrile derivatives. (United States)

    Guo, Ning; Alagille, David; Tamagnan, Gilles; Price, Ronald R; Baldwin, Ronald M


    The meta-halo-3-methylbenzonitrile derivatives (-F, -Cl, -Br, -I) were synthesized as model compounds to study reactivity towards aromatic nucleophilic substitution. A single-mode microwave system was incorporated into a commercial radiochemical synthetic module for (18)F labeling. Labeling yields of 64% for fluoro-, 13% for bromo- and 9% for chloro-precursors were achieved in DMSO in Br>Cl>I.

  11. Aromaticity of rings-in-molecules (RIMs) from electron localization-delocalization matrices (LDMs) (United States)

    Sumar, Ismat; Cook, Ronald; Ayers, Paul W.; Matta, Chérif F.


    A new and powerful molecular descriptor termed the LDM (localization-delocalization matrix) has recently been proposed as a molecular fingerprinting tool and has been shown to yield robust quantitative-structure-to-activity/property-relationships (QSAR/QSPR). An LDM lists the average number of electrons localized within an atom in a molecule along its diagonal while the off-diagonal elements are the pair-wise average number of electrons shared between every pair of atoms in the molecule, bonded or not. Hence, the LDM is a representation of a fuzzy molecular graph that accounts for the whereabouts of all electron(s) in the molecule and can be expected to encode for several facets of its chemistry at once. We show that the LDM captures the aromatic character of a ring-in-a-molecule by comparing the aromaticity ranking based on the LDMs and their eigenvalues of 6-membered carbon rings within (polycyclic) benzenoid hydrocarbons with the ranking based on four well-established local aromaticity measures (harmonic oscillator model of aromaticity, acromatic fluctuation index, para delocalization index, and nucleus independent chemical shift(0)). This paper is dedicated to the memory of Professor Paul von Ragué Schleyer (1930-2014).

  12. Role of aromatic rings in the molecular recognition of aminoglycoside antibiotics: implications for drug design. (United States)

    Vacas, Tatiana; Corzana, Francisco; Jiménez-Osés, Gonzalo; González, Carlos; Gómez, Ana M; Bastida, Agatha; Revuelta, Julia; Asensio, Juan Luis


    Aminoglycoside antibiotics participate in a large variety of binding processes involving both RNA and proteins. The description, in recent years, of several clinically relevant aminoglycoside/receptor complexes has greatly stimulated the structural-based design of new bioactive derivatives. Unfortunately, design efforts have frequently met with limited success, reflecting our incomplete understanding of the molecular determinants for the antibiotic recognition. Intriguingly, aromatic rings of the protein/RNA receptors seem to be key actors in this process. Indeed, close inspection of the structural information available reveals that they are frequently involved in CH/pi stacking interactions with sugar/aminocyclitol rings of the antibiotic. While the interaction between neutral carbohydrates and aromatic rings has been studied in detail during past decade, little is known about these contacts when they involve densely charged glycosides. Herein we report a detailed experimental and theoretical analysis of the role played by CH/pi stacking interactions in the molecular recognition of aminoglycosides. Our study aims to determine the influence that the antibiotic polycationic character has on the stability, preferred geometry, and dynamics of these particular contacts. With this purpose, different aminoglycoside/aromatic complexes have been selected as model systems. They varied from simple bimolecular interactions to the more stable intramolecular CH/pi contacts present in designed derivatives. The obtained results highlight the key role played by electrostatic forces and the desolvation of charged groups in the molecular recognition of polycationic glycosides and have clear implications for the design of improved antibiotics.

  13. Synthesis of Volumetric Ring Antenna Array for Terrestrial Coverage Pattern

    Directory of Open Access Journals (Sweden)

    Alberto Reyna


    Full Text Available This paper presents a synthesis of a volumetric ring antenna array for a terrestrial coverage pattern. This synthesis regards the spacing among the rings on the planes X-Y, the positions of the rings on the plane X-Z, and uniform and concentric excitations. The optimization is carried out by implementing the particle swarm optimization. The synthesis is compared with previous designs by resulting with proper performance of this geometry to provide an accurate coverage to be applied in satellite applications with a maximum reduction of the antenna hardware as well as the side lobe level reduction.

  14. Synthesis of Volumetric Ring Antenna Array for Terrestrial Coverage Pattern (United States)

    Reyna, Alberto; Panduro, Marco A.; Del Rio Bocio, Carlos


    This paper presents a synthesis of a volumetric ring antenna array for a terrestrial coverage pattern. This synthesis regards the spacing among the rings on the planes X-Y, the positions of the rings on the plane X-Z, and uniform and concentric excitations. The optimization is carried out by implementing the particle swarm optimization. The synthesis is compared with previous designs by resulting with proper performance of this geometry to provide an accurate coverage to be applied in satellite applications with a maximum reduction of the antenna hardware as well as the side lobe level reduction. PMID:24701150

  15. Aromaticity Competition in Differentially Fused Borepin-Containing Polycyclic Aromatics. (United States)

    Messersmith, Reid E; Siegler, Maxime A; Tovar, John D


    This report describes the synthesis and characterization of a series of borepin-based polycyclic aromatics bearing two different arene fusions. The borepin synthesis features streamlined Ti-mediated alkyne reduction, leading to Z-olefins, followed by direct lithiation and borepin formation. These molecules allow for an assessment of aromatic competition between the fused rings and the central borepin core. Crystallographic, magnetic, and computational studies yielded insights about the aromaticity of novel, differentially fused [b,f]borepins and allowed for comparison to literature compounds. Multiple borepin motifs were also incorporated into polycyclic aromatics with five or six rings in the main backbone, and their properties were also evaluated.

  16. Synthesis and characterization of organosoluble aromatic copolyimids

    Institute of Scientific and Technical Information of China (English)

    YANG Jintian; HUANG Wei; ZHOU Yongfeng; YAN Deyue


    A series of aromatic copolyimides was success fully synthesized from the commercial pyromellitic dianhy dride (PMDA) with a commercial diamine p-phenyldiamine (PDA) and a diamine 4,4'-methylenebis-(2-tert-butylaniline)(MBTBA) specially designed by the authors.The copoly imides were characterized by Infra-red (IR),Nuclear Magnetic Resonance (NMR),Gel Permeation Chromato graphy (GPC),Ultraviolet Visual (UV-Vis),Thermogra vimetic Analysis (TGA) and Dynamic Mechanical Analysis (DMA).The copolyimide was precipitated in m-cresol in the polymerization process when the molar ratio of MBTBA and PDA was lower than 6/4.The number-average molecular weight of the soluble copolyimides measured by GPC was larger than 4.0 x 104,and the polydispersity index was higher than 1.5.Only one glass transition temperature of these copolyimdies was detected around 360℃ by DMA.The copolyimides did not show appreciable decomposition up to 500℃ under N2,and the thermal stability of the copolyimide increased a little with the introduction of PDA into the polyimide main chain.

  17. Ozonolysis of surface adsorbed methoxyphenols: kinetics of aromatic ring cleavage vs. alkene side-chain oxidation

    Directory of Open Access Journals (Sweden)

    E. M. O'Neill


    Full Text Available Lignin pyrolysis products, which include a variety of substituted methoxyphenols, constitute a major component of organics released by biomass combustion and may play a central role in the formation of atmospheric brown carbon. Understanding the atmospheric fate of these compounds upon exposure to trace gases is therefore critical to predicting the chemical and physical properties of biomass burning aerosol. We used diffuse reflectance infrared spectroscopy to monitor the heterogeneous ozonolysis of 4-propylguaiacol, eugenol, and isoeugenol adsorbed on NaCl and α-Al2O3 substrates. Adsorption of gaseous methoxyphenols onto these substrates produced near monolayer surface concentrations of 3 × 1018 molecules m-2. The subsequent dark heterogeneous ozonolysis of adsorbed 4-propylguaiacol cleaved the aromatic ring between the methoxy and phenol groups with the product conclusively identified by GC-MS and 1H-NMR. Kinetic analysis of eugenol and isoeugenol dark ozonolysis also suggested the formation of ring-cleaved products, although ozonolysis of the unsaturated substituent groups forming carboxylic acids and aldehydes was an order of magnitude faster. Average uptake coefficients for NaCl-adsorbed methoxyphenols were γ = 2.3 (±0.8 × 10-7 and 2 (±1 × 10-6 for ozonolysis of the aromatic ring and the unsaturated side chain, respectively, and reactions on α-Al2O3 were approximately two times slower. UV-visible radiation (λ>300 nm enhanced eugenol ozonolysis of the aromatic ring by a factor of 4(±1 but had no effect on ozonolysis of the alkene side-chain.

  18. Synthesis of Pyridoacridines through Anionic Cascade Ring Closure

    DEFF Research Database (Denmark)

    Petersen, I.N.; Kristensen, Jesper Langgaard


    A new synthesis of 13-deazaascididemin (AK-37) based on a recently developed anionic cascade ring closure is presented. Although the isolated yields are modest, the approach provides ready access to new substituted derivatives of 13-deazaascididemin. © Georg Thieme Verlag.......A new synthesis of 13-deazaascididemin (AK-37) based on a recently developed anionic cascade ring closure is presented. Although the isolated yields are modest, the approach provides ready access to new substituted derivatives of 13-deazaascididemin. © Georg Thieme Verlag....

  19. Substituent effects on non-covalent interactions with aromatic rings: insights from computational chemistry. (United States)

    Raju, Rajesh K; Bloom, Jacob W G; An, Yi; Wheeler, Steven E


    Non-covalent interactions with aromatic rings pervade modern chemical research. The strength and orientation of these interactions can be tuned and controlled through substituent effects. Computational studies of model complexes have provided a detailed understanding of the origin and nature of these substituent effects, and pinpointed flaws in entrenched models of these interactions in the literature. Here, we provide a brief review of efforts over the last decade to unravel the origin of substituent effects in π-stacking, XH/π, and ion/π interactions through detailed computational studies. We highlight recent progress that has been made, while also uncovering areas where future studies are warranted.

  20. Substitution patterns in aromatic rings by increment analysis. Model development and application to natural organic matter. (United States)

    Perdue, E M; Hertkorn, N; Kettrup, A


    The aromatic region of two-dimensional heteronuclear 1H, 13C NMR spectra of natural organic matter and related materials (e.g., 1H and 13C chemical shifts ranging from approximately 5 to 10 and 80 to 140 ppm, respectively) is highly complex and difficult to interpret using conventional approaches. In principle, this region of the NMR spectrum should be amenable to detailed analysis, because the effects of many common substituents on the chemical shifts of aromatic carbon and hydrogen are well documented. This paper describes the development of a model for prediction of substitution patterns in aromatic rings by increment analysis (SPARIA). In the forward mode, SPARIA is used to predict the chemical shifts of 1H and 13C on aromatic moieties containing every possible combination of eight common substituents that are likely to be representative of substituents on aromatic moieties in natural organic matter. The accuracy of SPARIA in the forward mode is evaluated for 29 aromatic compounds (100 peaks) by comparison of predicted chemical shifts for 1H and 13C with experimental values and with predictions of commercially available software for prediction of NMR spectra. The most important development in this paper is the inverse mode that is built into SPARIA. Given chemical shifts for 1H and 13C (such as may be obtained from a two-dimensional, heteronuclear NMR spectrum), the inverse mode of SPARIA calculates all possible combinations of the eight selected substituents that yield chemical shifts within a specified window of chemical shift for both 1H and 13C. Both the distribution of possible substitution patterns and simple descriptive statistics of the distribution are thus obtained. The inverse mode of SPARIA has been tested on the 29 aromatic compounds (100 peaks) that were used to evaluate its forward mode, and the dependence of the inverse process on the size of the chemical shift window has been evaluated. Finally, the inverse mode of SPARIA has been applied to

  1. Synthesis of functional aromatic multisulfonyl chlorides and their masked precursors. (United States)

    Percec, V; Bera, T K; De, B B; Sanai, Y; Smith, J; Holerca, M N; Barboiu, B; Grubbs, R B; Fréchet, J M


    The synthesis of functional aromatic bis(sulfonyl chlorides) containing an acetophenone and two sulfonyl chloride groups, i.e., 3,5-bis[4-(chlorosulfonyl)phenyl]-1-acetophenone (16), 3,5-bis(chlorosulfonyl)-1-acetophenone (17), and 3,5-bis(4-(chlorosulfonyl)phenyloxy)-1-acetophenone (18) via a sequence of reactions, involving in the last step the quantitative oxidative chlorination of S-(aryl)- N,N'-diethylthiocarbamate, alkyl- or benzyl thiophenyl groups as masked nonreactive precursors to sulfonyl chlorides is described. A related sequence of reactions was used for the synthesis of the aromatic trisulfonyl chloride 1,1,1-tris(4-chlorosulfonylphenyl)ethane (24). 4-(Chlorosulfonyl)phenoxyacetic acid, 2,2-bis[[[4-(chlorosulfonyl)phenoxyacetyl]oxy]methyl]-1,3-propanediyl ester (27), 5,11,17,23-tetrakis(chlorosulfonyl)-25,26,27,28-tetrakis(ethoxycarbonylmethoxy)calix[4]arene (38), 5,11,17,23,29,35-hexakis(chlorosulfonyl)-37,38,39,40,41,42-hexakis(ethoxycarbonylmethoxy)calix[6]arene (39), 5,11,17,23,29,35,41,47-octakis(chlorosulfonyl)-49,50,51,52,53,54,55,56-octakis(ethoxycarbonylmethoxy)calix[8]arene (40), 5,11,17,23-tetrakis(tert-butyl)-25,26,27,28-tetrakis(chlorosulfonyl phenoxyacetoxy)calix[4]arene (44), 5,11,17,23,29,35-hexakis(tert-butyl)-37,38,39,40,41,42-hexakis(chlorosulfonylphenoxyacetoxy)calix[6]arene (45), and 5,11,17,23,29,35,41,47-octakis(tert-butyl)-49,40,51,52,53,54,55,56-octakis(chlorosulfonylphenoxyacetoxy)calix[8]arene (46) were synthesized by two different multistep reaction procedures, the last step of both methods consisting of the chlorosulfonation of compounds containing suitable activated aromatic positions. 2,4,6-Tris(chlorosulfonyl)aniline (47) was obtained by the chlorosulfonation of aniline. The conformation of two series of multisulfonyl chlorides i.e., 38, 39, 40 and 44, 45, 46, was investigated by (1)H NMR spectroscopy. The masked nonreactive precursor states of the functional aromatic multisulfonyl chlorides and the aromatic

  2. Stereochemical basis for a unified structure activity theory of aromatic and heterocyclic rings in selected opioids and opioid peptides. (United States)

    Goldberg, Joel S


    This paper presents a novel unified theory of the structure activity relationship of opioids and opioid peptides. It is hypothesized that a virtual or known heterocyclic ring exists in all opioids which have activity in humans, and this ring occupies relative to the aromatic ring of the drug, approximately the same plane in space as the piperidine ring of morphine. Since the rings of morphine are rigid, and the aromatic and piperidine rings are critical structural components for morphine's analgesic properties, the rigid morphine molecule allows for approximations of the aromatic and heterocyclic relationships in subsequent drug models where bond rotations are common. This hypothesis and five propositions are supported by stereochemistry and experimental observations.Proposition #1 The structure of morphine provides a template. Proposition #2 Steric hindrance of some centric portion of the piperidine ring explains antagonist properties of naloxone, naltrexone and alvimopam. Proposition #3 Methadone has an active conformation which contains a virtual heterocyclic ring which explains its analgesic activity and racemic properties. Proposition #4 The piperidine ring of fentanyl can assume the morphine position under conditions of nitrogen inversion. Proposition #5 The first 3 amino acid sequences of beta endorphin (l-try-gly-gly) and the active opioid dipeptide, l-tyr-pro, (as a result of a peptide turn and zwitterion bonding) form a virtual piperazine-like ring which is similar in size, shape and location to the heterocyclic rings of morphine, meperidine, and methadone. Potential flaws in this theory are discussed.This theory could be important for future analgesic drug design.

  3. Computer-aided rational design of novel EBF analogues with an aromatic ring. (United States)

    Wang, Shanshan; Sun, Yufeng; Du, Shaoqing; Qin, Yaoguo; Duan, Hongxia; Yang, Xinling


    Odorant binding proteins (OBPs) are important in insect olfactory recognition. These proteins bind specifically to insect semiochemicals and induce their seeking, mating, and alarm behaviors. Molecular docking and molecular dynamics simulations were performed to provide computational insight into the interaction mode between AgamOBP7 and novel (E)-β-farnesene (EBF) analogues with an aromatic ring. The ligand-binding cavity in OBP7 was found to be mostly hydrophobic due to the presence of several nonpolar residues. The interactions between the EBF analogues and the hydrophobic residues in the binding cavity increased in strength as the distance between them decreased. The EBF analogues with an N-methyl formamide or ester linkage had higher docking scores than those with an amide linkage. Moreover, delocalized π-π and electrostatic interactions were found to contribute significantly to the binding between the ligand benzene ring and nearby protein residues. To design new compounds with higher activity, four EBF analogues D1-D4 with a benzene ring were synthesized and evaluated based on their docking scores and binding affinities. D2, which had an N-methyl formamide group linkage, exhibited stronger binding than D1, which had an amide linkage. D4 exhibited particularly strong binding due to multiple hydrophobic interactions with the protein. This study provides crucial foundations for designing novel EBF analogues based on the OBP structure. Graphical abstract The design strategy of new EBF analogues based on the OBP7 structure.

  4. Writing with ring currents: selectively hydrogenated polycyclic aromatics as finite models of graphene and graphane. (United States)

    Fowler, Patrick W; Gibson, Christopher M; Bean, David E


    Alternating partial hydrogenation of the interior region of a polycyclic aromatic hydrocarbon gives a finite model system representing systems on the pathway from graphene to the graphane modification of the graphene sheet. Calculations at the DFT and coupled Hartree-Fock levels confirm that sp(2) cycles of bare carbon centres isolated by selective hydrogenation retain the essentially planar geometry and electron delocalization of the annulene that they mimic. Delocalization is diagnosed by the presence of ring currents, as detected by ipsocentric calculation and visualization of the current density induced in the π system by a perpendicular external magnetic field. These induced 'ring' currents have essentially the same sense, strength and orbital origin as in the free hydrocarbon. Subjected to the important experimental proviso of the need for atomic-scale control of hydrogenation, this finding predicts the possibility of writing single, multiple and concentric diatropic and/or paratropic ring currents on the graphene/graphane sheet. The implication is that pathways for free flow of ballistic current can be modelled in the same way.

  5. Compounds having aromatic rings and side-chain amide-functionality and a method for transporting monovalent anions across biological membranes using the same (United States)

    Davis, Jeffery T.; Sidorov, Vladimir; Kotch, Frank W.


    A compound containing at least two aromatic rings covalently bonded together, with each aromatic ring containing at least one oxyacetamide-based side chain, the compound being capable of forming a chloride ion channel across a lipid bilayer, and transporting chloride ion across the lipid bilayer.

  6. Aromatic ring formation in opposed-flow diffusive 1,3-butadiene flames

    KAUST Repository

    Moshammer, Kai


    This paper is concerned with the formation of one- and two-ring aromatic species in near atmospheric-pressure opposed-flow diffusion flames of 1,3-butadiene (1,3-CH). The chemical structures of two different 1,3-CH/Ar-O/Ar flames were explored using flame-sampling molecular-beam mass spectrometry with both electron and single-photon ionization. We provide mole fraction profiles of 47 components as function of distance from the fuel outlet and compare them to chemically detailed modeling results. To this end, the hierarchically developed model described by Seidel et al. [16] has been updated to accurately comprise the chemistry of 1,3-butadiene. Generally a very good agreement is observed between the experimental and modeling data, allowing for a meaningful reaction path analysis. With regard to the formation of aromatic species up to naphthalene, it was essential to improve the fulvene and the C chemistry description in the mechanism. In particular, benzene is found to be formed mainly via fulvene through the reactions of the CH isomers with CH The n-CH radical reacts with CH forming 1,3-pentadiene (CH), which is subsequently oxidized to form the naphthalene precursor cyclopentadienyl (CH). Oxidation of naphthalene is predicted to be a contributor to the formation of phenylacetylene (CH), indicating that consumption reactions can be of similar importance as molecular growth reactions.

  7. Influence of chemical structure on hypersensitivity reactions induced by antiepileptic drugs: the role of the aromatic ring.

    NARCIS (Netherlands)

    Handoko, K.B.; Puijenbroek, E.P. van; Bijl, A.H.; Hermens, W.A.; Rijkom, JE Zwart-van; Hekster, Y.A.; Egberts, T.C.G.


    OBJECTIVE: Antiepileptic drugs (AEDs) can cause various 'idiosyncratic' hypersensitivity reactions, i.e. the mechanism by which AEDs induce hypersensitivity is unknown. The aim of this study was to assess whether the presence of an aromatic ring as a commonality in chemical structures of AEDs can ex

  8. Influence of chemical structure on hypersensitivity reactions induced by antiepileptic drugs : the role of the aromatic ring

    NARCIS (Netherlands)

    Handoko, Kim B; van Puijenbroek, Eugène P; Bijl, Annemarie H; Hermens, Walter A J J; Zwart-van Rijkom, Jeannette E F; Hekster, Yechiel A; Egberts, Toine C G


    OBJECTIVE: Antiepileptic drugs (AEDs) can cause various 'idiosyncratic' hypersensitivity reactions, i.e. the mechanism by which AEDs induce hypersensitivity is unknown. The aim of this study was to assess whether the presence of an aromatic ring as a commonality in chemical structures of AEDs can ex

  9. Studies of the Intramolecular Aromatic-ring Stacking Interactions in the Ternary Platinum(Ⅱ) Complexes

    Institute of Scientific and Technical Information of China (English)

    SUN Hong-liang


    The stability constants of some ternary mixed-ligand complexes, Pt(Phen)(CA)+, where Phen=1,10-phenanthroline and CA- =carboxylate, were determined by means of potentiometric pH titration in aqueous solutions(I=0.1 mol/L, KNO3; 25 ℃), and the stability of them was compared with that of the corresponding binary complexes. It was revealed that the ternary complexes containing phenylalkane carboxylates ligands(PCA-) are much more stable than those formed with formate and acetate. The results indicate that there exist the intramolecular aromatic-ring interactions between the phenanthroline ring of Phen and the phenyl moiety of ligand PCA- in the ternary mixed-ligand Pt(Phen)(PCA)- complexes. The extent of the stacking interactions, which depends on the number of methylene groups between the phenyl moieties and the coordinated phenylalkane carboxylate groups, was calculated. The best-fitted stack was obtained for the complexes with 2-phenylacetate and 3-phenylpropionate as the ligands.

  10. Cytotoxic non-aromatic B-ring flavanones from Piper carniconnectivum C. DC. (United States)

    Freitas, Giovana C; Batista, João M; Franchi, Gilberto C; Nowill, Alexandre E; Yamaguchi, Lydia F; Vilcachagua, Janaina D; Favaro, Denize C; Furlan, Maysa; Guimarães, Elsie F; Jeffrey, Christopher S; Kato, Massuo J


    The EtOAc extract from the leaves of Piper carniconnectivum C. DC. was subjected to chromatographic separation to afford two non-aromatic B-ring flavanone compounds: 5-hydroxy-2-(1'-hydroxy-4'-oxo-cyclohex-2'-en-1'-yl)-6,7-dimethoxy-2,3-dihydro-4H-chromen-4-one (1) and 5-hydroxy-2-(1',2'-dihydroxy-4'-oxo-cyclohexyl)-6,7-dimethoxy-2,3-dihydro-4H-chromen-4-one (2). The absolute configuration of (+)-1 was unambiguously determined as 2S,1'R by electronic circular dichroism (ECD) spectroscopy and comparison to simulated spectra that were calculated using time-dependent density functional theory (TDDFT). This methodology allowed the assignment of the absolute configuration of (+)-2 also as 2S,1'R, except for the stereogenic center at C-2', which was assigned as R because of the evidence drawn from high resolution NMR experiments. The cytotoxic activity of both compounds and 3 (hydrogenated B-ring derivative of 1) was evaluated on twelve human leukemia cell lines, and the IC50 values (<10 μM) indicated the activity of 1 against seven cell lines.

  11. Study of the Formation of the First Aromatic Rings in the Pyrolysis of Cyclopentene. (United States)

    Herbinet, Olivier; Rodriguez, Anne; Husson, Benoit; Battin-Leclerc, Frédérique; Wang, Zhandong; Cheng, Zhanjun; Qi, Fei


    The thermal decomposition of cyclopentene was studied in a jet-stirred reactor operated at constant pressure and temperature to provide new experimental information about the formation of the first aromatic rings from cyclic C5 species. Experiments were carried out at a residence time of 1 s, a pressure of 106.7 kPa, temperatures ranging from 773 to 1073 K and under diluted conditions (cyclopentene inlet mole fraction of 0.04). Species were quantified using three analytical methods: gas chromatography, synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS), and single photon laser ionization mass spectrometry (SPI-MS). Several species could be quantified using both methods allowing comparison of experimental data obtained with the three apparatuses. Discrepancies observed in mole fraction profiles of some large aromatics suggest that the direct sampling in the gas phase (with a molecular beam or a capillary tube) provide more reliable results. The main reaction products are 1,3-cyclopentadiene and hydrogen. The formation of many unsaturated C2-C6 olefins, diolefins and alkynes was also observed but in smaller amounts. Benzene, toluene, styrene, indene, and naphthalene were detected from 923 K. SVUV-PIMS data allowed the identification of another C6H6 isomer which is 1,5-hexadien-3-yne rather than fulvene. The quantification of the cyclopentadienyl radical was obtained from SVUV-PIMS and SPI-MS data with some uncertainty induced by the possible contribution to the signal for m/z 65 of a fragment from the decomposition of a larger ion. This is the first time that a radical is quantified in a jet-stirred reactor using non-optical techniques. SPI-MS analyses allowed the detection of species likely being combination products of allyl and cyclopentadienyl radicals. A model was developed for the pyrolysis of cyclopentene. This model includes routes of formation of aromatics from the cyclopentadienyl radical. The comparison of experimental and

  12. Synthesis of Heteroaromatic Compounds by Oxidative Aromatization Using an Activated Carbon/Molecular Oxygen System

    Directory of Open Access Journals (Sweden)

    Masahiko Hayashi


    Full Text Available A variety of heteroaromatic compounds, such as substituted pyridines, pyrazoles, indoles, 2-substituted imidazoles, 2-substituted imidazoles, 2-arylbenzazoles and pyrimidin-2(1H-ones are synthesized by oxidative aromatization using the activated carbon and molecular oxygen system. Mechanistic study focused on the role of activated carbon in the synthesis of 2-arylbenzazoles is also discussed. In the final section, we will disclose the efficient synthesis of substituted 9,10-anthracenes via oxidative aromatization.

  13. Novel aromatic ring-hydroxylating dioxygenase genes from coastal marine sediments of Patagonia

    Directory of Open Access Journals (Sweden)

    Ferrero Marcela A


    Full Text Available Abstract Background Polycyclic aromatic hydrocarbons (PAHs, widespread pollutants in the marine environment, can produce adverse effects in marine organisms and can be transferred to humans through seafood. Our knowledge of PAH-degrading bacterial populations in the marine environment is still very limited, and mainly originates from studies of cultured bacteria. In this work, genes coding catabolic enzymes from PAH-biodegradation pathways were characterized in coastal sediments of Patagonia with different levels of PAH contamination. Results Genes encoding for the catalytic alpha subunit of aromatic ring-hydroxylating dioxygenases (ARHDs were amplified from intertidal sediment samples using two different primer sets. Products were cloned and screened by restriction fragment length polymorphism analysis. Clones representing each restriction pattern were selected in each library for sequencing. A total of 500 clones were screened in 9 gene libraries, and 193 clones were sequenced. Libraries contained one to five different ARHD gene types, and this number was correlated with the number of PAHs found in the samples above the quantification limit (r = 0.834, p nahAc-like genes, phnAc-like genes as identified in Alcaligenes faecalis AFK2, and phnA1-like genes from marine PAH-degraders from the genus Cycloclasticus. Conclusion These results show the presence of hitherto unidentified ARHD genes in this sub-Antarctic marine environment exposed to anthropogenic contamination. This information can be used to study the geographical distribution and ecological significance of bacterial populations carrying these genes, and to design molecular assays to monitor the progress and effectiveness of remediation technologies.

  14. Analysis of the magnetically induced current density of molecules consisting of annelated aromatic and antiaromatic hydrocarbon rings. (United States)

    Sundholm, Dage; Berger, Raphael J F; Fliegl, Heike


    Magnetically induced current susceptibilities and current pathways have been calculated for molecules consisting of two pentalene groups annelated with a benzene (1) or naphthalene (2) moiety. Current strength susceptibilities have been obtained by numerically integrating separately the diatropic and paratropic contributions to the current flow passing planes through chosen bonds of the molecules. The current density calculations provide novel and unambiguous current pathways for the unusual molecules with annelated aromatic and antiaromatic hydrocarbon moieties. The calculations show that the benzene and naphthalene moieties annelated with two pentalene units as in molecules 1 and 2, respectively, are unexpectedly antiaromatic sustaining only a local paratropic ring current around the ring, whereas a weak diatropic current flows around the C-H moiety of the benzene ring. For 1 and 2, the individual five-membered rings of the pentalenes are antiaromatic and a slightly weaker semilocal paratropic current flows around the two pentalene rings. Molecules 1 and 2 do not sustain any net global ring current. The naphthalene moiety of the molecule consisting of a naphthalene annelated with two pentalene units (3) does not sustain any strong ring current that is typical for naphthalene. Instead, half of the diatropic current passing the naphthalene moiety forms a zig-zag pattern along the C-C bonds of the naphthalene moiety that are not shared with the pentalene moieties and one third of the current continues around the whole molecule partially cancelling the very strong paratropic semilocal ring current of the pentalenes. For molecule 3, the pentalene moieties and the individual five-membered rings of the pentalenes are more antiaromatic than for 1 and 2. The calculated current patterns elucidate why the compounds with formally [4n + 2] π-electrons have unusual aromatic properties violating the Hückel π-electron count rule. The current density calculations also provide

  15. Electronic transport properties of molecular junctions based on the direct binding of aromatic ring to electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Lan, Tran Nguyen, E-mail:


    Highlights: • Transport properties of molecular junction having direct binding of aromatic ring to electrode have been investigated. • The conductance of junction with sp-type electrode is higher than that of junction with sd-type electrode. • The rectifying mechanism critically depends on the nature of benzene–electrode coupling. • The p–n junction-like can be obtained even without heteroatom doping. • The negative differential resistance effect was observed for the case of sp-type electrode. - Abstract: We have used the non-equilibrium Green’s function in combination with the density functional theory to investigate the quantum transport properties of the molecular junctions including a terminated benzene ring directly coupled to surface of metal electrodes (physisorption). The other side of molecule was connected to electrode via thiolate bond (chemisorption). Two different electrodes have been studied, namely Cu and Al. Rectification and negative differential resistance behavior have been observed. We found that the electron transport mechanism is affected by the nature of benzene–electrode coupling. In other words, the transport mechanism depends on the nature of metallic electrode. Changing from sp- to sd-metallic electrode, the molecular junction changes from the Schottky to p–n junction-like diode. The transmission spectra, projected density of state, molecular projected self-consistent Hamiltonian, transmission eigenchannel, and Muliken population have been analyzed for explanation of electronic transport properties. Understanding the transport mechanism in junction having direct coupling of π-conjugate to electrode will be useful to design the future molecular devices.

  16. Water sandwiched by a pair of aromatic rings in a proton-conducting metal-organic framework. (United States)

    Dong, Xi-Yan; Li, Xue; Li, Bo; Zhu, Yan-Yan; Zang, Shuang-Quan; Tang, Ming-Sheng


    The interactions between water molecules and aromatic rings are known to be common and important in physics, chemistry and life sciences. Benzene-water complexes are the main prototype systems for O-Hπ and lone-pair (lp)π interactions in theoretical research, however solid state examples are very rare. Here, the solid state example of water sandwiched by a pair of aromatic rings is observed in a silver-mellitate framework, where lpπ and O-Hπ interactions coexist. The coexistence of these two interactions has been further verified by theoretical calculations. In addition, ammonium ions and water molecules as proton sources, and strongly H-bonded nets as the pathway of proton transport, make the reported MOFs (metal-organic frameworks) exhibit distinct proton conduction.

  17. A Macrocyclic 1,4-Diketone Enables the Synthesis of a p-Phenylene Ring That Is More Strained than a Monomer Unit of [4]Cycloparaphenylene. (United States)

    Mitra, Nirmal K; Corzo, Hector H; Merner, Bradley L


    The synthesis of a p-terphenyl-based macrocycle, containing a p-phenylene unit with 42.6 kcal/mol of strain energy (SE), is reported. The conversion of a macrocyclic 1,4-diketone to a highly strained arene system takes place over five synthetic steps, featuring iterative dehydrative reactions in the aromatization protocol. Spectroscopic data of the deformed benzenoid macrocycle are in excellent agreement with other homologues that have been reported, indicating that the central p-phenylene ring of 9 is aromatic.

  18. Synthesis of fused indazole ring systems and application to nigeglanine hydrobromide. (United States)

    Sather, Aaron C; Berryman, Orion B; Rebek, Julius


    The single-step synthesis of fused tricyclic pyridazino[1,2-a]indazolium ring systems is described. Structural details revealed by crystallography explain the unexpected reactivity. The method is applied to the gram scale synthesis of nigeglanine hydrobromide.

  19. Application of aromatization catalyst in synthesis of carbon nanotubes

    Indian Academy of Sciences (India)

    Song Rongjun; Yang Yunpeng; Ji Qing; Li Bin


    In a typical chemical vapour deposition (CVD) process for synthesizing carbon nanotubes (CNTs), it was found that the aromatization catalysts could promote effectively the formation of CNT. The essence of this phenomenon was attributed to the fact that the aromatization catalyst can accelerate the dehydrogenation–cyclization and condensation reaction of carbon source, which belongs to a necessary step in the formation of CNTs. In this work, aromatization catalysts, H-beta zeolite, HZSM-5 zeolite and organically modified montmorillonite (OMMT) were chosen to investigate their effects on the formation of multi-walled carbon nanotubes (MWCNTs) via pyrolysis method when polypropylene and 1-hexene as carbon source and Ni2O3 as the charring catalyst. The results demonstrated that the combination of those aromatization catalysts with nickel catalyst can effectively improve the formation of MWCNTs.

  20. π-Conjugated aromatics based on truxene: synthesis, self-assembly, and applications. (United States)

    Shi, Ke; Wang, Jie-Yu; Pei, Jian


    Recently, many efforts have been devoted to developing novel polycyclic aromatics due to their unique optical and electronic properties and broad applications, such as in organic field-effect transistors, organic photovoltaics, and organic light-emitting diodes. Among various π-conjugated molecules, many truxene derivatives have interesting characteristics such as C3 -symmetry, strong blue emission, and a planar rigid structure. Moreover, compared with many other π-conjugated aromatics, the synthesis and modification of truxene are particularly facile and diverse. In this account, we summarize investigations into truxene derivatives from synthesis and physical properties to applications in organic electronics.

  1. Upgrading of LCO by partial hydrogenation of aromatics and ring opening of naphthenes over bi-functional catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Calemma, Vincenzo; Giardino, Roberto; Ferrari, Marco [Eni R and M, Via Maritano 26, 20097 San Donato (Italy)


    Available options to upgrade LCO to diesel fuel are: i) aromatic saturation (ASAT) ii) mild hydrocracking and iii) aromatic saturation followed by selective ring opening (SRO) of naphthenic structures. Although the above mentioned routes lead to significant product quality enhancement, they suffer from several disadvantages. Hydrocracking leads to significant yields in gasoline-range products, ASAT is characterized by a relatively high consumption of hydrogen with only limited improvement of product quality in terms of density and cetane properties, ASAT + SRO route leads to higher improvements of product quality but it requires a very high hydrogen consumption which strongly affects the economics of the process. An alternative upgrading route consists in partial polyaromatic compound saturation and selective opening of both naphthenic and benzo-naphthenic structures to produce less condensed naphthenic structures and alkyl-benzenes respectively. In this case the hydrogen needed to improve product quality at the same level, of cetane properties and density, is lower in comparison with ASAT. This paper reports the results obtained during a research program aimed at upgrading LCO via selective ring opening. The hydroconversion of a low sulfur hydrotreated LCO has been studied over iridium and platinum loaded on different supports. The results of this study indicate that the properties of products heavily depend on the characteristics of the support and the metal used. The data obtained with the Ir/amorphous silica-alumina (MSA) show the possibility to get a clear increase of CN and decrease of density in comparison with the mere aromatic saturation. The practical consequence of this result is the possibility of producing products with CN and density similar to products obtained by complete dearomatization but still containing a significant percentage of aromatic structures so allowing a consistent saving of hydrogen. (author)

  2. Synthesis and Characterization of Aliphatic-Aromatic Hyperbranched Polyesters

    Institute of Scientific and Technical Information of China (English)

    唐黎明; 张晓龙; 邱藤; 刘德山


    Hyperbranched polymers possess special architectures and have potential applications in various areas. In this study, two AB2 monomers, dipropyl 5-(hydroxyethoxy) isophthalate (I) and 5-hydroxyethoxyisophthaic acid (II), were prepared. By bulk polycondensation of each monomer, two aliphatic-aromatic hyperbranched polyesters were prepared and characterized by 1H-nuclear magnetic resonance (1H-NMR), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), and scanning electron microscopy (SEM). Compared with all-aromatic hyperbranched polyesters, the prepared polymers showed lower glass transition temperatures in connection with the moderate decrease in their decomposition temperatures.

  3. Natural occurrence, biological activities and synthesis of eight-, nine-, and eleven-membered ring lactones

    Directory of Open Access Journals (Sweden)

    Helena M. C. Ferraz


    Full Text Available The natural occurrence, biological activities and synthetic approaches to natural eight-, nine-, and eleven-membered lactones is reviewed. These medium ring lactones are grouped according to ring size, and their syntheses are discussed. The structures of some natural products early identified as medium-ring lactones were revised after total synthesis.

  4. Quantum mechanical design of efficient second-order nonlinear optical materials based on heteroaromatic imido-substituted hexamolybdates: first theoretical framework of POM-based heterocyclic aromatic rings. (United States)

    Janjua, Muhammad Ramzan Saeed Ashraf


    This work was inspired by a previous report (Janjua et al. J. Phys. Chem. A 2009, 113, 3576-3587) in which the nonlinear-optical (NLO) response strikingly improved with an increase in the conjugation path of the ligand and the nature of hexamolybdates (polyoxometalates, POMs) was changed into a donor by altering the direction of charge transfer with a second aromatic ring. Herein, the first theoretical framework of POM-based heteroaromatic rings is found to be another class of excellent NLO materials having double heteroaromatic rings. First hyperpolarizabilities of a large number of push-pull-substituted conjugated systems with heteroaromatic rings have been calculated. The β components were computed at the density functional theory (DFT) level (BP86 geometry optimizations and LB94 time-dependent DFT). The largest β values are obtained with a donor (hexamolybdates) on the benzene ring and an acceptor (-NO(2)) on pyrrole, thiophene, and furan rings. The pyrrole imido-substituted hexamolybdate (system 1c) has a considerably large first hyperpolarizability, 339.00 × 10(-30) esu, and it is larger than that of (arylimido)hexamolybdate, calculated as 0.302 × 10(-30) esu (reference system 1), because of the double aromatic rings in the heteroaromatic imido-substituted hexamolybdates. The heteroaromatic rings act as a conjugation bridge between the electron acceptor (-NO(2)) and donor (polyanion). The introduction of an electron donor into heteroaromatic rings significantly enhances the first hyperpolarizabilities because the electron-donating ability is substantially enhanced when the electron donor is attached to the heterocyclic aromatic rings. Interposing five-membered auxiliary fragments between strong donor (polyanion) or acceptor (-NO(2)) groups results in a large computed second-order NLO response. The present investigation provides important insight into the NLO properties of (heteroaromatic) imido-substituted hexamolybdate derivatives because these compounds


    Institute of Scientific and Technical Information of China (English)

    LIN Qinghuang; WANG Huifen; LIU Deshan; ZHOU Qixiang


    Several novel aromatic liquid crystalline copolyesters with regular sequence structure were prepared by melt Schotten-Baumann polycondensation via complex monomer. Polarizing microscope with hot stage,thermal analysis and X-ray diffraction were used to investigate the structure and properties of the copolyesters . The effects of structural units, such as flexible spacer, noncolinear meta-linked phenylene unit, crankshaft unit, kink with flexible bridging unit and various substituted benzene rings on melting temperature of aromatic copolyesters were studied and discussed on the basis of crystalline structure of the polymers.

  6. Diels-Alder addition of some 6-and 5-member ring aromatic compounds on the Si(001)-2×1 surface: dependence of the binding energy on the resonance energy of the aromatic compounds

    Institute of Scientific and Technical Information of China (English)


    An energy decomposition scheme is proposed for understanding of the relative lowbinding energy of the [4+2] cycloaddition of benzene on the Si(001)-2×1 surface. By means ofdensity functional cluster model calculations, this scheme is demonstrated to be applicable tosome other 6-and 5-member ring aromatic compounds, giving a trend that the binding energy ofthe [4+2] cycloaddition products of those aromatic compounds on the Si(001) surface dependsstrongly on their resonance energy.

  7. Reaction of benzoxasilocines with aromatic aldehydes: Synthesis of homopterocarpans

    Directory of Open Access Journals (Sweden)

    Rodríguez-García Ignacio


    Full Text Available Abstract Condensation of 2H-benzo[g][1,2]oxasilocines with aromatic aldehydes in the presence of boron trifluoride affords mixtures of cis/trans 2-phenyl-3-vinylchromans with moderate yields. These can be transformed into homopterocarpans, a synthetic group of substances homologous to the natural isoflavonoid pterocarpans.

  8. Synthesis of Triarylmethane and Xanthene Dyes Using Electrophilic Aromatic Substitution Reactions (United States)

    McCullagh, James V.; Daggett, Kelly A.


    The synthesis of dyes has long been a popular topic in organic chemistry laboratory experiments because it allows students to see first hand that reactions learned in class can be used to make compounds with useful applications. In this experiment electrophilic aromatic substitution reactions are used to synthesize several triarylmethane and…

  9. Synthesis of aromatic glycoconjugates. Building blocks for the construction of combinatorial glycopeptide libraries

    Directory of Open Access Journals (Sweden)

    Markus Nörrlinger


    Full Text Available New aromatic glycoconjugate building blocks based on the trifunctional 3-aminomethyl-5-aminobenzoic acid backbone and sugars linked to the backbone by a malonyl moiety were prepared via peptide coupling. The orthogonally protected glycoconjugates, bearing an acetyl-protected glycoside, were converted into their corresponding acids which are suitable building blocks for combinatorial glycopeptide synthesis.

  10. On the Importance of the Aromatic Ring Parameter in Studies of the Solvolyses of Cinnamyl and Cinnamoyl Halides

    Directory of Open Access Journals (Sweden)

    Malcolm J. D'Souza


    Full Text Available In solvolysis studies using Grunwald-Winstein plots, dispersions were observed for substrates with aromatic rings at the α-carbon. Several examples for the unimolecular solvolysis of monoaryl benzylic derivatives and related diaryl- or naphthyl-substituted derivatives have now been reported, where the application of the aromatic ring parameter (I removes this dispersion. A recent claim suggesting the presence of an appreciable nucleophilic component to the I scale has now been shown, in a review of the solvolysis of highly-hindered alkyl halides, to be unlikely to be correct. Attention is now focused on the application of the hI term for the solvolysis of compounds containing a double bond in the vicinity of any developing carbocation. Available specific rates of solvolysis (plus some new values at 25°C of cinnamyl chloride, cinnamyl bromide, cinnamoyl chloride, p-chlorocinnamoyl chloride, and p-nitrocinnamoyl chloride are analyzed using the simple and extended (including the hI term Grunwald-Winstein equations.

  11. Functional characterization of diverse ring-hydroxylating oxygenases and induction of complex aromatic catabolic gene clusters in Sphingobium sp. PNB

    Directory of Open Access Journals (Sweden)

    Pratick Khara


    Full Text Available Sphingobium sp. PNB, like other sphingomonads, has multiple ring-hydroxylating oxygenase (RHO genes. Three different fosmid clones have been sequenced to identify the putative genes responsible for the degradation of various aromatics in this bacterial strain. Comparison of the map of the catabolic genes with that of different sphingomonads revealed a similar arrangement of gene clusters that harbors seven sets of RHO terminal components and a sole set of electron transport (ET proteins. The presence of distinctly conserved amino acid residues in ferredoxin and in silico molecular docking analyses of ferredoxin with the well characterized terminal oxygenase components indicated the structural uniqueness of the ET component in sphingomonads. The predicted substrate specificities, derived from the phylogenetic relationship of each of the RHOs, were examined based on transformation of putative substrates and their structural homologs by the recombinant strains expressing each of the oxygenases and the sole set of available ET proteins. The RHO AhdA1bA2b was functionally characterized for the first time and was found to be capable of transforming ethylbenzene, propylbenzene, cumene, p-cymene and biphenyl, in addition to a number of polycyclic aromatic hydrocarbons. Overexpression of aromatic catabolic genes in strain PNB, revealed by real-time PCR analyses, is a way forward to understand the complex regulation of degradative genes in sphingomonads.

  12. Enantioselective synthesis of the predominant AB ring system of the Schisandra nortriterpenoid natural products. (United States)

    Gockel, Birgit; Goh, Shermin S; Puttock, Emma J; Baars, Hannah; Chaubet, Guilhem; Anderson, Edward A


    An enantioselective synthesis of the AB ring system common to the majority of the Schisandra nortriterpenoid natural products is reported. Key steps include a stereospecific ring opening of a trisubstituted epoxide and the use of a β-lactone to enable installation of the gem-dimethyl functionality of the B ring. An acetalization strategy played a key role in a late-stage biomimetic AB ring bicyclization.

  13. Synthesis of a new aromatic dianhydride monomer and related polyimide

    Institute of Scientific and Technical Information of China (English)

    Yun Xia Wei; Ming Guang Ma; Guo Hu Zhao; Sheng Ying Li; Ming Kai Chen


    A novel aromatic dianhydride monomer,3,3'-oxybis[(3,4-dicarboxyphenoxy)phenol]dianhydride,was successfully synthe-sized in three steps using 3,3'-oxybis(phenol)as starting material,which was reacted with 4,4'-oxydianiline(ODA)via a conventional thermal or chemical imidization method to produce a new polyimide.The resulting polyimide exhibited excellent solubility,and film-forming capability.

  14. Concise synthesis of the A/BCD-ring fragment of gambieric acid A (United States)

    Fuwa, Haruhiko; Fukazawa, Ryo; Sasaki, Makoto


    Gambieric acid A (GAA) and its congeners belong to the family of marine polycyclic ether natural products. Their highly complex molecular architecture and unique biological activities have been of intense interest within the synthetic community. We have previously reported the first total synthesis, stereochemical reassignment, and preliminary structure–activity relationships of GAA. Here we disclose a concise synthesis of the A/BCD-ring fragment of GAA. The synthesis started from our previously reported synthetic intermediate that represents the A/B-ring. The C-ring was synthesized via an oxiranyl anion coupling and a 6-endo cyclization, and the D-ring was forged by means of an oxidative lactonization and subsequent palladium-catalyzed functionalization of the lactone ring. In this manner, the number of linear synthetic steps required for the construction of the C- and D-rings was reduced from 22 to 11. PMID:25629027

  15. Hydrogenation of carbon dioxide by hybrid catalysts, direct synthesis of aromatic from carbon dioxide and hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Kuei Chikung; Lee Mindar (National Taiwan Univ., Taipei (Taiwan))


    To improve climatic conditions and to solve the carbon resource problem, it is desirable to develop techniques whereby carbon dioxide can be converted to valuable liquid hydrocarbons which can be used either as fuels or industrial raw materials. Direct synthesis of aromatics from carbon dioxide hydrogenation was investigated in a single stage reactor using hybrid catalysts composed of iron catalysts and HZSM-5 zeolite. Carbon dioxide was first converted to CO by the reverse water gas shift reaction, followed by the hydrogenation of CO to hydrocarbons on iron catalyst, and finally the hydrocarbons were converted to aromatics in HZSM-5. Under the operating conditions of 350{degree}C, 2100 kilopascals and CO{sub 2}/H{sub 2}={1/2} the maximum aromatic selectivity obtained was 22% with a CO{sub 2} conversion of 38% using fused iron catalyst combined with the zeolite. Together with the kinetic studies, thermodynamic analysis of the CO{sub 2} hydrogenation was also conducted. It was found that unlike Fischer Tropsch synthesis, the formation of hydrocarbons from CO{sub 2} may not be thermodynamically favored at higher temperature. However, the sufficiently high yields of aromatics possible with this process provides a route for the direct synthesis of high-octane gasoline from carbon dioxide. 24 refs., 9 figs., 5 tabs.

  16. Aromatic character of planar boron-based clusters revisited by ring current calculations

    NARCIS (Netherlands)

    Hung Tan Pham, [Unknown; Lim, Kie Zen; Havenith, Remco W. A.; Minh Tho Nguyen, [No Value


    The planarity of small boron-based clusters is the result of an interplay between geometry, electron delocalization, covalent bonding and stability. These compounds contain two different bonding patterns involving both sigma and pi delocalized bonds, and up to now, their aromaticity has been assigne

  17. Polycyclic Aromatic Compounds as Anticancer Agents: Synthesis and Biological Evaluation of Methoxy Dibenzofluorene Derivatives

    Directory of Open Access Journals (Sweden)

    Bimal Krishna Banik


    Full Text Available Synthesis of a new methoxy dibenzofluorene through alkylation, cyclodehydration and aromatization in a one-pot operation is achieved for the first time. Using this hydrocarbon, a few derivatives are prepared through aromatic nitration, catalytic hydrogenation, coupling reaction with a side chain and reduction. The benzylic position of this hydrocarbon with the side chain is oxidized and reduced. Some of these derivatives have demonstrated excellent antitumor activities in vitro. This study confirms antitumor activity depends on the structures of the molecules.

  18. One-Pot Synthesis of Tetraphene and Construction of Expanded Conjugated Aromatics. (United States)

    Wang, Jianbo; Yao, Jinzhong; Wang, Hailong; Chen, Hao; Dong, Jingcheng; Zhou, Hongwei


    Acene derivatives as a class of polycyclic aromatic hydrocarbons have attracted considerable interest because of their outstanding semiconductor properties. We developed a one-pot synthesis for fully conjugated tetraphene via a sequence of propargyl-allenyl isomerization, phosphine addition, intramolecular Wittig reactions, and Diels-Alder cyclization reactions. The derivative-conjugated aromatic compounds including carbazole or triphenylamine have been constructed via Pd-catalyzed coupling reaction with dibromotetraphene. These compounds show superior photophysical and electrochemical properties, which make them possible candidates for optoelectronic conjugated materials.

  19. Identification and quantification of seven fused aromatic rings C26H14 peri-condensed benzenoid polycyclic aromatic hydrocarbons in a complex mixture of polycyclic aromatic hydrocarbons from coal tar. (United States)

    Oña-Ruales, Jorge O; Ruiz-Morales, Yosadara; Wise, Stephen A


    A methodology for the characterization of groups of polycyclic aromatic hydrocarbons (PAHs) using a combination of normal phase liquid chromatography with ultraviolet-visible spectroscopy (NPLC/UV-vis) and gas chromatography with mass spectrometry (GC/MS) was used for the identification and quantification of seven fused aromatic rings C26H14 peri-condensed benzenoid polycyclic aromatic hydrocarbons, PAHs, in standard reference material (SRM) 1597a, complex mixture of PAHs from coal tar. The NPLC/UV-vis isolated the fractions based on the number of aromatic carbons and the GC/MS allowed the identification and quantification of five of the nine C26H14 PAH isomers; naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[b,pqr]perylene, naphtho[8,1,2-bcd]perylene, and dibenzo[cd,lm]perylene using a retention time comparison with authentic reference standards. For the other four benzenoid isomers with no available reference standards the following two approaches were used. First, the annellation theory was used to achieve the potential identification of benzo[qr]naphtho[3,2,1,8-defg]chrysene, and second, the elution distribution in the GC fractions was used to support the potential identification of benzo[qr]naphtho[3,2,1,8-defg]chrysene and to reach the tentative identifications of dibenzo[a,ghi]perylene, naphtho[7,8,1,2,3-pqrst]pentaphene, and anthra[2,1,9,8-opqra]naphthacene. It is the first time that naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[b,pqr]perylene, naphtho[8,1,2-bcd]perylene, and dibenzo[cd,lm]perylene are quantified, and the first time that benzo[qr]naphtho[3,2,1,8-defg]chrysene is potentially identified, in any sample, in any context.


    Institute of Scientific and Technical Information of China (English)

    Xia Wang; W.J. Feast


    An epoxy-terminated hyperbranched aromatic polyester (P3) was synthesized from a hyperbranched aromaticpolyester containing carboxylic acid end groups (P1), which was derived from the condensation polymerization of the AB2monomer, 5-acetoxyisophthalic acid. Polymer P1 was converted into the polymeric acid chloride by reaction with thionylchloride. The acid chloride was reacted with ethanol and glycidol to form a poly(ethyl ester) (P2) and an epoxy terminatedmaterial (P3), respectively. The reaction conditions in each step of these processes had to be controlled very carefully toavoid unwanted cross-linking reactions. The characterization of products and intermediates, including molecular weightdistributions and thermal properties, are reported.

  1. Synthesis and Antileishmanial Activity of Lipophilic Aromatic Aminoalcohols

    Directory of Open Access Journals (Sweden)

    Roberta Novaes Reis Corrales


    Full Text Available In this work, we report on the preparation and evaluation of the in vitro antileishmanial activity of a series of lipophilic aromatic aminoalcohols. All compounds were assessed for their in vitro activity against promastigotes of three Leishmania species The most lipophilic aminoalcohols bearing an aliphatic moiety with eight to 12 carbon atoms displayed a good activity against L. amazonensis and L. major, and two of them also showed antiproliferative activity against L. chagasi. The best results were obtained for the N-dodecanoyl ethylenediamine derivative and for N-decyl aminoalcohol (IC50 = 5.2 and 0.7 μM, respectively.

  2. Sandwich Complexes of the As42-Aromatic Ring with Some Transition Metals

    Institute of Scientific and Technical Information of China (English)

    LI Zhi-Wei; ZHAO Cun-Yuan; WU Wen-Sheng; CHEN Liu-Ping


    The equilibrium geometries, energies, harmonic vibrational frequencies, and nuc- leus independent chemical shifts (NICS) of the new type sandwich structures [As4MAs4]n- (M = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt; n = 0, 1 or 2) are investigated at the B3LYP level.All the [As4MAs4]n- species adopt staggered (D4d) conformations as their stable structures and eclipsed (D4h) conformations as their transition states, and once the sandwich complexes are formed, the As42- square properties remain unchanged.The NICS calculation confirms that the complexes of Fe, Co, and Ni are aromatic with negative NICS values, and those of Ru, Rh, and Ir exhibit slight aromaticity, while those of Pd, Os, and Pt show slight antiaromaticity.

  3. A novel synthesis of hemispherands

    NARCIS (Netherlands)

    Ostaszewski, Ryszard; Verboom, Willem; Reinhoudt, David N.


    A novel, flexible synthesis of hemispherands {2,5,8-trioxa[9](3,3″) m-terphenylophanes 5a-d} with different central aromatic groups is described. The key step comprises the introduction of the central aromatic ring in the last step of the synthesis via a Suzuki cross-coupling reaction using palladiu

  4. Water flow in carbon-based nanoporous membranes impacted by interactions between hydrated ions and aromatic rings (United States)

    Liu, Jian; Shi, Guosheng; Fang, Haiping


    Carbon-based nanoporous membranes, such as carbon nanotubes (CNTs), graphene/graphene oxide and graphyne, have shown great potential in water desalination and purification, gas and ion separation, biosensors, and lithium-based batteries, etc. A deep understanding of the interaction between hydrated ions in an aqueous solution and the graphitic surface in systems composed of water, ions and a graphitic surface is essential for applications with carbon-based nanoporous membrane platforms. In this review, we describe the recent progress of the interaction between hydrated ions and aromatic ring structures on the carbon-based surface and its applications in the water flow in a carbon nanotube. We expect that these works can be extended to the understanding of water flow in other nanoporous membranes, such as nanoporous graphene, graphyne and stacked sheets of graphene oxide.

  5. Exploring mild enzymatic sustainable routes for the synthesis of bio-degradable aromatic-aliphatic oligoesters. (United States)

    Pellis, Alessandro; Guarneri, Alice; Brandauer, Martin; Acero, Enrique Herrero; Peerlings, Henricus; Gardossi, Lucia; Guebitz, Georg M


    The application of Candida antarctica lipase B in enzyme-catalyzed synthesis of aromatic-aliphatic oligoesters is here reported. The aim of the present study is to systematically investigate the most favorable conditions for the enzyme catalyzed synthesis of aromatic-aliphatic oligomers using commercially available monomers. Reaction conditions and enzyme selectivity for polymerization of various commercially available monomers were considered using different inactivated/activated aromatic monomers combined with linear polyols ranging from C2 to C12 . The effect of various reaction solvents in enzymatic polymerization was assessed and toluene allowed to achieve the highest conversions for the reaction of dimethyl isophthalate with 1,4-butanediol and with 1,10-decanediol (88 and 87% monomer conversion respectively). Mw as high as 1512 Da was obtained from the reaction of dimethyl isophthalate with 1,10-decanediol. The obtained oligomers have potential applications as raw materials in personal and home care formulations, for the production of aliphatic-aromatic block co-polymers or can be further functionalized with various moieties for a subsequent photo- or radical polymerization.

  6. Synthesis of a tricyclic lactam via Beckmann rearrangement and ring-rearrangement metathesis as key steps. (United States)

    Kotha, Sambasivarao; Ravikumar, Ongolu; Majhi, Jadab


    A tricyclic lactam is reported in a four step synthesis sequence via Beckmann rearrangement and ring-rearrangement metathesis as key steps. Here, we used a simple starting material such as dicyclopentadiene.

  7. Benzoylureas as removable cis amide inducers: synthesis of cyclic amides via ring closing metathesis (RCM). (United States)

    Brady, Ryan M; Khakham, Yelena; Lessene, Guillaume; Baell, Jonathan B


    Rapid and high yielding synthesis of medium ring lactams was made possible through the use of a benzoylurea auxiliary that serves to stabilize a cisoid amide conformation, facilitating cyclization. The auxiliary is released after activation under the mild conditions required to deprotect a primary amine, such as acidolysis of a Boc group in the examples given here. This methodology is a promising tool for the synthesis of medium ring lactams, macrocyclic natural products and peptides.

  8. Synthesis of alkenyl boronates from allyl-substituted aromatics using an olefin cross-metathesis protocol. (United States)

    Hemelaere, Rémy; Carreaux, François; Carboni, Bertrand


    An efficient synthesis of 3-aryl-1-propenyl boronates from pinacol vinyl boronic ester and allyl-substituted aromatics by cross metathesis is reported. Although the allylbenzene derivatives are prone to isomerization reaction under metathesis conditions, we found that some ruthenium catalysts are effective for this methodology. This strategy thus provides an interesting alternative approach to alkyne hydroboration, leading to the preparation of unknown compounds. Moreover, the boron substituent can be replaced by various functional groups in good yields.

  9. On the lack of ring-current aromaticity of (heteroatom) [N]radialenes and their dianions

    NARCIS (Netherlands)

    Domene, C.; Fowler, P.W.; Jenneskens, L.W.; Steiner, E.


    Current-density maps, calculated at the ab initio RHF//6-31G**/ CTOCD-DZ level, show no significant π ring current in planar equilateral geometries ofneutral and dianionic [N]radialenes, oxocarbons and thiocarbons CNYNq- (Y=CH2, O, S; N=4, 5, 6; q=0 (1a-12 a), 2 (1b-12b)). Only the N=3 deltate diani


    Institute of Scientific and Technical Information of China (English)

    Xiao-hua Huang; Wei Huang; Yong-feng Zhou; De-yue Yan


    Two highly soluble aromatic polyimides were synthesized successfully from a diamine with two tert-butyl groups (MBTBA) and dianhydrides with a thioether or sulfone moiety (DTDA and DSDA). Both of them showed excellent solubility in common solvents such as chloroform, tetrahydrofuran and dioxane at the room temperature. The numberaverage molecular weight was 6.0 × 104 and 8.3 × 104 according to gel permeation chromatography relative to a polystyrene standard, and the polydispersity index was 1.80 and 1.82 respectively. The glass-transition temperatures of them were 286℃and 314℃ (or 315℃ and 358℃) respectively, as measured by differential scanning calorimetry (or dynamic mechanical analysis). The 5% weight loss temperature of both was near 490℃ in N2 by thermogravimetric analysis. These results indicated that the tert-butyl pendent groups reduced the interactions among polymer chains and the thioether or sulfone moiety was flexible which may improve their solubility in conventional organic solvents without the loss of thermal stability.Transparent and flexible films of the two polyimides were obtained via solution casting. The MBTBA-DTDA membrane had higher storage moduli than those of the MBTBA-DSDA membrane.

  11. Synthesis, Characterization, and Pharmacological Evaluation of Selected Aromatic Amines

    Directory of Open Access Journals (Sweden)

    Hammad Ismail


    Full Text Available Aromatic amines 1-amino-4-phenoxybenzene (A-1A, 2-(4-aminophenoxy naphthalene (A-2A, and 1-(4-aminophenoxy naphthalene (A-3A were synthesized by the reduction of corresponding nitroaromatics with hydrazine monohydrate and Pd/C 5% (w/w. The newly synthesized compounds were characterized by FTIR, 1H NMR, 13C NMR, UV-visible spectrophotometer, and mass spectrometry and their biological activities were investigated along with structurally similar 4-(4-aminophenyloxy biphenyl (A-A. Results of brine shrimp cytotoxicity assay showed that almost all of the compounds had LD50 values <1 μg/mL. The compounds also showed significant antitumor activity with IC50 values ranging from 67.45 to 12.2 µgmL−1. The cytotoxicity and antitumor studies correlate the results which suggests the anticancerous nature of compounds. During the interaction study of these compounds with DNA, all of the compounds showed hyperchromic effect indicating strong interaction through binding with the grooves of DNA. Moreover, A-3A also showed decrease in λmax confirming higher propensity for DNA groove binding. In DPPH free radical scavenging assay, all the compounds showed potential antioxidant capability. The compounds were highly active in protecting DNA against hydroxyl free radicals. DNA interaction and antioxidant results back up each other indicating that these compounds have potential to be used as cancer chemopreventive agents. Additionally, one compound (A-1A showed significant antibacterial and antifungal activity as well.

  12. Effects of polycyclic aromatic hydrocarbons on microbial community structure and PAH ring hydroxylating dioxygenase gene abundance in soil. (United States)

    Sawulski, Przemyslaw; Clipson, Nicholas; Doyle, Evelyn


    Development of successful bioremediation strategies for environments contaminated with recalcitrant pollutants requires in-depth knowledge of the microorganisms and microbial processes involved in degradation. The response of soil microbial communities to three polycyclic aromatic hydrocarbons, phenanthrene (3-ring), fluoranthene (4-ring) and benzo(a)pyrene (5-ring), was examined. Profiles of bacterial, archaeal and fungal communities were generated using molecular fingerprinting techniques (TRFLP, ARISA) and multivariate statistical tools were employed to interpret the effect of PAHs on community dynamics and composition. The extent and rate of PAH removal was directly related to the chemical structure, with the 5-ring PAH benzo(a)pyrene degraded more slowly than phenathrene or fluoranthene. Bacterial, archaeal and fungal communities were all significantly affected by PAH amendment, time and their interaction. Based on analysis of clone libraries, Actinobacteria appeared to dominate in fluoranthene amended soil, although they also represented a significant portion of the diversity in phenanthrene amended and unamended soils. In addition there appeared to be more γ-Proteobacteria and less Bacteroidetes in soil amended with either PAH compared to the control. The soil bacterial community clearly possessed the potential to degrade PAHs as evidenced by the abundance of PAH ring hydroxylating (PAH-RHDα) genes from both gram negative (GN) and gram positive (GP) bacteria in PAH-amended and control soils. Although the dioxygenase gene from GP bacteria was less abundant in soil than the gene associated with GN bacteria, significant (p PAH-RHDα gene were observed during phenanthrene and fluoranthene degradation, whereas there was no significant difference in the abundance of the GN PAH-RHDα gene during the course of the experiment. Few studies to-date have examined the effect of pollutants on more than one microbial community in soil. The current study provides

  13. Advance in the synthesis of aromatic amine via direct amination

    Institute of Scientific and Technical Information of China (English)


    Arylamines are very common and important organic molecules. Acting as important intermediates in medical and chemical industry, they are widely used in the synthesis of pharmaceuticals, dyes, pesticides, rubber additives, isocyanates and heterocyclic compounds. The traditional methods for the synthesis of arylamines include several steps. The production of aniline, for example, includes the following steps: the production of nitro-benzene by the nitration of benzene, and the reduction of the resulting nitro-benzene by catalytic hydrogenation or other reduction ways[1-6]; or the substitution of phenol or chlorbenzene by amino groups, etc.[7-10]. There are several disadvantages for these methods: low atom utilization, strict operation condition, large amount of by-products and serious environmental pollution, which could not afford for the needs of a sustainable civilization. So there has been growing interest in the direct amination to produce arylamines recently. With the direct methods, the multi- step reaction may change into one step, the atom utilization can be evidently improved, and the by-products H2 or/and H2O are harmless to the environment.

  14. Efficient oxidative dechlorination and aromatic ring cleavage of chlorinated phenols catalyzed by iron sulfophthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Sorokin, A.; Meunier, B. [Laboratoire de Chimie de Coordination du CNRS, Toulouse (France); Seris, J.L. [Elf-Aquitaine, Artix (France)


    An efficient method has been developed for the catalytic oxidation of pollutants that are not easily degraded. The products of the hydrogen peroxide (H{sub 2}O{sub 2}) oxidation of 2,4,6-trichlorophenol (TCP) catalyzed by the iron complex 2,9,16,23-tetrasulfophthalocyanine (FePcS) were observed to be chloromaleic, chlorofumaric, maleic, and fumaric acids from dechlorination and aromatic cycle cleavage, as well as additional products that resulted from oxidative coupling. Quantitative analysis of the TCP oxidation reaction revealed that up to two chloride ions were released per TCP molecule. This chemical system, consisting of an environmentally safe oxidant (H{sub 2}O{sub 2}) and an easily accessible catalyst (FePcS), can perform several key steps in the oxidative mineralization of TCP, a paradigm of recalcitrant pollutants. 20 refs., 4 figs., 2 tabs.

  15. Recent applications of ring-rearrangement metathesis in organic synthesis

    Directory of Open Access Journals (Sweden)

    Sambasivarao Kotha


    Full Text Available Ring-rearrangement metathesis (RRM involves multiple metathesis processes such as ring-opening metathesis (ROM/ring-closing metathesis (RCM in a one-pot operation to generate complex targets. RRM delivers complex frameworks that are difficult to assemble by conventional methods. The noteworthy point about this type of protocol is multi-bond formation and it is an atom economic process. In this review, we have covered literature that appeared during the last seven years (2008–2014.

  16. Efficient synthesis of enantiopure conduritols by ring-closing metathesis

    DEFF Research Database (Denmark)

    Jørgensen, Morten; Iversen, Erik Høgh; Paulsen, Andreas Lundtang;


    Two short synthetic approaches to enantiopure conduritols are described starting from the chiral pool. In both cases, the cyclohexene ring is assembled via ring-closing olefin metathesis. The terminal diene precursers for the metathesis reaction are prepared either from octitols or from tartaric...

  17. Low-pressure effective fluorescence lifetimes and photo-physical rate constants of one- and two-ring aromatics (United States)

    Benzler, Thorsten; Faust, Stephan; Dreier, Thomas; Schulz, Christof


    One- and two-ring aromatics such as toluene and naphthalene are frequently used molecular tracer species in laser-induced fluorescence (LIF) imaging diagnostics. Quantifying LIF signal intensities requires knowledge of the photo-physical processes that determine the fluorescence quantum yield. Collision-induced and intramolecular energy transfer processes in the excited electronic state closely interact under practical conditions. They can be separated through experiments at variable low pressures. Effective fluorescence lifetimes of gaseous toluene, 1,2,4-trimethylbenzene, anisole, naphthalene, and 1-methylnaphthalene diluted in CO2 were measured after picosecond laser excitation at 266 nm and time-resolved detection of fluorescence intensities. Measurements in an optically accessible externally heated cell between 296 and 475 K and 0.010-1 bar showed that effective fluorescence lifetimes generally decrease with temperature, while the influence of the bath-gas pressure depends on the respective target species and temperature. The results provide non-radiative and fluorescence rate constants and experimentally validate the effect of photo-induced cooling.

  18. Unravelling airborne polycyclic aromatic hydrocarbons (PAHs in southern China using tree-rings of 100-yr old Pinus Kwangtungensis

    Directory of Open Access Journals (Sweden)

    L. B. Huang


    Full Text Available Reliable perennial biomonitoring of airborne polycyclic aromatic hydrocarbons (PAHs is urgently necessary to detect long-term impacts of anthropogenic emission, in response to industrial policies and combustion technology adoption. One hundred records of airborne PAHs were novelly demonstrated by analyzing the tree-rings of Kwangtung pine (Pinus kwangtungensis formed from 1883 to 2007 at Naling Mountains of southern China. The total concentrations of PAHs (∑PAHs detected in the tree xylem did not progressively increase against the time. Temporal increase of high molecular-weight PAHs (HMW-PAHs coincided well to the historical-socioeconomic status in China, suggesting HMW-PAHs in old trees growing at high mountains were more indicative of regionally historical changes in airborne PAHs compared with ∑PAHs. Compositional analysis indicated airborne PAHs absorbed and accumulated in tree tissues were pyrogenic origination. Principal component analysis revealed PAHs inputs were quite historically diversiform and unevenly distributed in the atmosphere of Nanling Mountains of southern China. Dendroanalysis of old trees grown at geographically sink locations could be a useful biomonitoring technique for unravelling historical changes in PAHs composition and intensity in the atmosphere, in relation to regional industrial development and fuel consumptions.

  19. On the synthesis, measurement and applications of octanuclear heterometallic rings (United States)

    Faust, T. B.

    Inorganic macrocycles have stimulated interest in recent years for their magnetic properties, their associated host-guest chemistry and their aesthetically appealing structures. These characteristics have led to suggestions that they could be exploited for the purposes of ion recognition, catalysis, as single molecule magnets, MRI agents, antibacterial agents and as part of larger architectures in a molecular machine. This thesis explores the properties of a group of chromium(III) macrocycles, with functionality tailored towards different pursuits. Firstly the magnetic properties of a newly synthesised family of ring dimers are investigated. The nature of magnetic exchange within each ring leads to a net electronic spin which, it has been proposed, could represent a quantum binary digit within a quantum information processing system. By linking together pairs of rings, the degree of inter-ring communication can be determined. Such interactions are important for the correlation of spin as initiation of quantum entanglement, a pre-requisite for quantum computing. The rings can also act as fluoro-metallocrown, hosting the molecule which templated their formation. A range of rings with different guests are synthesised and their solid and solution state structures are explored. On templating about bulky dialykyl amines hybrid organic-inorganic rotaxanes are formed where the guest is fixed. In contrast when using small amines and alkali metals, exchange of guests is possible. The dynamics of all of these systems are investigated with proton NMR, quite remarkable for such highly paramagnetic complexes.

  20. Unravelling airborne polycyclic aromatic hydrocarbons (PAHs) in southern China using tree-rings of 100-yr old Pinus Kwangtungensis


    Kuang, Y. W.; Huang, Z.H.; Wen, D Z; Li, J; L. B. Huang


    Reliable perennial biomonitoring of airborne polycyclic aromatic hydrocarbons (PAHs) is urgently necessary to detect long-term impacts of anthropogenic emission, in response to industrial policies and combustion technology adoption. One hundred records of airborne PAHs were novelly demonstrated by analyzing the tree-rings of Kwangtung pine (Pinus kwangtungensis) formed from 1883 to 2007 at Naling Mountains of southern China. The total concentrations of PAHs (∑PAHs) detec...

  1. Structure-activity study on the spatial arrangement of the third aromatic ring of endomorphins 1 and 2 using an atypical constrained C terminus. (United States)

    Yu, Ye; Shao, Xuan; Cui, Yun; Liu, Hong-mei; Wang, Chang-ling; Fan, Ying-zhe; Liu, Jing; Dong, Shou-liang; Cui, Yu-xing; Wang, Rui


    The discovery of endomorphins (EMs) has opened the possibility of searching for new analgesics. However, the design of peptide analgesics has proven to be very difficult as a result of their conformational flexibility and a lack of clarity in structure-activity relationships (SAR). In EMs, the amino acid side chains exhibit considerable conformational flexibility, especially in the third aromatic ring, which is free to adopt a bioactive conformation. To resolve these problems, a series of C terminus EM analogues, [Xaa(4)-R]EMs, modified through the substitution of Phe(4) with nonaromatic residues and termination with benzyl groups, were designed to generate conformational constrains of the third aromatic ring by amide bond and torsion angles (phi(4) and psi(4)) of Xaa(4). Introduction of (S)-alpha-methyl or (S)/(R)-alpha-carboxamide on the methylene unit of the benzyl group was designed to produce an atypical topographical constraint (phi(5)) of the third aromatic ring rotation. Interestingly, some EM derivatives, with elimination of the C-terminal carboxamide group and significant changes in the address sequence (Phe(4)-NH(2)), still exhibited higher mu-opioid receptor (MOR) affinity than unmodified EMs. In contrast, some analogues with incorrectly constrained C termini displayed very low affinity and pharmacological activities. Thus, our results indicate that these EM analogues, with atypical constrained C termini, provide model compounds with potent MOR agonism. They also give evidence that the proper spatial orientation and conformational restriction of the third aromatic ring are crucial for the interaction of EMs with MOR.

  2. Copper Causes Regiospecific Formation of C4F8-Containing Six-Membered Rings and their Defluorination/Aromatization to C4F4-Containing Rings in Triphenylene/1,4-C4F8I2 Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Rippy, Kerry C.; Bukovsky, Eric V.; Clikeman, Tyler T.; Chen, Yu-Sheng; Hou, Gao-Lei; Wang, Xue B.; Popov, Alexey; Boltalina, Olga V.; Strauss, Steven H.


    The presence of Cu in reactions of triphenylene (TRPH) and 1,4-C4F8I2 at 360 °C led to regiospecific substitution of TRPH ortho C(β) atoms to form C4F8-containing rings, completely suppressing substitution on C(α) atoms. In addition, Cu caused selective reductive-defluorination/aromatization (RD/A) to form C4F4- containing aromatic rings. Without Cu, the reactions of TRPH and 1,4- C4F8I2 were not regiospecific and no RD/A was observed. These results, supported by DFT calculations, are the first examples of Cupromoted (i) regiospecific perfluoroannulation, (ii) preparative C–F activation, and (iii) RD/A. HPLC-purified products were characterized by X-ray diffraction, low-temperature PES, and 1H/19F NMR.

  3. Secondary Structures in a Freeze-Dried Lignite Humic Acid Fraction Caused by Hydrogen-Bonding of Acidic Protons with Aromatic Rings. (United States)

    Cao, Xiaoyan; Drosos, Marios; Leenheer, Jerry A; Mao, Jingdong


    A lignite humic acid (HA) was separated from inorganic and non-HA impurities (i.e., aluminosilicates, metals) and fractionated by a combination of dialysis and XAD-8 resin. Fractionation revealed a more homogeneous structure of lignite HA. New and more specific structural information on the main lignite HA fraction is obtained by solid-state nuclear magnetic resonance (NMR) spectroscopy. Quantitative (13)C multiple cross-polarization (multiCP) NMR indicated oxidized phenyl propane structures derived from lignin. MultiCP experiments, conducted on potassium HA salts titrated to pH 10 and pH 12, revealed shifts consistent with carboxylate and phenolate formation, but structural changes associated with enolate formation from aromatic beta keto acids were not detected. Two-dimensional (1)H-(13)C heteronuclear correlation (2D HETCOR) NMR indicated aryl-aliphatic ketones, aliphatic and aromatic carboxyl groups, phenol, and methoxy phenyl ethers. Acidic protons from carboxyl groups in both the lignite HA fraction and a synthetic HA-like polycondensate were found to be hydrogen-bonded with electron-rich aromatic rings. Our results coupled with published infrared spectra provide evidence for the preferential hydrogen bonding of acidic hydrogens with electron-rich aromatic rings rather than adjacent carbonyl groups. These hydrogen-bonding interactions likely result from stereochemical arrangements in primary structures and folding.

  4. Ring Walking/Oxidative Addition Reactions for the Controlled Synthesis of Conjugated Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Bazan, Guillermo C


    Power conversion efficiencies of plastic solar cells depend strongly on the molecular weight characteristics of the semiconducting polymers used for their fabrication. The synthesis of these materials typically relies on transition metal mediated catalytic reactions. In many instances, the ideal structures cannot be attained because of deficiencies in these reactions, particularly when it comes to being able to achieve high number average molecular weights and narrow molecular weight distributions. Another important conjugated polymer structure of interest is one in which a single functional group is attached at the end group of the chain. Such systems would be ideal for modifying surface properties at interfaces and for labeling biomolecular probes used in fluorescent biosensors. To respond to the challenges above, our efforts have centered on the design of homogenous transition metal complexes that are easy to prepare and effective in carrying out living, or quasi-living, condensative chain polymerization reactions. The key mechanistic challenge for the success of this reaction is to force the insertion of one monomer unit at a time via a process that involves migration of the transition metal-containing fragment to one terminus of the polymer chain. Chain growth characteristics are therefore favored when the metal does not dissociate from the newly formed reductive elimination product. We have proposed that dissociation is disfavored by the formation of a -complex, in which the metal can sample various locations of the electronically delocalized framework, a process that we term ring-walking , and find the functionality where oxidative addition takes place. Success has been achieved in the nickel-mediated cross coupling reaction of Grignard reagents with aromatic halides by using bromo[1,2-bis(diphenylphosphino)ethane]phenylnickel. This reagent can yield poly(thiophene)s (one of the most widely used type of polymer in plastic solar cells) with excellent

  5. Analysis of polycyclic aromatic hydrocarbons in tree-rings of Masson pine (Pinus massoniana L.) from two industrial sites in the Pearl River Delta, south China. (United States)

    Kuang, Yuan-wen; Zhou, Guo-yi; Wen, Da-zhi; Li, Jiong; Sun, Fang-fang


    Concentrations of polycyclic aromatic hydrocarbons (PAHs) were examined and potential sources of PAHs were identified from the dated tree-rings of Masson pine (Pinus massoniana L.) near two industrial sites (Danshuikeng, DSK and Xiqiaoshan, XQS) in the Pearl River Delta of south China. Total concentrations of PAHs (∑PAHs) were revealed with similar patterns of temporal trends in the tree-rings at both sites, suggesting tree-rings recorded the historical variation in atmospheric PAHs. The differences of individual PAHs and of ∑PAHs detected in the tree-rings between the two sites reflected the historical differences of airborne PAHs. Regional changes in industrial activities might contribute to the site-specific and period-specific patterns of the tree-ring PAHs. The diagnostic PAH ratios of Ant/(Ant + PA), FL/(FL + Pyr), and BaA/(BaA + Chr)) revealed that PAHs in the tree-rings at both sites mainly stemmed from the combustion process (pyrogenic sources). Principal component analysis further confirmed that wood burning, coal combustion, diesel, and gasoline-powered vehicular emissions were the dominant contributors of PAHs sources at DSK, while diesel combustion, gasoline and natural gas combustion, and incomplete coal combustion were responsible for the main origins of PAHs at XQS. Tree-ring analysis of PAHs was indicative of PAHs from a mixture of sources of combustion, thus minimizing the bias of short-term active air sampling.

  6. Controlled synthesis of monodisperse gold nanorods with different aspect ratios in the presence of aromatic additives (United States)

    Wang, Yun; Wang, Feihu; Guo, Yuan; Chen, Rongjun; Shen, Yuanyuan; Guo, Aijie; Liu, Jieying; Zhang, Xiao; Zhou, Dejian; Guo, Shengrong


    This paper reports the synthesis of monodisperse gold nanorods (GNRs) via a simple seeded growth approach in the presence of different aromatic additives, such as 7-bromo-3-hydroxy-2-naphthoic acid (7-BrHNA), 3-hydroxy-2-naphthoic acid (HNA), 5-bromosalicylic acid (5-BrSA), salicylic acid (SA), or phenol (PhOH). Effects of the aromatic additives and hydrochloric acid (HCl) on the structure and optical properties of the synthesized GNRs were investigated. The longitudinal surface plasmon resonance (LSPR) peak wavelength of the resulting GNRs was found to be dependent on the aromatic additive in the following sequence: 5-BrSA (778 nm) > 7-BrHNA (706 nm) > SA (688 nm) > HNA (676 nm) > PhOH (638 nm) without the addition of HCl, but this was changed to 7-BrHNA (920 nm) > SA (890 nm) > HNA (872 nm) > PhOH (858 nm) > 5-BrSA (816 nm) or 7-BrHNA (1,005 nm) > PhOH (995 nm) > SA (990 nm) > HNA (980 nm) > 5-BrSA (815 nm) with the addition of HCl or HNO3, respectively. The LSPR peak wavelength was increased with the increasing concentration of 7-BrHNA without HCl addition; however, there was a maximum LSPR peak wavelength when HCl was added. Interestingly, the LSPR peak wavelength was also increased with the amount of HCl added. The results presented here thus established a simple approach to synthesize monodisperse GNRs of different LSPR wavelengths.

  7. Nano-rings with a handle – Synthesis of substituted cycloparaphenylenes

    Directory of Open Access Journals (Sweden)

    Anne-Florence Tran-Van


    Full Text Available The research of cycloparaphenylenes (CPPs, the smallest armchair carbon nanotube, has been a quest for the past decades which experienced a revival in 2008 when the first synthesis was achieved. Since then CPPs with various ring sizes have been realized. The incorporation of substituents and the synthesis of CPPs with building blocks different from phenyl rings bear challenges of their own. Such structures, however, are highly interesting, as they allow for an incorporation of CPPs as defined nano-objects for other applications. Therefore, this review provides a status report about the current efforts in synthesizing CPPs beyond the parent unsubstituted oligo-phenylene structure.

  8. Synthesis of benzamides by microwave assisted ring opening of less reactive dimethylaminobenzylidene oxazolone

    Directory of Open Access Journals (Sweden)

    Saurabh C. Khadse


    Full Text Available This paper presents the synthesis of some benzamide compounds (B1–B10 by microwave-assisted ring opening of 4-(4-dimethylaminobenzylidene-2-phenyl-5-oxazolone (AZ4. By conventional synthesis involving heating, it was found difficult to obtain ring-opened products, probably due to poor tendency of the carbonyl carbon (C5 of AZ4 to undergo nucleophilic attack by mono/or disubstituted anilines. Microwave assisted reactions were easy to perform, have reduced the reaction time and produced good yields.

  9. (Thio)urea-mediated synthesis of functionalized six-membered rings with multiple chiral centers (United States)

    Koutoulogenis, Giorgos; Kaplaneris, Nikolaos


    Summary Organocatalysis, now running its second decade of life, is being considered one of the main tools a synthetic chemist has to perform asymmetric catalysis. In this review the synthesis of six-membered rings, that contain multiple chiral centers, either by a ring closing process or by a functionalization reaction on an already existing six-membered ring, utilizing bifunctional (thio)ureas will be summarized. Initially, the use of primary amine-thioureas as organocatalysts for the above transformation is being discussed, followed by the examples employing secondary amine-thioureas. Finally, the use of tertiary amine-thioureas and miscellaneous examples are presented. PMID:27340441

  10. (Thiourea-mediated synthesis of functionalized six-membered rings with multiple chiral centers

    Directory of Open Access Journals (Sweden)

    Giorgos Koutoulogenis


    Full Text Available Organocatalysis, now running its second decade of life, is being considered one of the main tools a synthetic chemist has to perform asymmetric catalysis. In this review the synthesis of six-membered rings, that contain multiple chiral centers, either by a ring closing process or by a functionalization reaction on an already existing six-membered ring, utilizing bifunctional (thioureas will be summarized. Initially, the use of primary amine-thioureas as organocatalysts for the above transformation is being discussed, followed by the examples employing secondary amine-thioureas. Finally, the use of tertiary amine-thioureas and miscellaneous examples are presented.

  11. Synthetic studies on maitotoxin. 1. Stereoselective synthesis of the C'D'E'F'-ring system having a side chain. (United States)

    Morita, Masayuki; Ishiyama, Seishi; Koshino, Hiroyuki; Nakata, Tadashi


    The stereoselective synthesis of the maitotoxin C'D'E'F'-ring system having a side chain has been accomplished through a convergent strategy. The key reactions include Horner-Wadsworth-Emmons coupling of the C'D'E'-ring and the side chain and subsequent construction of the F'-ring by silane reduction of dihydropyran.

  12. Allylsilanes in the synthesis of three to seven membered rings: the silylcuprate strategy

    Directory of Open Access Journals (Sweden)

    Sañudo M Carmen


    Full Text Available Abstract Addition of low order phenyldimethylsilylcyanocuprates to allenes followed by "in situ" reaction of the intermediate silylcuprate with electrophiles ("the silylcuprate strategy" provides new routes for the synthesis of functionalised allylsilanes, which undergo highly stereocontrolled silicon-assisted intramolecular cyclizations leading to three to seven membered ring-formation.

  13. Synthesis of Gabosine A and N from Ribose by the Use of Ring-Closing Metathesis

    DEFF Research Database (Denmark)

    Monrad, Rune Nygaard; Fanefjord, Mette; Hansen, Flemming Gundorph;


    -methylallyl bromide. The functionalized octa-1,7-diene, thus obtained, is converted into the six-membered gabosine skeleton by ring-closing olefin metathesis. Subsequent protective group manipulations and oxidation gives rise to gabosine N in a total of 8 steps from ribose while the synthesis of gabosine...

  14. Synthesis of tetrahydrokhusitone. Annulation of the cyclohexane ring by free radical and carbanionic sequence of reactions

    Directory of Open Access Journals (Sweden)



    Full Text Available The synthesis of norcadinane sesquiterpene tetrahydrokhusitone 1 has been achieved by a new method for annulation of cyclohexane ring involving a sequence of free radical d-alkylation of the non-activated carbon atom and intramolecular carbanionic alkylation. (–-Menthol was used as the starting compound.

  15. Synthesis and Structure of 1D Na6 Cluster Chain with Short Na-Na Distance: Organic like Aromaticity in Inorganic Metal Cluster

    CERN Document Server

    Khatua, S; Chattaraj, P K; Roy, D R; Bhattacharjee*, Manish; Chattaraj*, Pratim K.; Khatua, Snehadrinarayan; Roy, Debesh R.


    A unique 1D chain of sodium cluster containing (Na6) rings stabilized by a molybdenum containing metalloligand has been synthesized and characterized. DFT calculations show striking resemblance in their aromatic behaviour with the corresponding hydrocarbon analogues

  16. π-Extended Star-Shaped Polycyclic Aromatic Hydrocarbons based on Fused Truxenes: Synthesis, Self-Assembly, and Facilely Tunable Emission Properties. (United States)

    Cheng, Cheng; Jiang, Yi; Liu, Cheng-Fang; Zhang, Jian-Dong; Lai, Wen-Yong; Huang, Wei


    A new set of star-shaped polycyclic aromatic hydrocarbons (PAHs) based on naphthalene-fused truxenes, TrNaCn (n=1-4), were synthesized and characterized. The synthesis involved a microwave-assisted six-fold Suzuki coupling reaction, followed by oxidative cyclodehydrogenation. Multiple dehydrocyclization products could be effectively isolated in a single reaction, thus suggesting that the oxidative cyclodehydrogenation reaction involved a stepwise ring-closing process. The thermal, optical, and electrochemical properties and the self-assembly behavior of the resulting oxidized samples were investigated to understand the impact of the ring-fusing process on the properties of the star-shaped PAHs. Distinct bathochromic shift of the absorption maxima (λmax ) revealed that the molecular conjugation extended with the stepwise ring-closing reactions. The optical band-gap energy of these PAHs varied significantly on increasing the number of fused rings, thereby resulting in readily tunable emissive properties of the resultant star-shaped PAHs. Interestingly, the generation of rigid "arms" by using perylene analogues caused TrNaC2 and TrNaC3 to show significantly enhanced photoluminescence quantum yields (PLQYs) in solution (η=0.65 and 0.66, respectively) in comparison with those of TrNa and TrNaC1 (η=0.08 and 0.16, respectively). Owing to strong intermolecular interactions, the TrNa precursor was able to self-assemble into rod-like microcrystals, which could be facilely identified by the naked eye, whilst TrNaC1 self-assembled into nanosheets once the naphthalene rings had fused. This study offers a unique platform to gain further insight into-and a better understanding of-the photophysical and self-assembly properties of π-extended star-shaped PAHs.

  17. Rapid and efficient synthesis of new chiral aromatic amide molecular tweezers under solvent-free conditions using microwave

    Institute of Scientific and Technical Information of China (English)

    Xiao Xiang Zhao; Zhi Gang Zhao; Xing Li Liu; Xiu Ming Wu


    An efficient and simple method for the synthesis of new chiral aromatic amide molecular tweezers by irradiation with microwave under solvent-free conditions has been developed.Its main advantages are short reaction times.good conversions and the environmentally friendly nature of the process.

  18. Selective synthesis of Rh5 carbonyl clusters within a polyamine dendrimer for chemoselective reduction of nitro aromatics. (United States)

    Maeno, Zen; Mitsudome, Takato; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi


    The selective synthesis of the [Rh5(CO)15](-) cluster within the PPI dendrimer was successfully demonstrated. The dendrimer-encapsulated [Rh5(CO)15](-) was resistant to decomposition under the catalytic reaction conditions and exhibited extremely high selectivity for the chemoselective reduction of nitro groups of various nitro aromatics with other reducible groups using CO/H2O as a reductant.

  19. Study towards diversity oriented synthesis of optically active substituted cyclopentane fused carbocyclic and oxacyclic medium-sized rings: Competition between Grubbs-II catalyzed ring closing olefin metathesis and ring closing carbonyl-olefin metathesis

    Indian Academy of Sciences (India)



    A study towards diversity-oriented synthesis of optically active cyclopentane fused bicyclic frameworks has been accomplished. The common intermediate was prepared from commercially available starting material (S)-carvone. The observations on competition between Grubbs-II catalyzed ring closing metathesis (RCM) and ring closing carbonyl-olefin metathesis (RCCOM) were the key features of the study.

  20. Controlled synthesis of monodisperse gold nanorods with different aspect ratios in the presence of aromatic additives

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yun; Wang, Feihu [Shanghai Jiao Tong University, School of Pharmacy (China); Guo, Yuan [University of Leeds, School of Chemistry and Astbury Centre for Structural Molecular Biology (United Kingdom); Chen, Rongjun, E-mail: [Imperial College London, Department of Chemical Engineering (United Kingdom); Shen, Yuanyuan; Guo, Aijie; Liu, Jieying; Zhang, Xiao [Shanghai Jiao Tong University, School of Pharmacy (China); Zhou, Dejian, E-mail: [University of Leeds, School of Chemistry and Astbury Centre for Structural Molecular Biology (United Kingdom); Guo, Shengrong, E-mail: [Shanghai Jiao Tong University, School of Pharmacy (China)


    This paper reports the synthesis of monodisperse gold nanorods (GNRs) via a simple seeded growth approach in the presence of different aromatic additives, such as 7-bromo-3-hydroxy-2-naphthoic acid (7-BrHNA), 3-hydroxy-2-naphthoic acid (HNA), 5-bromosalicylic acid (5-BrSA), salicylic acid (SA), or phenol (PhOH). Effects of the aromatic additives and hydrochloric acid (HCl) on the structure and optical properties of the synthesized GNRs were investigated. The longitudinal surface plasmon resonance (LSPR) peak wavelength of the resulting GNRs was found to be dependent on the aromatic additive in the following sequence: 5-BrSA (778 nm) > 7-BrHNA (706 nm) > SA (688 nm) > HNA (676 nm) > PhOH (638 nm) without the addition of HCl, but this was changed to 7-BrHNA (920 nm) > SA (890 nm) > HNA (872 nm) > PhOH (858 nm) > 5-BrSA (816 nm) or 7-BrHNA (1,005 nm) > PhOH (995 nm) > SA (990 nm) > HNA (980 nm) > 5-BrSA (815 nm) with the addition of HCl or HNO{sub 3}, respectively. The LSPR peak wavelength was increased with the increasing concentration of 7-BrHNA without HCl addition; however, there was a maximum LSPR peak wavelength when HCl was added. Interestingly, the LSPR peak wavelength was also increased with the amount of HCl added. The results presented here thus established a simple approach to synthesize monodisperse GNRs of different LSPR wavelengths.

  1. Synthesis and stereochemistry of 6-membered ring phosphonates

    Directory of Open Access Journals (Sweden)

    Michael D. Pungente


    Full Text Available Background: Organophosphorus compounds have important industrial and biomedical applications as pharmaceutical and agrochemical agents, as well as transition state analogs for the production of monoclonal antibodies. Methods: Two diastereomers of a 6-membered ring, cyclic phenyl phosphonate were synthesized in 8 steps from 1,3-butanediol. Results: The stereochemistry of the diastereomers was elucidated on the basis of H NMR nuclear Overhauser effects (NOE difference experiments. Conclusions: Such cyclic phosphonates may have utility serving as transition state analogs for the production of monoclonal antibodies.

  2. Unexpected Scholl Reaction of 6,7,13,14-Tetraarylbenzo[k]tetraphene: Selective Formation of Five-Membered Rings in Polycyclic Aromatic Hydrocarbons. (United States)

    Liu, Junzhi; Narita, Akimitsu; Osella, Silvio; Zhang, Wen; Schollmeyer, Dieter; Beljonne, David; Feng, Xinliang; Müllen, Klaus


    Cyclodehydrogenation is a versatile reaction that has enabled the syntheses of numerous polycyclic aromatic hydrocarbons (PAHs). We now describe a unique Scholl reaction of 6,7,13,14-tetraarylbenzo[k]tetraphene, which "unexpectedly" forms five-membered rings accompanying highly selective 1,2-shift of aryl groups. The geometric and optoelectronic nature of the resulting bistetracene analogue with five-membered rings is comprehensively investigated by single-crystal X-ray, NMR, UV-vis absorption, and cyclic voltammetry analyses. Furthermore, a possible mechanism is proposed to account for the selective five-membered-ring formation with the rearrangement of the aryl groups, which can be rationalized by density functional theory (DFT) calculations. The theoretical results suggest that the formation of the bistetracene analogue with five-membered rings is kinetically controlled while an "expected" product with six-membered rings is thermodynamically more favored. These experimental and theoretical results provide further insights into the still controversial mechanism of the Scholl reaction as well as open up an unprecedented entry to extend the variety of PAHs by programing otherwise unpredictable rearrangements during the Scholl reaction.

  3. Two-dimensional inorganic–organic hybrid semiconductors composed of double-layered ZnS and monoamines with aromatic and heterocyclic aliphatic rings: Syntheses, structures, and properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Sujing; Li, Jing, E-mail:


    As an addition to the II–VI based inorganic–organic hybrid semiconductor family, five new two-dimensional (2D) double-layered structures have been synthesized employing monoamines with different aromatic or heterocyclic aliphatic rings. Zn{sub 2}S{sub 2}(bza) (1), Zn{sub 2}S{sub 2}(mbza) (2), Zn{sub 2}S{sub 2}(fbza) (3), Zn{sub 2}S{sub 2}(pca) (4), and Zn{sub 2}S{sub 2}(thfa) (5) (bza=benzylamine, mbza=4-methoxybenzylamine, fbza=4-flurobenzylamine, pca=3-picolylamine, and thfa=tetrahydrofurfurylamine) are prepared by solvothermal reactions and characterized by different analytical methods, including powder X-ray diffraction, optical diffuse reflection, thermogravimetric analysis and photoluminescence spectroscopy. The powder X-ray diffraction patterns show that all five compounds adopt 2D double-layered structures. Optical diffuse reflectance spectra of these compounds suggest that they have notably lower band gaps than those of the similar compounds composed of aliphatic alkyl amines. Their photoluminescence properties and thermal stability are also analyzed. - Graphical abstract: Five new members of two-dimensional double-layered 2D-Zn{sub 2}S{sub 2}(L) (L=Ligand) structures employing monoamines with different aromatic or heterocyclic aliphatic rings have been designed, synthesized, and characterized. - Highlights: • A new sub-family of II-VI based hybrid semiconductors are designed, synthesized, and structurally characterized using amines with aromatic or aliphatic cyclic rings. • These compounds have notably lower band gaps than those made of aliphatic alkyl amines, greatly broadening the range of band gaps of this material family. • They emit strongly with systematically tunable emission intensity and energy.

  4. A Novel Approach in Cinnamic Acid Synthesis: Direct Synthesis of Cinnamic Acids from Aromatic Aldehydes and Aliphatic Carboxylic Acids in the Presence of Boron Tribromide


    Onciu, M.; Tanasa, F.; C. Chiriac


    Cinnamic acids have been prepared in moderate to high yields by a new direct synthesis using aromatic aldehydes and aliphatic carboxylic acids, in the presence of boron tribromide as reagent, 4-dimethylaminopyridine (4-DMAP) and pyridine (Py) as bases and N-methyl-2-pyrolidinone (NMP) as solvent, at reflux (180-190°C) for 8-12 hours.

  5. Targeting of arenavirus RNA synthesis by a carboxamide-derivatized aromatic disulfide with virucidal activity.

    Directory of Open Access Journals (Sweden)

    Claudia S Sepúlveda

    Full Text Available Several arenaviruses can cause severe hemorrhagic fever (HF in humans, representing a public health threat in endemic areas of Africa and South America. The present study characterizes the potent virucidal activity of the carboxamide-derivatized aromatic disulfide NSC4492, an antiretroviral zinc finger-reactive compound, against Junín virus (JUNV, the causative agent of Argentine HF. The compound was able to inactivate JUNV in a time and temperature-dependent manner, producing more than 99 % reduction in virus titer upon incubation with virions at 37 °C for 90 min. The ability of NSC4492-treated JUNV to go through different steps of the multiplication cycle was then evaluated. Inactivated virions were able to bind and enter into the host cell with similar efficiency as control infectious particles. In contrast, treatment with NSC4492 impaired the capacity of JUNV to drive viral RNA synthesis, as measured by quantitative RT-PCR, and blocked viral protein expression, as determined by indirect immunofluorescence. These results suggest that the disulfide NSC4492 targets on the arenavirus replication complex leading to impairment in viral RNA synthesis. Additionally, analysis of VLP produced in NSC4492-treated cells expressing JUNV matrix Z protein revealed that the compound may interact with Z resulting in an altered aggregation behavior of this protein, but without affecting its intrinsic self-budding properties. The potential perspectives of NSC4492 as an inactivating vaccinal compound for pathogenic arenaviruses are discussed.

  6. Targeting of arenavirus RNA synthesis by a carboxamide-derivatized aromatic disulfide with virucidal activity. (United States)

    Sepúlveda, Claudia S; García, Cybele C; Levingston Macleod, Jesica M; López, Nora; Damonte, Elsa B


    Several arenaviruses can cause severe hemorrhagic fever (HF) in humans, representing a public health threat in endemic areas of Africa and South America. The present study characterizes the potent virucidal activity of the carboxamide-derivatized aromatic disulfide NSC4492, an antiretroviral zinc finger-reactive compound, against Junín virus (JUNV), the causative agent of Argentine HF. The compound was able to inactivate JUNV in a time and temperature-dependent manner, producing more than 99 % reduction in virus titer upon incubation with virions at 37 °C for 90 min. The ability of NSC4492-treated JUNV to go through different steps of the multiplication cycle was then evaluated. Inactivated virions were able to bind and enter into the host cell with similar efficiency as control infectious particles. In contrast, treatment with NSC4492 impaired the capacity of JUNV to drive viral RNA synthesis, as measured by quantitative RT-PCR, and blocked viral protein expression, as determined by indirect immunofluorescence. These results suggest that the disulfide NSC4492 targets on the arenavirus replication complex leading to impairment in viral RNA synthesis. Additionally, analysis of VLP produced in NSC4492-treated cells expressing JUNV matrix Z protein revealed that the compound may interact with Z resulting in an altered aggregation behavior of this protein, but without affecting its intrinsic self-budding properties. The potential perspectives of NSC4492 as an inactivating vaccinal compound for pathogenic arenaviruses are discussed.

  7. Living Polycondensation: Synthesis of Well-Defined Aromatic Polyamide-Based Polymeric Materials

    KAUST Repository

    Alyami, Mram Z.


    Chain growth condensation polymerization is a powerful tool towards the synthesis of well-defined polyamides. This thesis focuses on one hand, on the synthesis of well-defined aromatic polyamides with different aminoalkyl pendant groups with low polydispersity and controlled molecular weights, and on the other hand, on studying their thermal properties. In the first project, well-defined poly (N-octyl-p-aminobenzoate) and poly (N-butyl-p-aminobenzoate) were synthesized, and for the first time, their thermal properties were studied. In the second project, ethyl4-aminobenzoate, ethyl 4-octyl aminobenzoate and 4-(hydroxymethyl) benzoic acid were used as novel efficient initiators of ε-caprolactone with t-BuP2 as a catalyst. Macroinitiator and Macromonomer of poly (ε-caprolactone) were synthesized with ethyl 4-octyl aminobenzoate and ethyl 4-aminobenzoate as initiators to afford polyamide-block-poly (ε-caprolactone) and polyamide-graft-poly (ε-caprolactone) by chain growth condensation polymerization (CGCP). In the third project, a new study has been done on chain growth condensation polymerization to discover the probability to synthesize new polymers and studied their thermal properties. For this purpose, poly (N-cyclohexyl-p-aminobenzoate) and poly (N-hexyl-p-aminobenzoate) were synthesized with low polydispersity and controlled molecular weights.

  8. Iodine-catalyzed aromatization of tetrahydrocarbazoles and its utility in the synthesis of glycozoline and murrayafoline A: a combined experimental and computational investigation. (United States)

    Humne, Vivek; Dangat, Yuvraj; Vanka, Kumar; Lokhande, Pradeep


    A new protocol for the aromatization of tetrahydrocarbazoles has been achieved using a catalytic amount of iodine, giving high yields. The role of iodine in the aromatization has been explained by DFT, and its wide scope is extended to the total synthesis of glycozoline and murrayafoline A. This method has proven to be tolerant of a broad range of functional groups.

  9. Inorganic chemistry. Synthesis and characterization of P₂N₃⁻: an aromatic ion composed of phosphorus and nitrogen. (United States)

    Velian, Alexandra; Cummins, Christopher C


    Aromaticity is predominantly associated with carbon-rich compounds but can also occur in all-inorganic ones. We report the synthesis of the diphosphatriazolate anion, a rare example of a planar aromatic inorganic species. Treatment of azide (N3(-)) in tetrahydrofuran solution with P2A2 (A = C14H10), a source of P2, produced P2N3(-), which we isolated as its [Na-kryptofix-221](+) salt in 22% yield and characterized by single-crystal x-ray diffraction. Salts [Na-kryptofix-221] [P2N3] and [Na-kryptofix-221] [P2(15)NN2] were analyzed by infrared and Raman spectroscopy, (15)N and (31)P nuclear magnetic resonance spectroscopy, and mass spectrometry. The formation of the P2N3(-) anion was investigated using density functional theory, and its aromatic character was confirmed by NICS (nucleus-independent chemical shift) and QTAIM (quantum theory of atoms in molecules) methods.

  10. Pioneering Metal-Free Oxidative Coupling Strategy of Aromatic Compounds Using Hypervalent Iodine Reagents. (United States)

    Kita, Yasuyuki; Dohi, Toshifumi


    We started our hypervalent iodine research about 30 years ago in the mid-1980s. We soon successfully developed the single-electron-transfer oxidation ability of a hypervalent iodine reagent, specifically, phenyliodine(III) bis(trifluoroacetate) (PIFA), toward aromatic rings of phenyl ethers for forming aromatic cation radicals. This was one of the exciting and unexpected events in our research studies so far, and the discovery was reported in 1991. It also led to the next challenge, developing the metal-free oxidative couplings for C-H functionalizations and direct couplings between the C-H bonds of valuable aromatic compounds in organic synthesis. In order to realize the effective oxidative coupling, pioneering new aromatic ring activations was essential and several useful methodologies have been found for oxidizable arenes. The achievements regarding this objective obtained in our continuous research are herein summarized with classification of the aromatic ring activation strategies.

  11. Synthesis and structure of a sodium complex of an aromatic beta-diketone and pyrazolylpyridine. (United States)

    Coelho, Ana C; Paz, Filipe A Almeida; Klinowski, Jacek; Pillinger, Martyn; Gonçalves, Isabel S


    Reaction of NaH with a THF solution of Eu(BTA)3(pypzH) [BTA = 1-benzoyl-3,3,3-trifluoroacetonate, pypzH = 2-(3-pyrazolyl)pyridine] leads to the formation of the europium-free tetrasodium complex [Na(4)(pypzH)(2)(micro4-BTA)(2)(micro2-BTA)(2)]. Single-crystal X-ray diffraction studies revealed the presence of a centrosymmetric Na+ hybrid tetramer,which fully occupies the contents of the triclinic unit cell. The crystal structure contains two individual Na+ cations, Na(1) and Na(2), which have highly irregular [NaN(2)O(3)] and[NaO(6)] local coordination environments, respectively. One of the key features is the presence of a central [Na(4)O(6)] core, which is unprecedented for Na+ . Externally to this [Na(4)O(6)] cluster pyrazolylpyridine organic molecules are N,N-chelated to Na(1). Even though all of the organic residues contain aromatic rings, the crystal packing of individual centrosymmetric tetrasodium [Na(4)(pypzH)(2)(micro4-BTA)(2)(micro2-BTA)(2)] molecular moieties is essentially driven through geometrical aspects combined with weak C-H...pi interactions, rather than the expected a priori pi-pi interactions. The material also contains classical strong hydrogen bonds, even though these do not directly contribute to the packing driving forces.

  12. Continuous-flow synthesis of primary amines: Metal-free reduction of aliphatic and aromatic nitro derivatives with trichlorosilane

    Directory of Open Access Journals (Sweden)

    Riccardo Porta


    Full Text Available The metal-free reduction of nitro compounds to amines mediated by trichlorosilane was successfully performed for the first time under continuous-flow conditions. Aromatic as well as aliphatic nitro derivatives were converted to the corresponding primary amines in high yields and very short reaction times with no need for purification. The methodology was also extended to the synthesis of two synthetically relevant intermediates (precursors of baclofen and boscalid.

  13. Synthesis, double-helix formation, and higher-assembly formation of chiral polycyclic aromatic compounds: conceptual development of polyketide aldol synthesis. (United States)

    Yamaguchi, Masahiko; Shigeno, Masanori; Saito, Nozomi; Yamamoto, Koji


    Polycyclic aromatic compounds are an important group of substances in chemistry, and the study of their properties is a subject of interest in the development of drugs and materials. We have been conducting studies to develop chiral polycyclic aromatic compounds, i.e., helicenes and equatorenes. These helical molecules showed notable aggregate-forming properties and the capability for chiral recognition exerted by noncovalent bond interactions, which were not observed in compounds with central chirality. Homo- and hetero-double-helix-forming helicene oligomers were developed, and the latter self-assembled to form gels and vesicles. In this article, we describe such hierarchical studies of polycyclic aromatic compounds, which were started from polyketide aldol synthesis.

  14. A highly sensitive monoclonal antibody based biosensor for quantifying 3–5 ring polycyclic aromatic hydrocarbons (PAHs in aqueous environmental samples

    Directory of Open Access Journals (Sweden)

    Xin Li


    Full Text Available Immunoassays based on monoclonal antibodies (mAbs are highly sensitive for the detection of polycyclic aromatic hydrocarbons (PAHs and can be employed to determine concentrations in near real-time. A sensitive generic mAb against PAHs, named as 2G8, was developed by a three-step screening procedure. It exhibited nearly uniformly high sensitivity against 3-ring to 5-ring unsubstituted PAHs and their common environmental methylated PAHs, with IC50 values between 1.68 and 31 μg/L (ppb. 2G8 has been successfully applied on the KinExA Inline Biosensor system for quantifying 3–5 ring PAHs in aqueous environmental samples. PAHs were detected at a concentration as low as 0.2 μg/L. Furthermore, the analyses only required 10 min for each sample. To evaluate the accuracy of the 2G8-based biosensor, the total PAH concentrations in a series of environmental samples analyzed by biosensor and GC–MS were compared. In most cases, the results yielded a good correlation between methods. This indicates that generic antibody 2G8 based biosensor possesses significant promise for a low cost, rapid method for PAH determination in aqueous samples.

  15. Synthesis, Structure and Noncovalent Interactions of Palladium(Ⅱ) Complexes with N-Benzoyl-β-phenylalaninate Dianion and Aromatic Diimine

    Institute of Scientific and Technical Information of China (English)

    CHEN,Yao-Feng(陈耀峰); GONG,Yu-Qiu(龚钰秋); ZHANG,Hua-Song(张华松)


    Two palladiun(Ⅱ) complexes, [Pd(bipy)(BzPhe-N,O) ] and [Pd(phen) (BzPhe-N,O) ] @4H2O were synthesized by reactions between Pd(bipy)Cl2 and BzPheH2 ( N-benzoyl- β-phenylalanine), Pd(phen) Cla and BzPheH2 in water at pH ~ 9, with their structrues determined by X-ray diffraction analysis. The Pd atom is coordinated by two nitrogen atoms of bipy (or phen), the deprotonated amido type nitrogen atom and one of the carboxylic oxygens of BzPhe (BzPhe = N-benzoyl-β-phenylalaninate dianion). In the complex [Pd(phen)(BzPhe-N,O)]@ 4H2O, the side chain of phenvlalanine is located above and approximately parallels to the coordination plane. Both the aromic-aromatic stacking interaction between the phenyl ring of phenylalanine and phen, and the metal ion-aromatic interaction between the phenyi ring of phenylalanine and Pd(Ⅱ) were observed. [Pd(bipy)(BzPhe-N,O) ] has the phenylalanyl side chain oriented outwards from the coordination plane, which is mainly due to the interaction between the carbonyl oxygen atom of the amido group and the phenyl ring of phenylalanine. The reason for the different orientation of phenylalanyl side chain in the complexes was suggested.

  16. A short designed semi-aromatic organic nanotube--synthesis, chiroptical characterization, and host properties. (United States)

    Wixe, Torbjörn; Christensen, Niels Johan; Lidin, Sven; Fristrup, Peter; Wärnmark, Kenneth


    The first generation of an organic nanotube based on the enantiomerically pure bicyclo[3.3.1]nonane framework is presented. The helical tube synthesised is the longest to date having its aromatic systems oriented parallel to the axis of propagation (length ∼26 Å and inner diameter ∼11 Å according to molecular dynamics simulations in chloroform). The synthesis of the tube, a heptamer, is based on a series of Friedländer condensations and the use of pyrido[3,2-d]pyrimidine units as masked 2-amino aldehydes, as a general means to propagate organic tubular structures and the introduction of a methoxy group for modification toward solubility and functionalization are described. The electronic CD spectra of the tube and molecular intermediates are correlated with theoretical spectra calculated with time-dependent density functional theory to characterize the chirality of the tube. Both experimental (NMR-titrations) and theoretical (molecular dynamics simulations) techniques are used to investigate the use of the tube as a receptor for the acetylcholine and guanidinium cations, respectively.

  17. A Novel Approach in Cinnamic Acid Synthesis: Direct Synthesis of Cinnamic Acids from Aromatic Aldehydes and Aliphatic Carboxylic Acids in the Presence of Boron Tribromide

    Directory of Open Access Journals (Sweden)

    M. Onciu


    Full Text Available Cinnamic acids have been prepared in moderate to high yields by a new direct synthesis using aromatic aldehydes and aliphatic carboxylic acids, in the presence of boron tribromide as reagent, 4-dimethylaminopyridine (4-DMAP and pyridine (Py as bases and N-methyl-2-pyrolidinone (NMP as solvent, at reflux (180-190°C for 8-12 hours.

  18. Immobilized Candida antarctica lipase B: Hydration, stripping off and application in ring opening polyester synthesis. (United States)

    Idris, Ani; Bukhari, Attaullah


    This work reviews the stripping off, role of water molecules in activity, and flexibility of immobilized Candida antarctica lipase B (CALB). Employment of CALB in ring opening polyester synthesis emphasizing on a polylactide is discussed in detail. Execution of enzymes in place of inorganic catalysts is the most green alternative for sustainable and environment friendly synthesis of products on an industrial scale. Robust immobilization and consequently performance of enzyme is the essential objective of enzyme application in industry. Water bound to the surface of an enzyme (contact class of water molecules) is inevitable for enzyme performance; it controls enzyme dynamics via flexibility changes and has intensive influence on enzyme activity. The value of pH during immobilization of CALB plays a critical role in fixing the active conformation of an enzyme. Comprehensive selection of support and protocol can develop a robust immobilized enzyme thus enhancing its performance. Organic solvents with a log P value higher than four are more suitable for enzymatic catalysis as these solvents tend to strip away very little of the enzyme surface bound water molecules. Alternatively ionic liquid can work as a more promising reaction media. Covalent immobilization is an exclusively reliable technique to circumvent the leaching of enzymes and to enhance stability. Activated polystyrene nanoparticles can prove to be a practical and economical support for chemical immobilization of CALB. In order to reduce the E-factor for the synthesis of biodegradable polymers; enzymatic ring opening polyester synthesis (eROPS) of cyclic monomers is a more sensible route for polyester synthesis. Synergies obtained from ionic liquids and immobilized enzyme can be much effective eROPS.

  19. Inner-shell excitation spectroscopy of fused-ring aromatic molecules by electron energy loss and X-ray Raman techniques

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, M.L.; Tulumello, D.; Cooper, G.; Hitchcock, A.P.; Glatzel, P.; Mullins, O.C.; Cramer, S.P.; Bergmann, U. [McMaster University, Hamilton, ON (Canada). Dept. of Chemistry


    Oscillator strengths for C 1s excitation spectra of gaseous benzene, naphthalene, anthracene, phenanthracene, triphenylene, pyrene, and 1,2-benzanthracene have been derived from inner-shell electron energy loss spectroscopy recorded under scattering conditions where electric dipole transitions dominate (2.5 keV residual energy, theta {>=} 2{sup o} corresponding to a product of momentum transfer and C 1s orbital size (qr) of 0.08). These spectra are interpreted with the aid of ab initio calculations on selected species. They are compared to the C 1s spectra of solid samples of benzene, naphththalene, anthracene, triphenylene, and 1,2-benzanthracene, recorded with inelastic X-ray Raman scattering in the dipole limit (qr < 0.5). When differences in resolution are taken into account, good agreement is found between the inelastic electron scattering spectra of the gases and the inelastic photon scattering spectra of the corresponding solid. Small differences are attributed to quenching of transitions to Rydberg states in the solids. Characteristic differences related to the degree of symmetry or spatial arrangement of the fused ring aromatic hydrocarbons (e.g., linear versus bent structures) indicate that C 1s X-ray Raman spectroscopy should be useful for characterizing aromatics in bulk samples that are opaque to soft X-rays, such as coals and heavy hydrocarbon deposits.

  20. Multicomponent reactions for synthesis of bioactive polyheterocyclic ring systems under controlled microwave irradiation

    Directory of Open Access Journals (Sweden)

    Eman M.H. Abbas


    Full Text Available The multi-component reaction of 1-benzothiopyran-4-ones with heterocyclic amines and dimethylformamide-dimethylacetal (DMFDMA in DMF at 150 °C under controlled microwave heating afforded novel poly-heterocyclic ring systems. Also, reaction of 3-dimethylaminomethylene-1-benzothiopyran-4-one with activemethylene derivatives was investigated. The structure of all products was established on the bases of spectral data and elemental analyses and alternative synthesis if possible. The prepared compounds were screened for their antitumor activity against HCT-116 “colon” cancer cell line and some derivatives showed promising activity.

  1. Synthesis and Thermal Behavior of a Fused, Tricyclic 1,2,3,4-Tetrazine Ring System. (United States)

    Chavez, David E; Bottaro, Jeffery C; Petrie, Mark; Parrish, Damon A


    This study presents the synthesis and characterization of a fused, tricyclic 1,2,3,4-tetrazine ring system. The molecule is synthesized in a three-step process from 5,5'-dinitro-bis,1,2,4-triazole via a di-N-amino compound. Oxidation to form the azo-coupled fused tricyclic 1,2,3,4-tetrazine is achieved using tert-butyl hypochlorite as the oxidant. The di-N-amino compound and the desired fused tricyclic 1,2,3,4-triazine display interesting thermal behavior and are predicted to be high-performance energetic materials.

  2. Synthesis of NLO polycarbonates via the ring-opening polymerization of macrocyclic prepolymers (United States)

    Kulig, Joseph B.; Moore, Collin G.; Brittain, William J.; Gilmour, Sandra; Perry, Joseph W.


    The synthesis and characterization of polycarbonates and polyformals is described. Copolymers of bisphenol A (BPA) and either a triphenyloxazole (1) or phenylquinoxaline (2) monomer were prepared. The polycarbonate copolymers were prepared by ring-opening polymerization of macrocyclic prepolymers using a solvent-free process. Preliminary electro- optic measurements have been performed on the polycarbonate copolymers of BPA and 1. Polyformals have also been prepared by a conventional polymerization process involving the reaction of dichloromethane with different feed ratios of BPA and either 1 or 2. The glass transition temperature of either the polyformals or polycarbonates is dramatically increased by increasing mole fractions of monomers 1 and 2.

  3. Synthesis of Calystegine A(3) from Glucose by the Use of Ring-Closing Metathesis

    DEFF Research Database (Denmark)

    Monrad, Rune Nygaard; Pipper, Charlotte Bressen; Madsen, Robert


    A synthesis of the nortropane alkaloid calystegine A(3) is described from D-glucose. The key step employs a zinc-mediated tandem reaction where a benzyl-protected methyl 6-iodo glucoside is fragmented to give an unsaturated aldehyde, which is then transformed into the corresponding benzylimine...... and allylated in the same pot. The functionalized nona-1,8-diene, thus obtained, is converted into the seven-membered carbon skeleton in calystegine A(3) by ring-closing olefin metathesis. Subsequent deoxygenation by the Barton-McCombie protocol, hydroboration and oxidative workup followed by hydrogenolysis...... affords calystegine A(3). The synthesis uses a total of 13 steps from glucose and confirms the absolute configuration of the natural product....

  4. Vernier templating and synthesis of a 12-porphyrin nano-ring. (United States)

    O'Sullivan, Melanie C; Sprafke, Johannes K; Kondratuk, Dmitry V; Rinfray, Corentin; Claridge, Timothy D W; Saywell, Alex; Blunt, Matthew O; O'Shea, James N; Beton, Peter H; Malfois, Marc; Anderson, Harry L


    Templates are widely used to arrange molecular components so they can be covalently linked into complex molecules that are not readily accessible by classical synthetic methods. Nature uses sophisticated templates such as the ribosome, whereas chemists use simple ions or small molecules. But as we tackle the synthesis of larger targets, we require larger templates-which themselves become synthetically challenging. Here we show that Vernier complexes can solve this problem: if the number of binding sites on the template, n(T), is not a multiple of the number of binding sites on the molecular building blocks, n(B), then small templates can direct the assembly of relatively large Vernier complexes where the number of binding sites in the product, n(P), is the lowest common multiple of n(B) and n(T) (refs 8, 9). We illustrate the value of this concept for the covalent synthesis of challenging targets by using a simple six-site template to direct the synthesis of a 12-porphyrin nano-ring with a diameter of 4.7 nm, thus establishing Vernier templating as a powerful new strategy for the synthesis of large monodisperse macromolecules.

  5. Substrate-dependent aromatic ring fission of catechol and 2-aminophenol with O2 catalyzed by a nonheme iron complex of a tripodal N4 ligand. (United States)

    Lakshman, Triloke Ranjan; Chatterjee, Sayanti; Chakraborty, Biswarup; Paine, Tapan Kanti


    The catalytic reactivity of an iron(ii) complex [(TPA)Fe(II)(CH3CN)2](2+) (1) (TPA = tris(2-pyridylmethyl)amine) towards oxygenative aromatic C-C bond cleavage of catechol and 2-aminophenol is presented. Complex 1 exhibits catalytic and regioselective C-C bond cleavage of 3,5-di-tert-butylcatechol (H2DBC) to form intradiol products, whereas it catalyzes extradiol-type C-C bond cleavage of 2-amino-4,6-di-tert-butylphenol (H2AP). The catalytic reactions are found to be pH-dependent and the complex exhibits maximum turnovers at pH 5 in acetonitrile-phthalate buffer. An iron(iii)-catecholate complex [(TPA)Fe(III)(DBC)](+) (2) is formed in the ring cleavage of catechol. In the extradiol-type cleavage of H2AP, an iron(iii)-2-iminobenzosemiquinonate complex [(TPA)Fe(III)(ISQ)](2+) (3) (ISQ = 4,6-di-tert-butyl-2-iminobenzosemiquinonate radical anion) is observed in the reaction pathway. This work shows the importance of the nature of 'redox non-innocent' substrates in governing the mode of ring fission reactivity.

  6. A new type of excited-state intramolecular proton transfer: proton transfer from phenol OH to a carbon atom of an aromatic ring observed for 2-phenylphenol. (United States)

    Lukeman, Matthew; Wan, Peter


    The photochemical deuterium incorporation at the 2'- and 4'-positions of 2-phenylphenol (4) and equivalent positions of related compounds has been studied in D(2)O (CH(3)OD)-CH(3)CN solutions with varying D(2)O (CH(3)OD) content. Predominant exchange was observed at the 2'-position with an efficiency that is independent of D(2)O (MeOD) content. Exchange at the 2'-position (but not at the 4'-position) was also observed when crystalline samples of 4-OD were irradiated. Data are presented consistent with a mechanism of exchange that involves excited-state intramolecular proton transfer (ESIPT) from the phenol to the 2'-carbon position of the benzene ring not containing the phenol, to generate the corresponding keto tautomer (an o-quinone methide). This is the first explicit example of a new class of ESIPT in which an acidic phenolic proton is transferred to an sp(2)-hybridized carbon of an aromatic ring. The complete lack of exchange observed for related substrates 6-9 and for planar 4-hydroxyfluorene (10) is consistent with a mechanism of ESIPT that requires an initial hydrogen bonding interaction between the phenol proton and the benzene pi-system. Similar exchange was observed for 2,2'-biphenol (5), suggesting that this new type of ESIPT is a general reaction for unconstrained 2'-aryl-substituted phenols and other related hydroxyarenes.

  7. Enzyme-catalyzed polycondensation reactions for the synthesis of aromatic polycarbonates and polyesters. (United States)

    Rodney, R L; Allinson, B T; Beckman, E J; Russell, A J


    Aromatic polymers are widely used in products ranging from optical lenses to milk bottles because of their strength, thermal durability, and high glass transition temperatures. All of the commonly used routes employed to generate aromatic polycarbonates and polyesters generate large amounts of waste as by-products and require high energy input. For these reasons, alternate routes to aromatic polymers which involve either less energy input or less waste generation are being investigated. One such route may be enzymatic. Herein we describe enzyme-catalyzed AA-BB condensation polymerizations to form aromatic polycarbonates and polyesters with six different aromatic diols and molecular weights of up to 5,200 Daltons are generated. In addition, for reactions with benzenedimethanol the enzyme exhibits regioselectivity for parahydroxyls over meta- and orthohydroxyls.

  8. Aromaticity-controlled thermal stability of photochromic systems based on a six-membered ring as ethene bridges: photochemical and kinetic studies. (United States)

    Yang, Yuheng; Xie, Yongshu; Zhang, Qiong; Nakatani, Keitaro; Tian, He; Zhu, Weihong


    Three photochromic compounds--2-butyl-5,6-bis[5-(4-methoxyphenyl)-2-methylthiophen-3-yl]-1 H-benzo[de]isoquinoline-1,3(2 H)-dione (BTE-NA), 4,5-bis[5-(4-methoxyphenyl)-2-methylthiophen-3-yl]benzo[c][1,2,5]thiadiazole (BTA), and BTTA, which contain naphthalimide, benzothiadiazole, and benzobisthiadiazole as six-membered ethene bridges with different aromaticities--were systematically studied in solution, sol-gel, and single-crystal states. They exhibit typical photochromic performance with considerably high cyclization quantum yields. BTE-NA, BTA, and BTTA form a typical donor-π-acceptor (D-π-A) system with significant intramolecular charge transfer (ICT) between HOMO and LUMO upon excitation, thus realizing the fluorescence modulation by both photochromism and solvatochromism. The three ethene bridges with different degrees of aromaticity can provide a systematic comparison of the thermal stability evolution for their corresponding closed forms (c-BTE-NA, c-BTA, and c-BTTA). c-BTE-NA shows first-order decay in various solvents from cyclohexane to acetonitrile. c-BTA only shows first-order decay in polar solvents such as chloroform, whereas it is stable in nonpolar solvents like toluene. In contrast, the less aromatic property of BTTA gives rise to its unprecedented thermal stability in various solvents even at elevated temperatures in toluene (328 K). Moreover, the small energy barrier between the parallel and antiparallel conformers allows the full conversion from BTTA to c-BTTA. In well-ordered crystal states, all three compounds adopt a parallel conformation. Interestingly, BTTA forms a twin crystal of asymmetric nature with interactions between the electron-rich oxygen atom of the methoxy group and the carbon atom of the electron-deficient benzobisthiadiazole moiety. This work contributes to the understanding of aromaticity-controlled thermal stability of photochromic systems based on a six-membered ring as an ethene bridge, and a broadening of the

  9. The effect of β-saturated pyrrolic rings on the electronic structures and aromaticity of magnesium porphyrin derivatives: a density functional study. (United States)

    Wan, Liang; Qi, Dongdong; Zhang, Yuexing


    Density functional theory (DFT) calculation on the molecular structures, molecular orbitals, electronic absorption spectra, and magnetic properties of magnesium porphyrin (MgPor) and a series of five hydrogenated magnesium porphyrin complexes with different number of β-saturated pyrrolic rings, namely MgPor-β-1Hy, MgPor-β-opp-2Hy, MgPor-β-adj-2Hy, MgPor-β-3Hy, and MgPor-β-4Hy, clarifies the red-shift of the lowest energy absorption band from chlorophyll a to bacteriochlorophyll and reveals the strong chemical stability for both of them. The energy levels of highest occupied molecular orbitals (HOMO) and HOMO-1 for MgPor are reversed upon hydrogenation at β-positions (2 and 3, 7 and 8, 12 and 13, and 17 and 18) of porphyrin ring. Along with the increase of β-saturated pyrrolic rings from 1, 2, 3, to 4, the HOMO energy increases from -4.78 eV to -3.10 eV in a regular manner. In contrast, the lowest unoccupied molecular orbitals (LUMO) energy levels of MgPor, MgPor-β-1Hy, and MgPor-β-opp-2Hy are very similar with each other. As a result, the lowest energy absorption band involving main transition from HOMO to LUMO is red-shifted from MgPor-β-1Hy to MgPor-β-opp-2Hy which is representative of chlorophyll a and bacteriochlorophyll, respectively. Natural hydroporphyrins represented by MgPor, MgPor-β-1Hy, and MgPor-β-opp-2Hy have turned out to be aromatic and stable enough, in good accordance with the ubiquity of their derivatives in the nature. In contrast, MgPor-β-adj-2Hy, MgPor-β-3Hy, and MgPor-β-4Hy with relatively weak aromaticity seem to be unstable and therefore were not found in nature.

  10. A new paradigm for designing ring construction strategies for green organic synthesis: implications for the discovery of multicomponent reactions to build molecules containing a single ring (United States)


    A new way of developing novel synthesis strategies for the construction of monocyclic rings found in organic molecules is presented. The method is based on the visual application of integer partitioning to chemical structures. Two problems are addressed: (1) the determination of the total number of possible ways to construct a given ring by 2-, 3-, and 4-component couplings; and (2) the systematic enumeration of those possibilities. The results of the method are illustrated using cyclohexanone, pyrazole, and the Biginelli adduct as target ring systems with a view to discover new and greener strategies for their construction using multicomponent reactions. The application of the method is also extended to various heterocycles found in many natural products and pharmaceuticals. PMID:28144310

  11. A new paradigm for designing ring construction strategies for green organic synthesis: implications for the discovery of multicomponent reactions to build molecules containing a single ring. (United States)

    Andraos, John


    A new way of developing novel synthesis strategies for the construction of monocyclic rings found in organic molecules is presented. The method is based on the visual application of integer partitioning to chemical structures. Two problems are addressed: (1) the determination of the total number of possible ways to construct a given ring by 2-, 3-, and 4-component couplings; and (2) the systematic enumeration of those possibilities. The results of the method are illustrated using cyclohexanone, pyrazole, and the Biginelli adduct as target ring systems with a view to discover new and greener strategies for their construction using multicomponent reactions. The application of the method is also extended to various heterocycles found in many natural products and pharmaceuticals.

  12. A new paradigm for designing ring construction strategies for green organic synthesis: implications for the discovery of multicomponent reactions to build molecules containing a single ring

    Directory of Open Access Journals (Sweden)

    John Andraos


    Full Text Available A new way of developing novel synthesis strategies for the construction of monocyclic rings found in organic molecules is presented. The method is based on the visual application of integer partitioning to chemical structures. Two problems are addressed: (1 the determination of the total number of possible ways to construct a given ring by 2-, 3-, and 4-component couplings; and (2 the systematic enumeration of those possibilities. The results of the method are illustrated using cyclohexanone, pyrazole, and the Biginelli adduct as target ring systems with a view to discover new and greener strategies for their construction using multicomponent reactions. The application of the method is also extended to various heterocycles found in many natural products and pharmaceuticals.

  13. Convergent solid-phase and solution approaches in the synthesis of the cysteine-rich Mdm2 RING finger domain. (United States)

    Vasileiou, Zoe; Barlos, Kostas; Gatos, Dimitrios


    The RING finger domain of the Mdm2, located at the C-terminus of the protein, is necessary for regulation of p53, a tumor suppressor protein. The 48-residues long Mdm2 peptide is an important target for studying its interaction with small anticancer drug candidates. For the chemical synthesis of the Mdm2 RING finger domain, the fragment condensation on solid-phase and the fragment condensation in solution were studied. The latter method was performed using either protected or free peptides at the C-terminus as the amino component. Best results were achieved using solution condensation where the N-component was applied with the C-terminal carboxyl group left unprotected. The developed method is well suited for large-scale synthesis of Mdm2 RING finger domain, combining the advantages of both solid-phase and solution synthesis.

  14. Enantioselective synthesis of angularly substituted 1-azabicylic rings: coupled dynamic kinetic epimerization and chirality transfer. (United States)

    Aron, Zachary D; Ito, Tatsuya; May, Tricia L; Overman, Larry E; Wang, Jocelyn


    A new strategy for enantioselective synthesis of azacyclic molecules in which dynamic kinetic equilibration of diastereomeric iminium ions precedes a stereochemistry-determining sigmatropic rearrangement is reported. The method is illustrated by the synthesis, in high enantiomeric purity (generally 95-99% ee), of a variety of 1-azabicyclic molecules containing angular allyl or 3-substituted 2-propenyl side chains adjacent to nitrogen and up to three stereogenic centers. In these products, the size of the carbocyclic ring is varied widely (5-12 membered); however, useful yields are obtained in forming 1-azabicyclic products containing only fused pyrrolidine and piperidine rings. Chirality transfer from substituents at carbons 1 and 2 of the 3-butenylamine fragment of the starting material is investigated, with methyl and phenyl substituents at the allylic position shown to provide exquisite stereocontrol (generally 98-99% chirality transfer). An attractive feature of the method is the ability to carry out the key transformation in the absence of solvent. Illustrated also is the high yielding conversion of four such products to a new family of bicyclic β-amino acids of high enantiomeric purity.

  15. Structural basis for the RING catalyzed synthesis of K63 linked ubiquitin chains (United States)

    Branigan, Emma; Plechanovová, Anna; Jaffray, Ellis; Naismith, James H.; Hay, Ronald T.


    The RING E3 ligase catalysed formation of lysine 63 linked ubiquitin chains by the Ube2V2–Ubc13 E2 complex is required for many important biological processes. Here we report the structure of the RING domain dimer of rat RNF4 in complex with a human Ubc13~Ub conjugate and Ube2V2. The structure has captured Ube2V2 bound to the acceptor (priming) ubiquitin with Lys63 in a position that could lead to attack on the linkage between the donor (second) ubiquitin and Ubc13 that is held in the active “folded back” conformation by the RING domain of RNF4. The interfaces identified in the structure were verified by in vitro ubiquitination assays of site directed mutants. This represents the first view of the synthesis of Lys63 linked ubiquitin chains in which both substrate ubiquitin and ubiquitin-loaded E2 are juxtaposed to allow E3 ligase mediated catalysis. PMID:26148049

  16. Efficient Synthesis of 2-Ethyl-A-ring Analogues of 19-Nor-1α,25-dihydroxy Vitamin D3

    Institute of Scientific and Technical Information of China (English)


    The novel 19-nor-lα,25-dihydroxy vitamin D3 analogues possessing an ethyl at the 2-position(4 and 5), were synthesized by coupling 25-hydroxy Windaus-Grundmann ketone derivative 20 with A-ring synthons(15 and 19) respectively. The enantioselective synthesis of substituted bicyclic[3,1,0] hexanes structure A-ring synthons, started from all-cis-3,5-dihydroxy-4-ethyl-1-(methoxycarbonyl)cyclohexane via lipase-catalyzd asymmetrization, was demonstrated.

  17. Novel Easy Preparations of Some Aromatic Iodine(I, III, and V Reagents, Widely Applied in Modern Organic Synthesis

    Directory of Open Access Journals (Sweden)

    Lech Skulski


    Full Text Available We report our novel (or considerably improved methods for the synthesis of aromatic iodides, (dichloroiodoarenes, (diacetoxyiodoarenes, [bis(trifluoroacetoxy-iodo]arenes, iodylarenes and diaryliodonium salts, as well as some facile, oxidative anion metatheses in crude diaryliodonium or tetraalkylammonium halides and, for comparison, potassium halides. All our formerly published papers were discussed and explained in our review “Organic Iodine(I, III, and V Chemistry: 10 Years of Development at the Medical University of Warsaw, Poland” (1990-2000 [1]. Our newest results are discussed below.

  18. Synthesis of o-Carboxyarylacrylic Acids by Room Temperature Oxidative Cleavage of Hydroxynaphthalenes and Higher Aromatics with Oxone. (United States)

    Parida, Keshaba Nanda; Moorthy, Jarugu Narasimha


    A simple procedure for the synthesis of a variety of o-carboxyarylacrylic acids has been developed with Oxone (2KHSO5·KHSO4·K2SO4); the oxidation reaction involves the stirring of methoxy/hydroxy-substituted naphthalenes, phenanthrenes, anthracenes, etc. with Oxone in an acetonitrile-water mixture (1:1, v/v) at rt. Mechanistically, the reaction proceeds via initial oxidation of naphthalene to o-quinone, which undergoes cleavage to the corresponding o-carboxyarylacrylic acid. The higher aromatics are found to yield carboxymethyl lactones derived from the initially formed o-carboxyarylacrylic acids.

  19. Synthesis and antiproliferative activity of aromatic and aliphatic bis[aminomethylidene(bisphosphonic)] acids. (United States)

    Goldeman, Waldemar; Nasulewicz-Goldeman, Anna


    A series of aromatic and aliphatic bis[aminomethylidene(bisphosphonic)] acids was synthesized in the reaction of triethylphosphite with isonitriles followed by hydrolysis or dealkylation. The in vitro anti-proliferative effect of all synthesized tetraphosphonic acids against MCF-7 breast cancer cells, J774E macrophages and HL-60 promyelocytic leukemia cells was determined. Three aromatic derivatives (5a, 5f and 5j) showed a similar or higher anti-proliferative activity than zoledronic acid.

  20. In vitro and in vivo characterization of opioid activities of endomorphins analogs with novel constrained C-terminus: evidence for the important role of proper spatial disposition of the third aromatic ring. (United States)

    Yu, Ye; Shao, Xuan; Wang, Chang-Lin; Liu, Hong-Mei; Cui, Yun; Fan, Ying-Zhe; Liu, Jing; Wang, Rui


    In the present study, the C-terminus of endomorphin (Tyr(1)-Pro(2)-Trp/Phe(3)-Phe(4)-NH(2), EMs) analogs [Xaa(4)-R]EMs, modified by substitution of a non-aromatic residue for Phe(4) and ending up with -NH-benzyl, were designed to generate an atypical conformationally constrained peptide set. We investigated the effects of these analogs on the opioid receptors affinity, guinea pig ileum (GPI) and mouse vas deferens (MVD) activity, system arterial pressure (SAP), heart rate (HR), antinociception and colonic motility. Analogs 5 ([D-V(4)-Bzl]EM1) and 10 ([D-V(4)-Bzl]EM2), which exhibit appropriate spatial orientations of the third aromatic ring, were about 3-4 times more potent than their parents both in vivo and in vitro. However, a drastic loss of activity was found in analogs 2 ([A(4)-Bzl]EM1) and 7 ([A(4)-Bzl]EM2), which possess improper spatial orientations of the third aromatic ring. Interestingly, analog 7 or 3 ([G(4)-Bzl]EM1), when injected intravenously (i.v.), produced significantly different changes in SAP from their parents. Surprisingly, analog 4 displayed relatively higher vasodepressor activity but significantly less potent colonic contractile activity than analog 5. This may be elicited by the differences in the spatial disposition of the third aromatic ring, which were verified by molecular modeling. Our results indicate that the proper spatial disposition of the third aromatic ring plays an important role in the regulation of pharmacological activities of EMs.

  1. Synthesis of the furo[2,3-b]chromene ring system of hyperaspindols A and B

    Directory of Open Access Journals (Sweden)

    Danielle L. Paterson


    Full Text Available The synthesis of the unique furo[2,3-b]chromene ring system found in hyperaspidinols A and B, acylphloroglucinols from Hypericum chinense has been achieved in twelve steps. By comparison of the NMR spectra of the synthesized compounds with those of the natural products, a relative stereochemistry is suggested, especially that of the ketal carbon.

  2. Gaining Control over Radiolytic Synthesis of Uniform Sub-3-nanometer Palladium Nanoparticles: Use of Aromatic Liquids in the Electron Microscope. (United States)

    Abellan, Patricia; Parent, Lucas R; Al Hasan, Naila; Park, Chiwoo; Arslan, Ilke; Karim, Ayman M; Evans, James E; Browning, Nigel D


    Synthesizing nanomaterials of uniform shape and size is of critical importance to access and manipulate the novel structure-property relationships arising at the nanoscale, such as catalytic activity. In this work, we synthesize Pd nanoparticles with well-controlled size in the sub-3 nm range using scanning transmission electron microscopy (STEM) in combination with an in situ liquid stage. We use an aromatic hydrocarbon (toluene) as a solvent that is very resistant to high-energy electron irradiation, which creates a net reducing environment without the need for additives to scavenge oxidizing radicals. The primary reducing species is molecular hydrogen, which is a widely used reductant in the synthesis of supported metal catalysts. We propose a mechanism of particle formation based on the effect of tri-n-octylphosphine (TOP) on size stabilization, relatively low production of radicals, and autocatalytic reduction of Pd(II) compounds. We combine in situ STEM results with insights from in situ small-angle X-ray scattering (SAXS) from alcohol-based synthesis, having similar reduction potential, in a customized microfluidic device as well as ex situ bulk experiments. This has allowed us to develop a fundamental growth model for the synthesis of size-stabilized Pd nanoparticles and demonstrate the utility of correlating different in situ and ex situ characterization techniques to understand, and ultimately control, metal nanostructure synthesis.

  3. Recent advances in the ruthenium-catalyzed hydroarylation of alkynes with aromatics: synthesis of trisubstituted alkenes. (United States)

    Manikandan, Rajendran; Jeganmohan, Masilamani


    The hydroarylation of alkynes with substituted aromatics in the presence of a metal catalyst via chelation-assisted C-H bond activation is a powerful method to synthesize trisubstituted alkenes. Chelation-assisted C-H bond activation can be done by two ways: (a) an oxidative addition pathway and (b) a deprotonation pathway. Generally, a mixture of cis and trans stereoisomeric as well as regioisomeric trisubstituted alkenes was observed in an oxidative addition pathway. In the deprotonation pathway, the hydroarylation reaction can be done in a highly regio- and stereoselective manner, and enables preparation of the expected trisubstituted alkenes in a highly selective manner. Generally, ruthenium, rhodium and cobalt complexes are used as catalysts in the reaction. In this review, a ruthenium-catalyzed hydroarylation of alkynes with substituted aromatics is covered completely. The hydroarylation reaction of alkynes with amide, azole, carbamate, phosphine oxide, amine, acetyl, sulfoxide and sulphur directed aromatics is discussed.

  4. The stability of biradicaloid versus closed-shell [E(μ-XR)]2 (E = P, As; X = N, P, As) rings. Does aromaticity play a role? (United States)

    Grande-Aztatzi, Rafael; Mercero, Jose M; Ugalde, Jesus M


    High-level multiconfigurational self-consistent field calculations, supplemented with multiconfigurational quasi-degenerate perturbation theory ab initio calculations with the aug-cc-pVTZ basis set, demonstrate that the [E(μ-XH)]2 (E = P, As; X = N, P, As) compounds possess one planar and one butterfly-like isomer. The calculations predict that for X = N, planar isomers, which bear substantial biradicaloid character, are more stable than their butterfly-like counterpart isomers, which feature closed-shell electronic structures. This has been ascribed to the fact that the increased bond angle strain at E-N-E is not compensated by the E-E σ (deformed) bond formation in the butterfly-like isomers, yielding the planar structures, which hold wider E-N-E bond angles, as the most stable isomers. As N is substituted by heavier atoms, either P or As, the E-P(As)-E bond angle strain is released and, additionally, as the formed E-E σ-bond is less deformed, the butterfly isomer becomes the most stable isomer. Subsequent evaluation of the normalized Giambiagi multicenter electron delocalization indices revealed no sign of electron delocalization in the four-membered rings and consequently, it is concluded that aromaticity does not play any role in the stabilization of the planar isomers.

  5. Cardiac toxicity of 5-ring polycyclic aromatic hydrocarbons is differentially dependent on the aryl hydrocarbon receptor 2 isoform during zebrafish development

    Energy Technology Data Exchange (ETDEWEB)

    Incardona, John P., E-mail:; Linbo, Tiffany L.; Scholz, Nathaniel L.


    Petroleum-derived compounds, including polycyclic aromatic hydrocarbons (PAHs), commonly occur as complex mixtures in the environment. Recent studies using the zebrafish experimental model have shown that PAHs are toxic to the embryonic cardiovascular system, and that the severity and nature of this developmental cardiotoxicity varies by individual PAH. In the present study we characterize the toxicity of the relatively higher molecular weight 5-ring PAHs benzo[a]pyrene (BaP), benzo[e]pyrene (BeP), and benzo[k]fluoranthene (BkF). While all three compounds target the cardiovascular system, the underlying role of the ligand-activated aryl hydrocarbon receptor (AHR2) and the tissue-specific induction of the cytochrome p450 metabolic pathway (CYP1A) were distinct for each. BaP exposure (40 {mu}M) produced AHR2-dependent bradycardia, pericardial edema, and myocardial CYP1A immunofluorescence. By contrast, BkF exposure (4-40 {mu}M) caused more severe pericardial edema, looping defects, and erythrocyte regurgitation through the atrioventricular valve that were AHR2-independent (i.e., absent myocardial or endocardial CYP1A induction). Lastly, exposure to BeP (40 {mu}M) yielded a low level of CYP1A+ signal in the vascular endothelium of the head and trunk, without evident toxic effects on cardiac function or morphogenesis. Combined with earlier work on 3- and 4-ring PAHs, our findings provide a more complete picture of how individual PAHs may drive the cardiotoxicity of mixtures in which they predominate. This will improve toxic injury assessments and risk assessments for wild fish populations that spawn in habitats altered by overlapping petroleum-related human impacts such as oil spills, urban stormwater runoff, or sediments contaminated by legacy industrial activities. -- Highlights: Black-Right-Pointing-Pointer PAH compounds with 5 rings in different arrangements caused differential tissue-specific patterns of CYP1A induction in zebrafish embryos. Black

  6. Synthesis of Fluoroalkoxy Substituted Arylboronic Esters by Iridium-Catalyzed Aromatic C–H Borylation

    KAUST Repository

    Batool, Farhat


    The preparation of fluoroalkoxy arylboronic esters by iridium-catalyzed aromatic C–H borylation is described. The fluoroalkoxy groups employed include trifluoromethoxy, difluoromethoxy, 1,1,2,2-tetrafluoroethoxy, and 2,2-difluoro-1,3-benzodioxole. The borylation reactions were carried out neat without the use of a glovebox or Schlenk line. The regioselectivities available through the iridium-catalyzed C–H borylation are complementary to those obtained by the electrophilic aromatic substitution reactions of fluoroalkoxy arenes. Fluoroalkoxy arylboronic esters can serve as versatile building blocks.

  7. Systematic Introduction of Aromatic Rings to Diphosphine Ligands for Emission Color Tuning of Dinuclear Copper(I) Iodide Complexes. (United States)

    Okano, Yuka; Ohara, Hiroki; Kobayashi, Atsushi; Yoshida, Masaki; Kato, Masako


    We have newly synthesized two solution-stable luminescent dinuclear copper(I) complexes, [Cu2(μ-I)2(dpppy)2] (Cu-py) and [Cu2(μ-I)2(dpppyz)2] (Cu-pyz), where dpppy = 2,3-bis(diphenylphosphino)pyridine and dpppyz = 2,3-bis(diphenylphosphino)pyrazine, using chelating diphosphine ligands composed of N-heteroaromatic rings. X-ray analysis clearly indicates that the molecular structures of Cu-py and Cu-pyz are almost identical with that of the parent complex, [Cu2(μ-I)2(dppb)2] [Cu-bz; dppb = 2,3-bis(diphenylphosphino)benzene]. Complexes Cu-py and Cu-pyz exhibit luminescence [emission quantum yield (Φem) = 0.48 and 0.02, respectively] in the solid state at 298 K. A wide emission color tuning, from 497 to 638 nm (energy = 0.55 eV, with an emission color ranging from green to reddish-orange), was achieved in the solid state by the introduction of pyridinic N atoms into the bridging phenyl group between the two diphenylphosphine groups. Density functional theory calculations suggest that the emission could originate from the effective combination of the metal-to-ligand charge-transfer excited state with the halide-to-ligand charge-transfer excited state. Thus, the emission color change is due to stabilization of the π* levels of the central aryl group in the diphosphine ligand. Furthermore, these copper(I) complexes exhibit thermally activated delayed fluorescence at 298 K because of the small singlet-triplet energy difference (ΔE = 523 and 564 cm(-1) for Cu-py and Cu-pyz, respectively). The stability of these complexes in chloroform, due to the rigid bonds between the diphosphine ligands and the Cu(I) ions, enables the preparation of emissive poly(methyl methacrylate) films by the solution-doping technique.

  8. A short designed semi-aromatic organic nanotube – synthesis, chiroptical characterization, and host properties

    DEFF Research Database (Denmark)

    Wixe, Torbjörn; Christensen, Niels Johan; Lidin, Sven


    The first generation of an organic nanotube based on the enantiomerically pure bicyclo[3.3.1]nonane framework is presented. The helical tube synthesised is the longest to date having its aromatic systems oriented parallel to the axis of propagation (length 26 Å and inner diameter 11 Å according t...

  9. An Efficient Synthesis of Functionalized 3-(α-amidobenzyl-4-hydroxycoumarin Derivatives by ZnO Nanoparticles Promoted Condensation Reaction Between Aromatic Aldehyde, 4-hydroxycoumarin, and Amides

    Directory of Open Access Journals (Sweden)

    Hossein Anaraki-Ardakani


    Full Text Available An efficient and green protocol for the synthesis of 3-(α-amidobenzyl-4-hydroxycoumarin derivatives by one pot, three component coupling reaction of aromatic aldehyde, 4-hydroxycoumarin, and amides has been developed using ZnO nanoparticles (NPs as the catalyst. The procedure is formed in high yields, short reaction time and an environmentally friendly specificity.

  10. Synthesis of Aryl-Substituted 2,4-Dinitrophenylamines: Nucleophilic Aromatic Substitution as a Problem-Solving and Collaborative-Learning Approach (United States)

    Santos, Elvira Santos; Garcia, Irma Cruz Gavilan; Gomez, Eva Florencia Lejarazo; Vilchis-Reyes, Miguel Angel


    A series of experiments based on problem-solving and collaborative-learning pedagogies are described that encourage students to interpret results and draw conclusions from data. Different approaches including parallel library synthesis, solvent variation, and leaving group variation are used to study a nucleophilic aromatic substitution of…

  11. Two-electron Oxidation of a Twisted Non Anti-aromatic 40π Expanded Isophlorin

    Indian Academy of Sciences (India)



    Expanded isophlorins are typical examples for stable anti-aromatic systems. Paratropic ring current effects are observed in their NMR spectra mainly due to their planar conformation. Herein we report the synthesis of the first twisted 40π expanded isophlorin and also its two-electron oxidation to a 38π dication. It sustains the twisted conformation for the 4nπ and (4n+2)π electrons. Due to the non-planar conformation, they do not display ring current effects in their respective 1H NMR spectrum. NICS calculations reveal the non-(anti)aromatic features for the neutral 40π and the 38π dication species.

  12. Asymmetric synthesis of a functionalized tricyclo[,6]decane ring system present in kelsoene and poduran

    Indian Academy of Sciences (India)

    Amrita Ghosh; Subrata Ghosh


    Synthesis of a functionalized tricyclo[,6]decane derivative in enantiomerically pure form, the core structure present in the natural products kelsoene and poduran, is described. The key steps involve a stereocontrolled copper (I)-catalyzed intramolecular [2+2] photocycloaddition of a 1, 6-diene prepared from D-mannitol to form a substituted bicyclo[3.2.0]heptane derivative and a ring closing olefin metathesis involving the vicinal substituents on the five-membered ring of the bicyclo[3.2.0]heptane derivative.


    Directory of Open Access Journals (Sweden)

    Ticuţa Negreanu-Pîrjol


    Full Text Available In this paper we report the synthesis, physical-chemical characterization and antimicrobial activity of some new complex compounds of hetero-aromatic biguanides ligands, chlorhexidine base (CHX and chlorhexidine diacetate (CHXac2 with metallic ions Cu(II and Zn(II, in different molar ratio. The synthesized complexes were characterized by elemental chemical analysis and differential thermal analysis. The stereochemistry of the metallic ions was determined by infrared spectra, UV-Vis, EPR spectroscopy and magnetic susceptibility in the aim to establish the complexes structures. The biological activity of the new complex compounds was identified in solid technique by measuring minimum inhibition diameter of bacterial and fungal culture, against three standard pathogen strains, Escherichia coli ATCC 25922, Staphilococcus aureus ATCC 25923 and Candida albicans ATCC 10231. The results show an increased specific antimicrobial activity for the complexes chlorhexidine:Cu(II 1:1 and 1:2 compared with the one of the Zn(II complexes.

  14. Synthesis of Aromatic Retinoids and Curcuminoids and Evaluation of their Antiproliferative, Antiradical, and Anti‐inflammatory Activities (United States)

    Morzycki, Jacek W.; Rárová, Lucie; Grúz, Jiři; Sawczuk, Tomasz; Kiełczewska, Urszula; Siergiejczyk, Leszek


    Abstract Natural retinoids and curcuminoids are known for their broad spectrum of biological properties, such as antioxidant, anti‐inflammatory, antitumor, and so forth. In this work, a convenient synthesis of aromatic retinoids and curcuminoids from vinyl or allyl ketones, and the corresponding alcohols, using olefin metathesis as a key reaction, was elaborated. The best yields and diastereoselectivities were obtained from allylic or homoallylic alcohols by employing the two‐step cross‐metathesis/oxidation procedure. The synthesized analogues were tested for their antiproliferative activity on human cancer cell lines of various origin (leukemia CEM, adenocarcinoma MCF7, cervical carcinoma HeLa) as well as for their antioxidant and anti‐inflammatory activity in vitro. All examined derivatives exhibited strong anti‐inflammatory activity in vitro without affecting cell viability. They also showed strong cytotoxicity against leukemia cell line CEM, except for 18 and 35. The antioxidant activity of the tested compounds was rather weak. PMID:27547644

  15. A New Membrane Protein Sbg1 Links the Contractile Ring Apparatus and Septum Synthesis Machinery in Fission Yeast (United States)

    Sethi, Kriti; Palani, Saravanan; Cortés, Juan C. G.; Sato, Mamiko; Sevugan, Mayalagu; Ramos, Mariona; Vijaykumar, Shruthi; Osumi, Masako; Naqvi, Naweed I.; Ribas, Juan Carlos; Balasubramanian, Mohan


    Cytokinesis in many organisms requires a plasma membrane anchored actomyosin ring, whose contraction facilitates cell division. In yeast and fungi, actomyosin ring constriction is also coordinated with division septum assembly. How the actomyosin ring interacts with the plasma membrane and the plasma membrane-localized septum synthesizing machinery remains poorly understood. In Schizosaccharomyces pombe, an attractive model organism to study cytokinesis, the β-1,3-glucan synthase Cps1p / Bgs1p, an integral membrane protein, localizes to the plasma membrane overlying the actomyosin ring and is required for primary septum synthesis. Through a high-dosage suppressor screen we identified an essential gene, sbg1+ (suppressor of beta glucan synthase 1), which suppressed the colony formation defect of Bgs1-defective cps1-191 mutant at higher temperatures. Sbg1p, an integral membrane protein, localizes to the cell ends and to the division site. Sbg1p and Bgs1p physically interact and are dependent on each other to localize to the division site. Loss of Sbg1p results in an unstable actomyosin ring that unravels and slides, leading to an inability to deposit a single contiguous division septum and an important reduction of the β-1,3-glucan proportion in the cell wall, coincident with that observed in the cps1-191 mutant. Sbg1p shows genetic and / or physical interaction with Rga7p, Imp2p, Cdc15p, and Pxl1p, proteins known to be required for actomyosin ring integrity and efficient septum synthesis. This study establishes Sbg1p as a key member of a group of proteins that link the plasma membrane, the actomyosin ring, and the division septum assembly machinery in fission yeast. PMID:27749909

  16. Synthesis and Properties of Novel Aromatic Azo Compounds from Hydroxyazobenzene and Cyanuric Chloride

    Institute of Scientific and Technical Information of China (English)

    李巍巍; 徐冬梅; 张志兰; 徐颖


    A new series of aromatic azo compounds with one, two, three and five azobenzene units were facilely constructed by dehydrochlorination reaction between p-hydroxyazobenzene, 4,4'-dihydroxyazobenzene and cyanuric chloride under very mild conditions. Their solubility, crystallinity, thermostability, UV-vis absorption properties and photoisomerization behaviors were carefully examined. When the number of azobenzene unit grew, the solubility of the synthesized compounds basically decreased, the crystallinity of the synthesized compounds firstly rose then dropped, while the thermostability and UV-vis absorption ability of the synthesized compounds greatly im- proved. All the aromatic azo compounds exhibited typical reversible photoisomerization behaviors and were expected to be applied in photosensitive material areas.


    Institute of Scientific and Technical Information of China (English)

    Han Peng; Di Chang; Ben-zhong Tang


    Novel fluorene-based poly(aromatic diacetylene)s have been synthesized by CuCl-catalyzed oxidative coupling ofaromatic diynes. New aromatic diynes 2,7-diethynyl-9,9-bis(triphenylamine)fluorene (M1) is synthesized by multistepreactions. The structures and properties of the polymers are characterized and evaluated by IR, NMR, TGA, UV,photoluminescence (PL), and cyclic voltammetry analyses. These polymers possess good thermal stability. All the polymersare completely soluble in coammon solvents such as toluene, THF, chloroform, and dichloromethane. The polymers exhibitstrong blue photoluminescence in solution and green photoluminescence in the solid state. The polymer containingtriphenylamine-substituted fluorene has lower oxidation potential (-5.45 eV) than the previous polyfluorenes (-5.80 eV).

  18. Rhodium-catalyzed intramolecular hydroarylation of 1-halo-1-alkynes: regioselective synthesis of semihydrogenated aromatic heterocycles. (United States)

    Murase, Hirohiko; Senda, Kousuke; Senoo, Masato; Hata, Takeshi; Urabe, Hirokazu


    The regioselective intramolecular hydroarylation of (3-halo-2-propynyl)anilines, (3-halo-2-propynyl) aryl ethers, or (4-halo-3-butynyl) aryl ethers was efficiently catalyzed by Rh2(OCOCF3)4 to give semihydrogenated aromatic heterocycles, such as 4-halo-1,2-dihydroquinolines, 4-halo-3-chromenes, or 4-(halomethylene)chromans, in good to excellent yields. Some synthetic applications taking advantage of the halo-substituents of the products are also illustrated.

  19. Heptaphyrins: Expanded porphyrins with seven heterocyclic rings

    Indian Academy of Sciences (India)

    Venkataramanarao G Anand; Simi K Pushpan; Sundararaman Venkatraman; Tavarekere K Chandrashekar


    Expanded porphyrins containing seven pyrrole/heterocyclic rings linked in a cyclic fashion are termed heptaphyrins. The number of -electrons in heptaphyrins depends on the number of meso carbon bridges used to link the heterocyclic rings, accordingly heptaphyrins with 28-electrons and 30 -electrons are reported to date. Both condensation reactions of the appropriate precursors and acid-catalysed oxidative coupling reactions have been utilized to synthesise the heptaphyrins. The 30 heptaphyrins exhibit rich structural diversity where some of the heterocyclic rings in the macrocycle undergo a 180° ring flipping. An overview of the synthetic methods employed for the synthesis of heptaphyrins, their spectroscopic properties, structural behaviour and aromatic properties are highlighted in this paper.

  20. Quantification of carcinogenic 4- to 6-ring polycyclic aromatic hydrocarbons in human urine by solid-phase microextraction gas chromatography-isotope dilution mass spectrometry. (United States)

    Campo, Laura; Fustinoni, Silvia; Bertazzi, Pieralberto


    Polycyclic aromatic hydrocarbons (PAHs) are pollutants found in living and working environments. The aim of this study was to develop a solid-phase microextraction (SPME) gas chromatography (GC)-isotope dilution mass spectrometry method for the quantification of 10 four- to six-ring PAHs in urine samples. Seven of the selected PAHs have been classified as carcinogenic. Under the final conditions, analytes were sampled with a 100-μm polydimethylsiloxane SPME fibre for 60 min at 80 °C and desorbed in the injection port of the GC at 270 °C. Fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, indeno[1,2,3-cd]pyrene and benzo[ghi]perylene were separated using a highly arylene-modified phase capillary column and quantified by MS using eight deuterated PAHs as surrogate internal standards. Limits of quantification (LOQ) were in the 0.5- to 2.2-ng/L range. Validation showed linear dynamic ranges up to 340 ng/L, inter- and intra-run precisions <20%, and accuracies within 20% of spiked concentrations. Matrix effect evaluation and the use of control charts to monitor process performances showed that the isotope dilution approach allowed for the control of bias sources. Urinary PAHs were above or equal to LOQ, depending on different compounds, in 58-100% (min-max), 40-100% and 5-39% of samples from coke oven workers (n = 12), asphalt workers (n = 10) and individuals not occupationally exposed to PAHs (n = 18), respectively. Chrysene was the most abundant PAH determined with median levels of 62.6, 6.9 and <0.6 ng/L, respectively. These results show that the method is suitable for quantifying carcinogenic PAHs in specimens from individuals with different levels of PAH exposure.

  1. One-pot three-component synthesis of quinoxaline and phenazine ring systems using Fischer carbene complexes

    Directory of Open Access Journals (Sweden)

    Priyabrata Roy


    Full Text Available One-pot three-component coupling of o-alkynylheteroaryl carbonyl derivatives with Fischer carbene complexes and dienophiles leading to the synthesis of quinoxaline and phenazine ring systems has been investigated. This involves the generation of furo[3,4-b]pyrazine and furo[3,4-b]quinoxaline as transient intermediates, which were trapped with Diels–Alder dienophiles. This is the first report on furo[3,4-b]pyrazine intermediates.

  2. Ring-closing metathesis for the synthesis of a highly G-quadruplex selective macrocyclic hexaoxazole having enhanced cytotoxic potency. (United States)

    Satyanarayana, Mavurapu; Rzuczek, Suzanne G; Lavoie, Edmond J; Pilch, Daniel S; Liu, Angela; Liu, Leroy F; Rice, Joseph E


    The synthesis of a 24-membered macrocyclic hexaoxazole via ring-closing metathesis is described. The target compound selectively stabilizes G-quadruplex DNA with no detectable stabilization of duplex DNA. An MTT cytotoxicity assay indicated that this unsaturated macrocyclic hexaoxazole exhibits significant cytotoxicity toward P388, RPMI 8402, and KB3-1 cell lines with IC50 values of 45, 25, and 38 nM, respectively.

  3. Synthesis and Nonlinear Optical Property of a Series of New Chromophores Containing Furan Ring as the Only Conjugation Bridge

    Institute of Scientific and Technical Information of China (English)


    This paper reports the synthesis and the nonlinear optical property of a series of new chromophores which contain furan ring as the only conjugation bridge for the first time. They are characterized by UV-VIS, FT-IR, 1H NMR, MS and elemental analysis. Their dipole moment and the first-order molecular hyperpolarizability (β) are calculated and compared with those of the analogues containing either benzene or thiophene as the conjugation bridge.

  4. Ring-Contraction Strategy for the Practical, Scalable, Catalytic Asymmetric Synthesis of Versatile γ-Quaternary Acylcyclopentenes

    KAUST Repository

    Hong, Allen Y.


    Contraction action! A simple protocol for the catalytic asymmetric synthesis of highly functionalized γ-quaternary acylcyclopentenes (see schematic) in up to 91 % overall yield and 92 % ee has been developed. The reaction sequence employs a palladium-catalyzed enantioselective alkylation reaction and exploits the unusual stability of β-hydroxy cycloheptanones to achieve a general and robust method for performing two-carbon ring contractions.

  5. Structural basis of enzymatic benzene ring reduction. (United States)

    Weinert, Tobias; Huwiler, Simona G; Kung, Johannes W; Weidenweber, Sina; Hellwig, Petra; Stärk, Hans-Joachim; Biskup, Till; Weber, Stefan; Cotelesage, Julien J H; George, Graham N; Ermler, Ulrich; Boll, Matthias


    In chemical synthesis, the widely used Birch reduction of aromatic compounds to cyclic dienes requires alkali metals in ammonia as extremely low-potential electron donors. An analogous reaction is catalyzed by benzoyl-coenzyme A reductases (BCRs) that have a key role in the globally important bacterial degradation of aromatic compounds at anoxic sites. Because of the lack of structural information, the catalytic mechanism of enzymatic benzene ring reduction remained obscure. Here, we present the structural characterization of a dearomatizing BCR containing an unprecedented tungsten cofactor that transfers electrons to the benzene ring in an aprotic cavity. Substrate binding induces proton transfer from the bulk solvent to the active site by expelling a Zn(2+) that is crucial for active site encapsulation. Our results shed light on the structural basis of an electron transfer process at the negative redox potential limit in biology. They open the door for biological or biomimetic alternatives to a basic chemical synthetic tool.

  6. Second generation benzofuranone ring substituted noscapine analogs: synthesis and biological evaluation. (United States)

    Mishra, Ram Chandra; Karna, Prasanthi; Gundala, Sushma Reddy; Pannu, Vaishali; Stanton, Richard A; Gupta, Kamlesh Kumar; Robinson, M Hope; Lopus, Manu; Wilson, Leslie; Henary, Maged; Aneja, Ritu


    Microtubules, composed of α/β tubulin heterodimers, represent a validated target for cancer chemotherapy. Thus, tubulin- and microtubule-binding antimitotic drugs such as taxanes and vincas are widely employed for the chemotherapeutic management of various malignancies. Although quite successful in the clinic, these drugs are associated with severe toxicity and drug resistance problems. Noscapinoids represent an emerging class of microtubule-modulating anticancer agents based upon the parent molecule noscapine, a naturally occurring non-toxic cough-suppressant opium alkaloid. Here we report in silico molecular modeling, chemical synthesis and biological evaluation of novel analogs derived by modification at position-7 of the benzofuranone ring system of noscapine. The synthesized analogs were evaluated for their tubulin polymerization activity and their biological activity was examined by their antiproliferative potential using representative cancer cell lines from varying tissue-origin [A549 (lung), CEM (lymphoma), MIA PaCa-2 (pancreatic), MCF-7 (breast) and PC-3 (prostate)]. Cell-cycle studies were performed to explore their ability to halt the cell-cycle and induce subsequent apoptosis. The varying biological activity of these analogs that differ in the nature and bulk of substituent at position-7 was rationalized utilizing predictive in silico molecular modeling.

  7. Synthesis, structural investigations, hydrogen-deuterium exchange studies, and molecular modeling of conformationally stablilized aromatic oligoamides. (United States)

    Yan, Yan; Qin, Bo; Ren, Changliang; Chen, Xiuying; Yip, Yeow Kwan; Ye, Ruijuan; Zhang, Dawei; Su, Haibin; Zeng, Huaqiang


    Biasing the conformational preferences of aromatic oligoamides by internally placing intramolecular hydrogen bonds has led to a series of stably folded molecular strands. This article presents the results from extensive solid-state, solution, and computational studies on these folding oligomers. Depending on its backbone length, an oligoamide adopts a crescent or helical conformation. Surprisingly, despite the highly repetitive nature of the backbone, the internally placed, otherwise very similar intramolecular hydrogen bonds showed significantly different stabilities as demonstrated by hydrogen-deuterium exchange data. It was also observed that the hydrogen-bonding strength can be tuned by adjusting the substituents attached to the exterior of the aromatic backbones. Examining the amide hydrogen-deuterium exchange rates of trimers revealed that a six-membered hydrogen bond nearing the ester end is the weakest among all the four intramolecular hydrogen bonds of a molecule. This observation was verified by ab initio quantum mechanical calculations at the level of B3LYP/6-31G*. Such a "weak point" creates the "battle of the bulge" where backbone twisting is centered, which is consistently observed in the solid-state structures of the four trimer molecules studied. In the solid state, the oligomers assemble into interesting one-dimensional structures. A pronounced columnar packing of short oligomers (i.e., dimers, trimers, and tetramer) and channel-like, potentially ion-conducting stacks of longer oligomers (i.e., tetramer, pentamer, and hexamer) were observed.


    Directory of Open Access Journals (Sweden)

    T. Yu. Archinova


    Full Text Available We have carried out preliminary analysis of foreseeable biological activity of some compounds derivants of 4-oxopyrimidine with a use of PASS program. We have established that they should have anti-inflammatory, benzothiazepine, analgesic, hypotensive, nootropic activity.Molecular docking method (Autodock 4.0 allowed modeling of interaction of 4-oxopyrimidine derivatives with GABA, dopamine and benzothiazepine receptors. On the basis of the data received we forecasted structures of N-aromatic derivatives of 4-oxopyrimidine. The derivatives of 4-xopyrimidine we received with a reaction of cyclocondensation of N-acyl-β-ketamides with aromatic amines. We have synthesized five compounds. Using IR, UV and NMR spectrometry we have established its presumable structure as well as some physical and optical parameters. We have elaborated methods of quantitative spectrophotometric determination of two synthesized compounds and made its validation estimation.

  9. Synthesis of aromatic polyimides with sulfone diamine moieties for a novel membrane oxygenator. (United States)

    Kawakami, H; Nagaoka, S


    The authors have synthesized soluble aromatic polyimides derived from 2,2'-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 3,3'- or 4,4'-diamino-diphenylsulfone (m-DDS or p-DDS) to develop a novel membrane oxygenator. Asymmetric gas exchange membranes for the oxygenator were prepared by a dry/wet phase inversion process. The resulting membrane structure consisted of an ultrathin, selective, and defect free skin layer supported by a porous substructure. The membranes exhibited extremely high gas flux and selectivity. CO2 flux through the polyimide membranes used in this study increased with a decrease in CO2 pressure and was in accordance with the dual mode transport described by a combination of the Henry and Langmuir modes. This indicates that CO2 is selectively removed from the membranes at low CO2 pressure as compared with presently available materials for membrane oxygenators, such as polydimethylsiloxane and polypropylene. The number of platelets adherent to the surface of the polyimide were significantly smaller than those on polydimethylsiloxane and polypropylene, and the deformation and aggregation of platelets on polyimide were not observed. These findings suggest that aromatic polyimides with sulfone diamine moieties are promising membrane materials for an oxygenator.

  10. Synthesis and Biological Evaluation of Norcantharidin Derivatives Possessing an Aromatic Amine Moiety as Antifungal Agents

    Directory of Open Access Journals (Sweden)

    Yang Wang


    Full Text Available Based on the structure of naturally produced cantharidin, different arylamine groups were linked to the norcantharidin scaffold to provide thirty six compounds. Their structures were confirmed by melting point, 1H-NMR, 13C-NMR and HRMS-ESI studies. These synthetic compounds were tested as fungistatic agents against eight phytopathogenic fungi using the mycelium growth rate method. Of these thirty six derivatives, seven displayed stronger antifungal activity than did norcantharidin, seven showed higher activity than did cantharidin and three exhibited more significant activity than that of thiabendazole. In particular, 3-(3′-chloro-phenylcarbamoyl norcantharidate II-8 showed the most significant fungicidal activity against Sclerotinia fructigena and S. sclerotiorum, with IC50 values of 0.88 and 0.97 μg/mL, respectively. The preliminary structure-activity relationship data of these compounds revealed that: (1 the benzene ring is critical for the improvement of the spectrum of antifungal activity (3-phenylcarbamoyl norcantharidate II-1 vs norcantharidin and cantharidin; (2 among the three sites, including the C-2′, C-3′ and C-4′ positions of the phenyl ring, the presence of a halogen atom at the C-3′position of the benzene ring caused the most significant increase in antifungal activity; (3 compounds with strongly electron-drawing or electron-donating groups substitutions were found to have a poor antifungal activity; and (4 compared with fluorine, bromine and iodine, chlorine substituted at the C-3′ position of the benzene ring most greatly promoted fungistatic activity. Thus, compound II-8 has emerged as new lead structure for the development of new fungicides.

  11. C-shaped diastereomers containing cofacial thiophene-substituted quinoxaline rings: synthesis, photophysical properties, and X-ray crystallography. (United States)

    DeBlase, Catherine R; Finke, Ryan T; Porras, Jonathan A; Tanski, Joseph M; Nadeau, Jocelyn M


    Synthesis and characterization of two diastereomeric C-shaped molecules containing cofacial thiophene-substituted quinoxaline rings are described. A previously known bis-α-diketone was condensed with an excess of 4-bromo-1,2-diaminobenzene in the presence of zinc acetate to give a mixture of two C-shaped diastereomers with cofacial bromine-substituted quinoxaline rings. After chromatographic separation, thiophene rings were installed by a microwave-assisted Suzuki coupling reaction, resulting in highly emissive diastereomeric compounds that were studied by UV-vis, fluorescence, and NMR spectroscopy, as well as X-ray crystallography. The unique symmetry of each diastereomer was confirmed by NMR spectroscopy. NMR data indicated that the syn isomer has restricted rotation about the bond connecting the thiophene and quinoxaline rings, which was also observed in the solid state. The spectroscopic properties of the C-shaped diastereomers were compared to a model compound containing only a single thiophene-substituted quinoxaline ring. Ground state intramolecular π-π interactions in solution were detected by NMR and UV-vis spectroscopy. Red-shifted emission bands, band broadening, and large Stokes shifts were observed, which collectively suggest excited state π-π interactions that produce excimer-like emissions, as well as a remarkable positive emission solvatochromism, indicating charge-transfer character in the excited state.

  12. Radical aryl migration enables diversity-oriented synthesis of structurally diverse medium/macro- or bridged-rings (United States)

    Li, Lei; Li, Zhong-Liang; Wang, Fu-Li; Guo, Zhen; Cheng, Yong-Feng; Wang, Na; Dong, Xiao-Wu; Fang, Chao; Liu, Jingjiang; Hou, Chunhui; Tan, Bin; Liu, Xin-Yuan


    Medium-sized and medium-bridged rings are attractive structural motifs in natural products and therapeutic agents. Due to the unfavourable entropic and/or enthalpic factors with these ring systems, their efficient construction remains a formidable challenge. To address this problem, we herein disclose a radical-based approach for diversity-oriented synthesis of various benzannulated carbon- and heteroatom-containing 8-11(14)-membered ketone libraries. This strategy involves 1,4- or 1,5-aryl migration triggered by radical azidation, trifluoromethylation, phosphonylation, sulfonylation, or perfluoroalkylation of unactivated alkenes followed by intramolecular ring expansion. Demonstration of this method as a highly flexible tool for the construction of 37 synthetically challenging medium-sized and macrocyclic ring scaffolds including bridged rings with diverse functionalities and skeletons is highlighted. Some of these products showed potent inhibitory activity against the cancer cell or derivative of human embryonic kidney line in preliminary biological studies. The mechanism of this novel strategy is investigated by control experiments and DFT calculations.

  13. Synthesis of branched dithiotrisaccharides via ring-opening reaction of sugar thiiranes. (United States)

    Repetto, Evangelina; Manzano, Verónica E; Uhrig, María Laura; Varela, Oscar


    Satisfactory procedures are described for the synthesis of 5,6- and 3,4-thiirane derivatives from the respective hexofuranose or hexopyranose epoxide precursors. The controlled ring-opening reaction of thiiranes by 1-thioaldoses was successfully accomplished to afford, regio- and stereoselectively, β-S-(1→4)-3,4-dithiodisaccharides. For instance, the regioselective attack of per-O-acetyl-1-thioglucose (16) to C-4 of 2-propyl 2,6-di-O-acetyl-3,4-epithio-α-D-galactopyranoside (14) gave the derivative of Glcp-β-S-(1→4)-3,4-dithioGlcp-O-iPr (17). This thiodisaccharide was accompanied by the (1→3)-disulfide 18, formed between 16 and 17, and the symmetric (3→3)-disulfide 19, which resulted from the oxidative dimerization of 17. However, the S-acetyl derivative of 17 could be obtained in good yield (62%) by LiAlH(4) reduction of the crude mixture 17-19, followed by acetylation. The same sequence of reactions starting from 14 and the 1-thiolate of Galp afforded the per-O,S-acetyl derivative of Galp-β-S-(1→4)-3,4-dithio-α-D-Glcp-O-iPr (23), which was selectively S-deacetylated to give 25. The dithiosaccharides 17 and 25 are 3,4-di-S-analogues of derivatives of the natural disaccharides cellobiose and lactose, respectively. The ring-opening reaction of 5,6-epithiohexofuranoses of D-galacto (8) or L-altro (11) configuration with 1-thioaldoses was also regio- and stereoselective to give the respective β-S-(1→6)-linked 5,6-dithiodisaccharides 26 or 29 in excellent yields. Glycosylation of the free thiol group of 17, 25, or 26, using trichloroacetimidates as glycosyl donors, led to the corresponding branched dithiotrisaccharides. Some of them are sulfur analogues of derivatives of branched trisaccharides found in natural polysaccharides.

  14. Synthesis, Fluorescence Properties and Biological Activity of 8-Hydroxyquinoline Conjugate Bonded Aromatic Heterocyclic Derivatives

    Institute of Scientific and Technical Information of China (English)


    Four kinds of 8-hydroxyquinoline conjugate bonded aromatic heterocyclic derivatives were designed and syn-thesized for potential use in the emission and electron conduction layers in organic light emitting devices, and as luminescent probes for metal ions. These novel compounds were characterized by IR, 1H NMR,13C NMR, Mass and UV-visible spectra. The photoluminescent properties of the new compounds including the spectra (shape of bands,λex, λem), quantum yield (pf) and lifetime (t) were investigated. Moreover, density functional theory method was used to study the relationship between the geometric configuration and emission wavelength. MTT assays of cell proliferation of rMSC and DPPH radical-scavenging tests suggested that the new compounds generate a sig-nificant increase of rMSC and demonstrate a good antioxidant activity.

  15. Polish turpentine as source of raw material for synthesis of aromatic substances

    Energy Technology Data Exchange (ETDEWEB)

    Wizner, I.


    This paper provides data on the volume of world-wide use of turpentine (Sk), essential directions of Sk utilization and trends in this area. The significant interest toward turpentine as a raw material for deriving aromatic substances, including linalool, geraniol, citronellol, verbenol, isoborneol, ionones, citrals, irone and menthol. Reaction schemes are provided for deriving from Poland's production of turpentine and its basic components the following: ..cap alpha..-pinene ( about54%), ..beta..-pinene ( about2.2%), and 3-carene ( about-40%) which are at the present time imported. Such use of turpentine, by providing the most valuable and high-demand production of its derivatives will be extremely efficient for Poland.

  16. Design, synthesis and biological activity of aromatic diketone derivatives as HIV-1 integrase inhibitors. (United States)

    Hu, Liming; Li, Zhipeng; Wang, Zhanyang; Liu, Gengxin; He, Xianzhuo; Wang, Xiaoli; Zeng, Chengchu


    A series of aromatic diketone derivatives were designed and synthesized as potential HIV-1 integrase (IN) inhibitors and evaluated to determine their ability to inhibit the strand transfer process of HIV-1 integrase. The results indicate that (Z)-1-(3-acetyl-2-hydroxy-4,6-dimethoxyphenyl)-3-hydroxy-3-(substituted)phenylprop-2-en-1-one (5a-5d) can moderately inhibit HIV-1 integrase. The cyclization and condensation products (6a-6c and 7e-7f) of compounds 5a-5d show poor inhibitory activity against HIV-1 integrase. The molecular docking results indicate that the different types of compounds act on HIV-1 integrase in different ways, and these results can explain the differences in the inhibitory activities.

  17. Synthesis of Oxygen Heterocycles via Aromatic C-O Bond Formation Using Arynes. (United States)

    Miyabe, Hideto


    Most of the synthetic approaches to the benzo-fused heterocycles containing an oxygen atom have involved the use of phenol derivatives as a starting material. This review highlights the new synthetic approaches involving the aromatic C-O bond-forming process using arynes. The insertion of arynes into the C=O bond gives the unstable intermediates, [2 + 2] cycloaddition-type adducts, which can be easily converted into a variety of oxygen atom-containing heterocycles in a single operation. In this review, the syntheses of oxygen heterocycles, such as coumarin, chromene, xanthene, dihydrobenzofuran and benzofuran derivatives, via the insertion of arynes into the C=O bond of aldehydes or formamides are summarized.


    Institute of Scientific and Technical Information of China (English)

    Xiao-ting Chen; Ming Zhang; Xu-dong Tang


    Aromatic copolyamides were synthesized by the Yamazaki phosphorylation method starting from bis(4-carboxyphenyl) phenyl phosphine oxide,terephthalic acid and 4,4'-diaminodiphenyl methane.The copolymers with inherent viscosities of 0.52-0.99 dL/g were obtained.The structures of the copolyamides were characterized by elemental analysis,FTIR and NMR.The glass transition temperatures were measured by DSC and DMA,respectively,and the results showed that the Tgs of the polymers were higher than 287℃.Thermal decomposition temperatures of the copolyamides at 5% weight loss were found in the range of 423-469℃ by TGA.Most of the copolymers were readily soluble in a variety of organic solvents such as NMP,DMAc,m-cresol and so on.The tensile experiments of the thin films showed that the polymers had good mechanical properties.

  19. Synthesis of Oxygen Heterocycles via Aromatic C-O Bond Formation Using Arynes

    Directory of Open Access Journals (Sweden)

    Hideto Miyabe


    Full Text Available Most of the synthetic approaches to the benzo-fused heterocycles containing an oxygen atom have involved the use of phenol derivatives as a starting material. This review highlights the new synthetic approaches involving the aromatic C-O bond-forming process using arynes. The insertion of arynes into the C=O bond gives the unstable intermediates, [2 + 2] cycloaddition-type adducts, which can be easily converted into a variety of oxygen atom-containing heterocycles in a single operation. In this review, the syntheses of oxygen heterocycles, such as coumarin, chromene, xanthene, dihydrobenzofuran and benzofuran derivatives, via the insertion of arynes into the C=O bond of aldehydes or formamides are summarized.

  20. Asymmetric synthesis of aromatic β-amino acids using ω-transaminase: Optimizing the lipase concentration to obtain thermodynamically unstable β-keto acids. (United States)

    Mathew, Sam; Jeong, Seong-Su; Chung, Taeowan; Lee, Sang-Hyeup; Yun, Hyungdon


    Synthesized aromatic β-amino acids have recently attracted considerable attention for their application as precursors in many pharmacologically relevant compounds. Previous studies on asymmetric synthesis of aromatic β-amino acids using ω-transaminases could not be done efficiently due to the instability of β-keto acids. In this study, a strategy to circumvent the instability problem of β-keto acids was utilized to generate β-amino acids efficiently via asymmetric synthesis. In this work, thermodynamically stable β-ketoesters were initially converted to β-keto acids using lipase, and the β-keto acids were subsequently aminated using ω-transaminase. By optimizing the lipase concentration, we successfully overcame the instability problem of β-keto acids and enhanced the production of β-amino acids. This strategy can be used as a general approach to efficiently generate β-amino acids from β-ketoesters.

  1. Allenylphosphonates with a 1,3,2-dioxaphosphorinane ring: Synthesis, structures, stability and utility

    Indian Academy of Sciences (India)

    N N Bhuvan Kumar; Manab Chakravarty; N Satish Kumar; K V Sajna; K C Kumara Swamy


    Synthesis, structures and stability (thermal and air) of allenylphosphonates of the type (OCH2CMe2CH2O)P(O)C(R)=C=CR'R" and [R"R'C=C=C(R)P(O)(OCH2)2]2C are discussed. Thermally activated dimerization (cycloaddition) of (OCH2CMe2CH2O)P(O)C(H)=C=CMe2 leads to the phosphonocyclobutane [(OCH2CMe2CH2O)P(O)C(H)=]2[C-CMe2]2 (18). Many of these allenes undergo addition of diethylamine to lead to enaminophosphonates that are readily hydrolysed by water to lead to -ketophosphonates. The latter compounds are useful as Horner-Wadsworth-Emmons (HWE) reagents. Molecular structures of (OCH2CMe2CH2O)P(O)C(CH2OH)=C=CH2 (6), [H2C=C=C(H)P(O)(OCH2)2]2C (9), (OCH2CMe2CH2O)P(O)CH=C=CH2 (12), [(OCH2CMe2CH2O)P(O)C(H)=]2[C-CMe2]2 (18), and the -ketophosphonate (OCH2CMe2CH2O)P(O)CH2)-C(O)CHMe2 (24) have been determined. In compound 6, intermolecular hydrogen bonding between the phosphoryl oxygen and the hydroxyl group leading to an infinite chain is observed. In 6, there is a significant deviation (ca 7°) from the orthogonality expected between the planes containing 4 atoms of (a) H2C=C and (b) C=C(H)P in the allene part. In 9, weak C-H…O interaction between the phosphoryl oxygen atom and a CH2 proton of the six-membered ring is present.

  2. One-step synthesis of α,β-unsaturated arylsulfones by a novel multicomponent reaction of aromatic aldehydes,chloroacetonitrile, benzenesulfinic acid sodium salt

    Institute of Scientific and Technical Information of China (English)

    Lei Zhang; Mao Hua Ding; Hong Yun Guo


    A new and green method for the synthesis of α,β-unsaturated arylsulfones had been achieved through the condensation of aromatic aldehydes,chloroacetonitrile,benzenesulfinic acid sodium salt in the presence of 1-butyl-3-methyl imidazolium hydroxide ([bmim]OH) in EtOH under reflux.The ionic liquid was recovered and recycled for subsequent reactions.The advantages of this protocol were non-toxic,easy work-up and good yields.

  3. TTF derivative of 2,5-aromatic disubstituted pyrrole, synthesis and electronic study (United States)

    Fomina, Lioudmila; León, Chistopher; Bizarro, Monserrat; Baeza, Alejandro; Gómez-Vidales, Virginia; Sansores, L. Enrique; Salcedo, Roberto


    TTF derivative of substituted pyrrole was obtained by means electrochemical synthesis, the resultant colored mix was characterized by Mass spectrometry, NMR and EPR studies, its intrinsic electronic behavior was measured by a four point probe method, besides theoretical calculations were carried out on the possible structures of the resultant molecular adduct. All the results show that there is a net transfer of an electron between both organic moieties in solution giving place to a semiconductor species.

  4. Synthesis and Evaluation of Changes Induced by Solvent and Substituent in Electronic Absorption Spectra of New Azo Disperse Dyes Containig Barbiturate Ring

    Directory of Open Access Journals (Sweden)

    Hooshang Hamidian


    Full Text Available Six azo disperse dyes were prepared by diazotizing 4-amino hippuric acid and coupled with barbituric acid and 2-thiobarbituric acid. Then, the products were reacted with aromatic aldehyde, sodium acetate, and acetic anhydride, and oxazolone derivatives were formed. Characterization of the dyes was carried out by using UV-Vis, FT-IR, 1H NMR and 13C NMR, and mass spectroscopic techniques. The solvatochromic behavior of azo disperse dyes was evaluated in various solvents. The effects of substituents of aromatic aldehyde, barbiturate, and thiobarbiturate ring on the color of dyes were investigated.

  5. [Synthesis of two-organic complexes and characterization of their adsorption behaviour of ten polycyclic aromatic hydrocarbons]. (United States)

    Meng, Jie; Sun, Yuxiu; Li, Yan


    Metal-organic frameworks (MOFs) are concerned mainly due to the unusual properties for diverse analytical applications, such as high surface area, good thermal stability, inpore functionally and outer-surface modification. Two metal-organic complexes were prepared by two methods of hydrothermal synthesis and room temperature synthesis, separately. The compositions, structures, thermal stability and adsorption properties of the two complexes were characterized by X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) method, which indicated that the two complexes have not only good thermal stability but also good adsorption for polycyclic aromatic hydrocarbons (PAHs). PAHs enter into environment leading to pollution by industrial and agricultural production and life, rooting in the incomplete combustion or pyrolysis of organism. PAHs are strongly carcinogenic and mutagenic. Some PAHs are considered as endocrine disruptors, and maybe have biological effects on human health. Regulations have thus been formulated for monitoring and controlling PAHs by the United States Environmental Protection Agency (U.S. EPA) and other government agencies. Adsorption kinetic of PAHs on the two complexes could be well described by the pseudo-second order kinetic model, and the adsorption behaviors of the two complexes on PAHs are in accord with Langmuir model. In addition, the adsorption capacities increase with the increasing adsorbent dosage. It is proved by the FT-IR data that pi-pi interactions between the PAHs and the framework terephthalic acid molecules. Ten PAHs were adsorbed well on the two complexes which have good adsorptive selectivity. By further optimizing of the two complex materials, it is promising to use them as chromatographic stationary phases.

  6. Photoaddition reactions of silyl ketene acetals with aromatic carbonyl compounds: a new procedure for {beta}-hydroxyester synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Ung Chan; Kim, Moon Jung; Moon, Jae Joon; Oh, Sun Wha; Kim, Hyun Jin [Pusan National Univ., Pusan (Korea, Republic of); Mariano, Patrick S. [University of New Mexico, Albuquerque (United States)


    Photochemical reactions of aromatic carbonyl compounds with silyl ketene acetals have been explored. Irradiation of acetonitrile or benzene solutions containing aryl aldehydes or ketones in the presence of silyl ketene acetals is observed to promote formation of {beta}-hydroxyester, 2,2-dioxyoxetane and 3,3-dioxyoxetane products. The ratios of these photoproducts, which arise by competitive single electron transfer (SET) and classical Paterno-Buchi mechanistic pathway, is found to be dependent on the degree of methyl-substitution on the vinyl moieties of the ketene acetals in a manner which reflects expected alkyl substituent effects on the oxidation potentials of these electron rich donors. An analysis of the product distribution arising by irradiation of a solution containing butyrophenone (6) and the silyl ketene acetal 9, derived from methyl isobutyrate, provides an estimate of the rate constants for the competitive Norrish type II, SET and Paterno-Buchi processes occurring. Finally, sequences involving silyl ketene acetal-aryl aldehyde or ketone photoaddition followed by 2,2-dioxyoxetane hydrolysis represent useful procedures for Claisen-condensation type, {beta}-hydroxyester synthesis.

  7. Orthogonal ring-closing alkyne and olefin metathesis for the synthesis of small GTPase-targeting bicyclic peptides. (United States)

    Cromm, Philipp M; Schaubach, Sebastian; Spiegel, Jochen; Fürstner, Alois; Grossmann, Tom N; Waldmann, Herbert


    Bicyclic peptides are promising scaffolds for the development of inhibitors of biological targets that proved intractable by typical small molecules. So far, access to bioactive bicyclic peptide architectures is limited due to a lack of appropriate orthogonal ring-closing reactions. Here, we report chemically orthogonal ring-closing olefin (RCM) and alkyne metathesis (RCAM), which enable an efficient chemo- and regioselective synthesis of complex bicyclic peptide scaffolds with variable macrocycle geometries. We also demonstrate that the formed alkyne macrocycle can be functionalized subsequently. The orthogonal RCM/RCAM system was successfully used to evolve a monocyclic peptide inhibitor of the small GTPase Rab8 into a bicyclic ligand. This modified peptide shows the highest affinity for an activated Rab GTPase that has been reported so far. The RCM/RCAM-based formation of bicyclic peptides provides novel opportunities for the design of bioactive scaffolds suitable for the modulation of challenging protein targets.

  8. Synthesis, Characterization, and Electropolymerization of Extended Fused-Ring Thieno[3,4-b]pyrazine-Based Terthienyls

    Directory of Open Access Journals (Sweden)

    Kristine L. Konkol


    Full Text Available The synthesis, characterization, and electropolymerization of a series of extended fused-ring thieno[3,4-b]pyrazine-based terthienyls are reported. The target terthienyls contain a central extended thieno[3,4-b]pyrazine analogue containing 2-thienyl units at the reactive α-positions of the central thiophene. The extended fused-ring thieno[3,4-b]pyrazine analogues studied include acenaphtho[1,2-b]thieno[3,4-e]pyrazine, dibenzo[f,h]thieno[3,4-b]quinoxaline, and thieno[3′,4′:5,6]-pyrazino[2,3-f][1,10]phenanthroline. Comparison of the electrochemical and photophysical properties to simple thieno[3,4-b]pyrazine-based terthienyls and their polymeric analogues are reported in order to provide structure-function relationships within this series of compounds and materials.

  9. Study on Tonghaosu and Its Analogs:Isolation, Structure Identification and Synthesis of Antifeedant B-ring-homo-tonghaosu

    Institute of Scientific and Technical Information of China (English)

    CHEN,Li(陈立); YIN,Biao-Lin(尹标林); XU,Han-Hong(徐汉虹); CHIU,Ming-Hua(邱明华); WU,Yu-Lin(吴毓林)


    The methanolic extract from a Chinese endemic Chrysanthemum plant, Dendranthema indicum var. aromaticum, was found to show high antifeeding activity against Pieris brassicae L., and by bioassay-guided separation, the active component, B-ring-homo-tonghaosu, 2-(2',4'-hexadiynylidene)-1,6-dioxaspiro-[4,5]-dec-3-ene (2) was isolated. Its structure was elucidated by comparing its spectroscopic data with those of 2 reported in the literatures. Furthermore new convenient total synthesis methods of B-ring-homo-tonghaosu were also developed to confirm its structure and make its further application in crop protection available. In addition, extensive comparison of spectroscopic data showed that the structure of compound 21 reported in literature should be revised to 2.

  10. Enzyme catalytic nitration of aromatic compounds. (United States)

    Kong, Mingming; Wang, Kun; Dong, Runan; Gao, Haijun


    Nitroaromatic compounds are important intermediates in organic synthesis. The classic method used to synthesize them is chemical nitration, which involves the use of nitric acid diluted in water or acetic acid, both harmful to the environment. With the development of green chemistry, environmental friendly enzyme catalysis is increasingly employed in chemical processes. In this work, we adopted a non-aqueous horseradish peroxidase (HRP)/NaNO2/H2O2 reaction system to study the structural characteristics of aromatic compounds potentially nitrated by enzyme catalysis, as well as the relationship between the charges on carbon atoms in benzene ring and the nitro product distribution. Investigation of various reaction parameters showed that mild reaction conditions (ambient temperature and neutral pH), plus appropriate use of H2O2 and NaNO2 could prevent inactivation of HRP and polymerization of the substrates. Compared to aqueous-organic co-solvent reaction media, the aqueous-organic two-liquid phase system had great advantages in increasing the dissolved concentration of substrate and alleviating substrate inhibition. Analysis of the aromatic compounds' structural characteristics indicated that substrates containing substituents of NH2 or OH were readily catalyzed. Furthermore, analysis of the relationship between natural bond orbital (NBO) charges on carbon atoms in benzene ring, as calculated by the density functional method, and the nitro product distribution characteristics, demonstrated that the favored nitration sites were the ortho and para positions of substituents in benzene ring, similar to the selectivity of chemical nitration.

  11. Synthesis of carbon materials via the cold compression of aromatic molecules and carbon nanostructures (United States)

    Fitzgibbons, Thomas C.

    Carbon's ability for catenation makes it a remarkable element and allows for many interesting and surprising properties and structures. Carbon can exist in one of its two thermodynamically stable bulk crystals, graphite or diamond, one of its several nanostructures: fullerene, nanotube, or graphene, or as an amorphous material with a mixed bonding pattern. Carbon also has an ability to bond heteroatoms such as hydrogen which can increase its properties and structures even further. Pressure has been shown to be able to drastically change the bonding in and structure of carbon based materials. In this dissertation I will present how pressure can be used to synthesize new amorphous hydrogenated carbons and how a battery of analytical techniques can be used to elicit the microstructure of the carbon networks. This microstructure can then be related back to the reaction conditions and more importantly the starting small molecule. This work has been expanded to looking for a molecular analogue to the cold compressed graphite system by investigating the high pressure stability and reactivity of 2-D polycyclic aromatic hydrocarbons. This work was followed by discovering the failure of Single Walled Carbon Nanotubes at high static pressures. When the tubes fail they transform into nano-graphitic polyhedra. It has been found that metallic tubes preferentially collapse, leaving the semiconducting tubes intact for the most part. Finally, the most influential work performed in my dissertation has been related to the kinetically controlled solid state reaction of molecular benzene to form diamond nanothreads. These nanothreads pack into hexagonal bundles without axial order. A combination of Raman spectroscopy, x-ray and neutron scattering, transmission electron microscopy, and first principles calculations were performed to confirm their existence. The three data chapters in this dissertation are enhanced by an introduction to carbon based materials and high pressure chemistry

  12. Synthesis, characterization and thermal properties of new aromatic quaternary ammonium bromides: precursors for ionic liquids and complexation studies (United States)

    Busi, Sara; Lahtinen, Manu; Ropponen, Jarmo; Valkonen, Jussi; Rissanen, Kari


    Series of new aromatic R2R‧2N+Br- (R=benzyl, 4-methylbenzyl, 2-phenylethyl, 3-phenylpropyl; R‧=ethyl, methyl, isopropyl) or RR‧2NH+Br--type (R=benzyl, R‧=isopropyl) quaternary ammonium bromides were prepared by using novel synthetic route in which a formamide (N,N-diethylformamide, N,N-dimethylformamide, N,N-diisopropylformamide) is treated with aralkyl halide in presence of a weak base. The compounds were characterized by 1H-NMR and 13C-NMR spectroscopy and mass spectrometry. Structures of the crystalline compounds were determined by X-ray single crystal diffraction, and in addition the powder diffraction method was used to study the structural similarities between the single crystal and microcrystalline bulk material. Three of the compounds crystallized in monoclinic, two in orthorhombic and one in triclinic crystal system, showing ion pairs, which are interconnected by weak hydrogen bonds and weak π - π interactions between the phenyl rings. Three of the compounds appeared as viscous oil or waxes. Finally, TG/DTA and DSC methods were used to analyze thermal properties of the prepared compounds. The lowest melting points were obtained for diethyldi-(2-phenylethyl)ammonium bromide (122.2 °C) and for diethyldi-(3-phenylpropyl)-ammonium bromide (109.1 °C). In general, decomposition of the compounds started at 170-190 °C without identifiable cleavages, thus liquid ranges of 30-70 °C were observed for some of the compounds.

  13. Synthesis and Structure of a Sodium Complex of an Aromatic β-Diketone and Pyrazolylpyridine

    Directory of Open Access Journals (Sweden)

    Isabel S. Gonçalves


    Full Text Available Reaction of NaH with a THF solution of Eu(BTA3(pypzH [BTA = 1-benzoyl-3,3,3-trifluoroacetonate, pypzH = 2-(3-pyrazolylpyridine] leads to the formation of theeuropium-free tetrasodium complex [Na4(pypzH2(μ4-BTA2(μ2-BTA2]. Single-crystal X-ray diffraction studies revealed the presence of a centrosymmetric Na hybrid tetramer,which fully occupies the contents of the triclinic unit cell. The crystal structure containstwo individual Na cations, Na(1 and Na(2, which have highly irregular {NaN2O3} and{NaO6} local coordination environments, respectively. One of the key features is thepresence of a central {Na4O6} core, which is unprecedented for Na . Externally to this{Na4O6} cluster pyrazolylpyridine organic molecules are N,N-chelated to Na(1. Eventhough all of the organic residues contain aromatic rings, the crystal packing of individualcentrosymmetric tetrasodium [Na4(pypzH2(μ4-BTA2(μ2-BTA2] molecular moieties isessentially driven through geometrical aspects combined with weak C–H···π interactions,rather than the expected a priori π-π interactions. The material also contains classicalstrong hydrogen bonds, even though these do not directly contribute to the packingdriving forces.

  14. Hybrid scorpionate/cyclopentadienyl magnesium and zinc complexes: synthesis, coordination chemistry, and ring-opening polymerization studies on cyclic esters. (United States)

    Garcés, Andrés; Sánchez-Barba, Luis F; Alonso-Moreno, Carlos; Fajardo, Mariano; Fernández-Baeza, Juan; Otero, Antonio; Lara-Sánchez, Agustín; López-Solera, Isabel; Rodríguez, Ana María


    The reaction of the hybrid scorpionate/cyclopentadienyl lithium salt [Li(bpzcp)(THF)] [bpzcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethylcyclopentadienyl] with 1 equiv of RMgCl proceeds cleanly to give very high yields of the corresponding monoalkyl kappa(2)-NN-eta(5)-C(5)H(4) magnesium complexes [Mg(R)(kappa(2)-eta(5)-bpzcp)] (R = Me 1, Et 2, (n)Bu 3, (t)Bu 4, CH(2)SiMe(3) 5, CH(2)Ph 6). Hydrolysis of the hybrid lithium salt [Li(bpzcp)(THF)] with NH(4)Cl/H(2)O in ether cleanly affords the two previously described regioisomers: (bpzcpH) 1-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethyl]-1,3-cyclopentadiene (a) and 2-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethyl]-1,3-cyclopentadiene (b). Subsequent reaction of the bpzcpH hybrid ligand with ZnR(2) quantitatively yields the monoalkyl kappa(2)-NN-eta(1)(pi)-C(5)H(4) zinc complexes [Zn(R){kappa(2)-eta(1)(pi)-bpzcp}] (R = Me 7, Et 8, (t)Bu 9, CH(2)SiMe(3) 10). Additionally, magnesium alkyls 1, 2, 4, and 5 can act as excellent cyclopentadienyl and alkyl transfers to the zinc metal center and yield zinc alkyls 7-10 in good yields. The single-crystal X-ray structures of the derivatives 4, 5, 7, and 10 confirm a 4-coordinative structure with the metal center in a distorted tetrahedral geometry. Interestingly, whereas alkyl magnesium derivatives 4 and 5 present a eta(5) coordination mode for the cyclopentadienyl fragment, zinc derivatives 7 and 10 feature a peripheral eta(1)(pi) arrangement in the solid state. Furthermore, the reaction of the hybrid lithium salt [Li(bpzcp)(THF)] with 1 equiv of ZnCl(2) in tetrahydrofuran (THF) affords very high yields of the chloride complex [ZnCl{kappa(2)-eta(1)(pi)-bpzcp}] (11). Compound 11 was used as a convenient starting material for the synthesis of the aromatic amide zinc compound [Zn(NH-4-MeC(6)H(4)){kappa(2)-eta(1)(pi)-bpzcp}] (12), by reaction with the corresponding aromatic primary amide lithium salt. Alternatively, aliphatic amide and alkoxide derivatives were

  15. Synthesis and Ring-Opening Metathesis Polymerization of Second-Generation Dendronized Poly(ether Monomers Initiated by Ruthenium Carbenes

    Directory of Open Access Journals (Sweden)

    Guzmán Pablo E.


    Full Text Available The Ring-Opening Metathesis Polymerization (ROMP of second-generation dendronized monomers is described. Using the highly active and fast-initiating third-generation ruthenium complex [(H2IMes(pyr2Cl2RuCHPh], moderate to high molecular weight polymers (430-2230 kDa are efficiently synthesized with low dispersities (Ð = 1.01-1.17. This study highlights the power of the metathesis approach toward polymer synthesis in a context where monomer structure can significantly impede polymerization.

  16. Bio-Based Aromatic Epoxy Monomers for Thermoset Materials. (United States)

    Ng, Feifei; Couture, Guillaume; Philippe, Coralie; Boutevin, Bernard; Caillol, Sylvain


    The synthesis of polymers from renewable resources is a burning issue that is actively investigated. Polyepoxide networks constitute a major class of thermosetting polymers and are extensively used as coatings, electronic materials, adhesives. Owing to their outstanding mechanical and electrical properties, chemical resistance, adhesion, and minimal shrinkage after curing, they are used in structural applications as well. Most of these thermosets are industrially manufactured from bisphenol A (BPA), a substance that was initially synthesized as a chemical estrogen. The awareness on BPA toxicity combined with the limited availability and volatile cost of fossil resources and the non-recyclability of thermosets implies necessary changes in the field of epoxy networks. Thus, substitution of BPA has witnessed an increasing number of studies both from the academic and industrial sides. This review proposes to give an overview of the reported aromatic multifunctional epoxide building blocks synthesized from biomass or from molecules that could be obtained from transformed biomass. After a reminder of the main glycidylation routes and mechanisms and the recent knowledge on BPA toxicity and legal issues, this review will provide a brief description of the main natural sources of aromatic molecules. The different epoxy prepolymers will then be organized from simple, mono-aromatic di-epoxy, to mono-aromatic poly-epoxy, to di-aromatic di-epoxy compounds, and finally to derivatives possessing numerous aromatic rings and epoxy groups.

  17. Bio-Based Aromatic Epoxy Monomers for Thermoset Materials

    Directory of Open Access Journals (Sweden)

    Feifei Ng


    Full Text Available The synthesis of polymers from renewable resources is a burning issue that is actively investigated. Polyepoxide networks constitute a major class of thermosetting polymers and are extensively used as coatings, electronic materials, adhesives. Owing to their outstanding mechanical and electrical properties, chemical resistance, adhesion, and minimal shrinkage after curing, they are used in structural applications as well. Most of these thermosets are industrially manufactured from bisphenol A (BPA, a substance that was initially synthesized as a chemical estrogen. The awareness on BPA toxicity combined with the limited availability and volatile cost of fossil resources and the non-recyclability of thermosets implies necessary changes in the field of epoxy networks. Thus, substitution of BPA has witnessed an increasing number of studies both from the academic and industrial sides. This review proposes to give an overview of the reported aromatic multifunctional epoxide building blocks synthesized from biomass or from molecules that could be obtained from transformed biomass. After a reminder of the main glycidylation routes and mechanisms and the recent knowledge on BPA toxicity and legal issues, this review will provide a brief description of the main natural sources of aromatic molecules. The different epoxy prepolymers will then be organized from simple, mono-aromatic di-epoxy, to mono-aromatic poly-epoxy, to di-aromatic di-epoxy compounds, and finally to derivatives possessing numerous aromatic rings and epoxy groups.

  18. From lignin to cycloparaffins and aromatics: directional synthesis of jet and diesel fuel range biofuels using biomass. (United States)

    Bi, Peiyan; Wang, Jicong; Zhang, Yajing; Jiang, Peiwen; Wu, Xiaoping; Liu, Junxu; Xue, He; Wang, Tiejun; Li, Quanxin


    The continual growth in commercial aviation fuels and more strict environmental legislations have led to immense interest in developing green aviation fuels from biomass. This paper demonstrated a controllable transformation of lignin into jet and diesel fuel range hydrocarbons, involving directional production of C8-C15 aromatics by the catalytic depolymerization of lignin into C6-C8 low carbon aromatic monomers coupled with the alkylation of aromatics, and the directional production of C8-C15 cycloparaffins by the hydrogenation of aromatics. The key step, the production of the desired C8-C15 aromatics with the selectivity up to 94.3%, was achieved by the low temperature alkylation reactions of the lignin-derived monomers using ionic liquid. The synthetic biofuels basically met the main technical requirements of conventional jet fuels. The transformation potentially provides a useful way for the development of cycloparaffinic and aromatic components in jet fuels using renewable lignocellulose biomass.

  19. Design and synthesis of aromatic molecules for probing electric-fields at the nanoscale

    CERN Document Server

    Faez, Sanli; Markoulides, Marios; Buda, Francesco; Gourdon, André; Orrit, Michel


    We propose using halogenated organic dyes as nanoprobes for electric field and show their greatly enhanced Stark coefficients using density functional theory (DFT) calculations. We analyse halogenated variants of three molecules that have been of interest for cryogenic single molecule spectroscopy, perylene, terrylene, and dibenzoterrylene, with the zero-phonon optical transitions at blue, red, and near infrared. Out of all the combinations of halides and binding sites that are calculated, we have found that fluorination of the optimum binding site induces a dipole difference between ground and excited states larger than 0.5 D for all three molecules with the highest value of 0.69 D for fluoroperylene. We also report on synthesis of 3-fluoroterrylene and bulk spectroscopy of this compound in liquid and solid organic environments.

  20. Pyrazine motif containing hexagonal macrocycles: synthesis, characterization, and host-guest chemistry with nitro aromatics. (United States)

    Bhowmick, Sourav; Chakraborty, Sourav; Das, Atanu; Nallapeta, Sivaramaiah; Das, Neeladri


    The synthesis and characterization of cationic two-dimensional metallamacrocycles having a hexagonal shape and cavity are described. Both macrocycles utilize a pyrazine motif containing an organometallic acceptor tecton with platinum(II) centers along with different donor ligands. While one macrocycle is a relatively larger [6 + 6], the other is a relatively smaller [2 + 2] polygon. A unique feature of the smaller ensemble is that it is an irregular polygon in which all six edges are not of equal length. Molecular modeling of these macrocycles confirmed the presence of hexagonal cavities. The ability of these π-electron rich macrocycles to act as potential hosts for relatively electron deficient nitroaromatics (DNT = 2,4-dinitrotoluene and PA = picric acid) has been studied using isothermal titration calorimetry (ITC) as a tool. Molecular dynamics simulation studies were subsequently performed to gain critical insight into the binding interactions between the nitroaromatic guest molecules (PA/DNT) and the ionic macrocycles reported herein.

  1. Synthesis, structure, redox and spectra of green iridium complexes of tridentate azo-aromatic ligands

    Indian Academy of Sciences (India)

    Manashi Panda; Chayan Das; Chen-Hsiung Hung; Sreebrata Goswami


    Reactions of IrCl3$\\cdot$ H2O with the ligands, 2-[(phenylamino)phenylazo]pyridine (HL1a) and 2-[(-tolylamino)phenylazo]pyridine (HL1b) produce [Ir(L1)2]Cl (L1 = L1a, [1]Cl and L1 = L1b, [2]Cl) along with many unidentified products. The iridium complexes have been characterized by various techniques such as X-ray crystallography, mass spectrometry, 1H and 13C NMR, cyclic voltammetry and absorption studies. The complex [1]ClO4 crystallises in triclinic space group. The crystallographic data have been determined. Notably, the Ir-N (azo) lengths are short (av. 1.9875(4) Å) as compared to the remaining four Ir-N lengths (av. 2.052(5) Å). There is significant degree of ligand backbone conjugation in the coordinated ligands, which result in shortening of the C-N lengths on the other side of the middle phenyl ring and also in lengthening of the diazo (N=N) lengths. The complexes display multiple low energy transitions ranging between 1010 and 450 nm. These are electro active and show three reversible redox responses in the potential range, +1.5 V to -1.5 V. The cathodic potential responses are ascribed as ligand reductions, while the redox process at the anodic potential occurs at a mixed metal-ligand (HOMO) orbital.

  2. Synthesis and characterization of ring-like {alpha}-Fe{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Li Lili; Chu Ying; Liu Yang [Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024 (China)


    A novel ring-like {alpha}-Fe{sub 2}O{sub 3} with a cave at the centre was first synthesized via the redox reaction of Fe{sup 2+} with S{sub 2}O{sub 8}{sup 2-} in solution. The samples were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), x-ray diffraction (XRD) and vibrating sample magnetometry (VSM). The possible mechanisms of shape evolution for the formation of ring-like {alpha}-Fe{sub 2}O{sub 3} were discussed. Magnetic hysteresis measurements revealed that the ring-like {alpha}-Fe{sub 2}O{sub 3} display a magnetic behaviour with a coercivity of 1690 Oe at room temperature. The photocatalytic degradation of salicylic acid revealed that ring-like {alpha}-Fe{sub 2}O{sub 3} exhibits a photocatalytic property.

  3. Synthesis and characterization of ring-like α-Fe2O3 (United States)

    Li, Lili; Chu, Ying; Liu, Yang


    A novel ring-like α-Fe2O3 with a cave at the centre was first synthesized via the redox reaction of Fe2+ with S2O82- in solution. The samples were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), x-ray diffraction (XRD) and vibrating sample magnetometry (VSM). The possible mechanisms of shape evolution for the formation of ring-like α-Fe2O3 were discussed. Magnetic hysteresis measurements revealed that the ring-like α-Fe2O3 display a magnetic behaviour with a coercivity of 1690 Oe at room temperature. The photocatalytic degradation of salicylic acid revealed that ring-like α-Fe2O3 exhibits a photocatalytic property.

  4. Design, Synthesis and Biological Properties of Seco-D-Ring Modified 1α,25-Dihydroxyvitamin D3 Analogues. (United States)

    Szybinski, Marcin; Sektas, Katarzyna; Sicinski, Rafal R; Plum, Lori A; Frelek, Jadwiga; DeLuca, Hector F


    As a continuation of our efforts directed to the structure-activity relationship studies of vitamin D compounds, we present in this paper the synthesis of new analogues of 1α,25-(OH)2D3 characterized by numerous structural modifications, especially a cleaved D ring. Total synthesis of the CD fragment required for the construction of the target vitamins was based on the Stork approach. The structure of the key intermediate - bicyclic hydroxy lactone - was established by crystallographic and electronic circular dichroism (ECD) spectral analysis. Following the attachment of the hydroxyalkyl side chain, the formed D-seco Grundmann ketone was subjected to Wittig-Horner coupling with the corresponding A-ring phosphine oxides providing two desired D-seco analogues of 19-nor-1α,25-(OH)2D3, one without a substituent at C-2 and the other possessing a 2-exomethylene group. Both compounds were biologically tested and the latter was found to be more active in in vitro tests. Despite so many structural changes introduced in its structure, the biological activity of the 2-methylene analogue approached that of the natural hormone. The synthesized D-seco vitamins, however, proved to be inactive on bone and intestine in vivo. High-resolution mass spectra were recorded on LCT (TOF) or Mass Quattro LC spectrometers using electrospray ionization (ESI) technique.

  5. Pericyclic and related rearrangements for the synthesis of nitrogen heterocyclic ring systems



    The thesis describes synthesis and reactions of allene azides tethered to various functional groups and the application of the discovered cascade transformations towards the synthesis of radianspene J model system. Chapter 1 covers reactions of simple allene azides containing alkyl and cycloalkyl substituents. Thermal rearrangements of these substrates delivered isocyanides and azadienes via the proposed azatrimethylenemethane (ATMM) intermediates. On the other hand, vinylidenecycloprop...

  6. Synthesis of Poly(aryl ether ketone) Copolymers Containing Adamantyl-substituted Naphthalene Rings

    Institute of Scientific and Technical Information of China (English)

    ZHU Xiao-liang; ZHANG Shu-ling; REN Dian-fu; GUAN Shao-wei; WANG Gui-bin; JIANG Zhen-hua


    @@ 1 Introduction High performance polymers have received considerable attention over the past decade owing to their increased demands as replacements for metals or ceramics in automotive,aerospace,and microelectronic industries.Poly(aryl ether ketone)s(PAEKs) are a class of important high-performance aromatic polymers with excellent mechanical properties,good solvent resistance,size-accuracy,electrical characteristics,and superior thermal stability[1-3].

  7. (CF3CO2O/CF3SO3H-mediated synthesis of 1,3-diketones from carboxylic acids and aromatic ketones

    Directory of Open Access Journals (Sweden)

    JungKeun Kim


    Full Text Available A very simple and convenient reaction for 1,3-diketone preparation from carboxylic acids and aromatic ketones in TFAA/TfOH system is described. When the β-phenylpropionic acids were used as starting materials, they initially gave 1-indanones and then underwent further acylation with the formation of 2-(β-phenylpropionyl-1-indanones as the main reaction products. In addition, the application of the proposed protocol allowed for the synthesis of selected polysubstituted pyrazoles in a one-pot procedure directly from acids and ketones.

  8. Synthesis and spectroscopic and computational characterization of Zn4O(alicyclic or aromatic carboxylate)6 complexes as potential MOF precursors. (United States)

    Otvös, Sándor B; Berkesi, Ottó; Körtvélyesi, Tamás; Pálinkó, István


    Potential metal-organic-framework precursors, Zn(4)O complexes with various alicyclic or aromatic carboxylate ligands, were prepared, in many cases quantitatively, from ZnO and the relevant carboxylic acids in the presence of trace amounts of water. The complexes obtained were characterized with various classical (titration) and instrumental (IR and NMR spectroscopies) methods and molecular modeling (PM3 and PM6 semiempirical quantum chemical methods and HF/6-31G** ab initio calculations). Structural peculiarities reflected in the success or failure in the synthesis could be rationalized with the combination of IR and NMR spectroscopies and molecular modeling.

  9. Synthesis of Bis (silyloxy) Cross-Conjugated Polyenes and Their Sequential Ring Formations via Electrocyclization


    Wada, Eiji; Kanemasa, Shuji; Kimura, Nobuo; KIMURA, Hirohiko; Tsuge, Otohiko


    Presented are the synthesis of several bis(silyloxy) cross-conjugated polyenes and some synthetic utilization of these new types of conjugation systems via thermal or photochemical electrocyclization.

  10. Synthesis of disubstituted homodiamantanes by acylative ring expansion using benzoyl trifluoromethanesulfonate

    Directory of Open Access Journals (Sweden)

    Takao Okazaki, Shusaku Mandai, Toshikazu Kitagawa and Ken'ichi Takeuchi


    Full Text Available Diamantane is a hydrocarbon whose carbon framework is a part of diamond lattices. Acylative ring expansion of 1- and 4-diamantanecarbaldehyde using benzoyl trifluoromethanesulfonate and trifluoromethanesulfonic acid yielded 10-hydroxyhomodiamant-9-yl benzoate and 7-hydroxyhomodiamant-8-yl benzoate, whose skeletal structures are same as pentacyclo[,13.02,7.06,12]tetradecane.

  11. Solvent-Free Microwave Synthesis of Aryloxypropanolamines by Ring Opening of Aryloxy Epoxides

    Directory of Open Access Journals (Sweden)

    Rukhsana I. Kureshy


    Full Text Available The ring opening reaction of aryloxyepoxides with isopropylamine under solvent-free microwave irradiation produced therapeutically useful -blockers-aryloxypropanolamines in excellent yield (up to 98% in 10 minutes which is considerably less than the time taken in classical heating (∼16 hours.

  12. Synthesis and Cytotoxicity of Derivatives of Fluorouracil Conjugated with Three-membered Ring

    Institute of Scientific and Technical Information of China (English)

    WANG, Le; ZHANG, Yunxiao; TAO, Jingchao


    A novel series of 3-membered ring fluorouracil conjugates including cyclopropylmethyl fluorouracil and (2,3- epoxypropyl) fluorouracil conjugates were synthesized via selective protection, and their structures were confirmed by IR, 1H NMR and HRMS. Cytotoxicities in vitro of these conjugates were evaluated. Compounds 7, 8, 12 and 13 have shown cytotoxicities against Ec9706 cells in different degrees.

  13. Sydnone C-4 heteroarylation with an indolizine ring via Chichibabin indolizine synthesis. (United States)

    Albota, Florin; Caira, Mino R; Draghici, Constantin; Dumitrascu, Florea; Dumitrescu, Denisa E


    The synthesis of sydnones heteroarylated at C-4 with an indolizine was achieved by Chichibabin (Tschitschibabin) indolizine synthesis starting from the corresponding sydnone-N-pyridinium bromides. The latter compounds were also transformed to sydnone-indolizines connected through a keto group at the C-4 position by refluxing them in 1,2-epoxybutane with an activated alkyne. The structures of the new compounds were assigned by FTIR, NMR spectroscopy and X-ray analysis.

  14. Synthesis of Diazepine-fused Porphyrinoids and Annulated Porphyrin Arrays




    PUBLISHED Porphyrins with exocyclic rings allow for significant modulation of the photochemical properties of the macrocycle via modulation of the aromatic system through electronic and conformational effects. Here we sought to generate such porphyrinoids via a stepwise strategy involving two cycloaddition steps, the first improving the synthesis of a relatively unstable dehydropurpurin intermediate which ring opens to form a key 1,5-diketone species. A library of a new clas...

  15. Elaboration of Sterically Hindered δ-Lactones through Ring-Closing Metathesis: Application to the Synthesis of the C1-C27 Fragment of Hemicalide. (United States)

    Lecourt, Camille; Boinapally, Srikanth; Dhambri, Sabrina; Boissonnat, Guillaume; Meyer, Christophe; Cossy, Janine; Sautel, François; Massiot, Georges; Ardisson, Janick; Sorin, Geoffroy; Lannou, Marie-Isabelle


    The synthesis of the C1-C27 fragment of hemicalide, a marine metabolite displaying a unique potent antiproliferative activity, has been accomplished. The synthetic approach highlights a remarkably efficient ring-closing metathesis reaction catalyzed by Nolan ruthenium indenylidene complexes to elaborate the highly substituted δ-lactone framework.

  16. Synthesis of cyclic 1-alkenylboronates via Zr-mediated double functionalization of alkynylboronates and sequential Ru-catalyzed ring-closing olefin metathesis. (United States)

    Nishihara, Yasushi; Suetsugu, Masato; Saito, Daisuke; Kinoshita, Megumi; Iwasaki, Masayuki


    Synthesis of novel cyclic 1-alkenylboronates is accomplished through the zirconium-mediated regio- and stereoselective double functionalization of 1-alkynylboronates and the subsequent ruthenium-catalyzed ring-closing metathesis (RCM). The obtained substituted cyclic 1-alkenylboronates are transformed into o-terphenyl and triphenylene derivatives.

  17. SnAP reagents for the one-step synthesis of medium-ring saturated N-heterocycles from aldehydes. (United States)

    Vo, Cam-Van T; Luescher, Michael U; Bode, Jeffrey W


    Interest in saturated N-heterocycles as scaffolds for the synthesis of bioactive molecules is increasing. Reliable and predictable synthetic methods for the preparation of these compounds, especially medium-sized rings, are limited. We describe the development of SnAP (Sn amino protocol) reagents for the transformation of aldehydes into seven-, eight- and nine-membered saturated N-heterocycles. This process occurs under mild, room-temperature conditions and offers exceptional substrate scope and functional-group tolerance. Air- and moisture-stable SnAP reagents are prepared on a multigram scale from inexpensive starting materials by simple reaction sequences. These new reagents and processes allow widely available aryl, heteroaryl and aliphatic aldehydes to be converted into diverse N-heterocycles, including diazepanes, oxazepanes, diazocanes, oxazocanes and hexahydrobenzoxazonines, by a single synthetic operation.

  18. Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products

    Directory of Open Access Journals (Sweden)

    Alexander O. Terent'ev


    Full Text Available The present review describes the current status of synthetic five and six-membered cyclic peroxides such as 1,2-dioxolanes, 1,2,4-trioxolanes (ozonides, 1,2-dioxanes, 1,2-dioxenes, 1,2,4-trioxanes, and 1,2,4,5-tetraoxanes. The literature from 2000 onwards is surveyed to provide an update on synthesis of cyclic peroxides. The indicated period of time is, on the whole, characterized by the development of new efficient and scale-up methods for the preparation of these cyclic compounds. It was shown that cyclic peroxides remain unchanged throughout the course of a wide range of fundamental organic reactions. Due to these properties, the molecular structures can be greatly modified to give peroxide ring-retaining products. The chemistry of cyclic peroxides has attracted considerable attention, because these compounds are used in medicine for the design of antimalarial, antihelminthic, and antitumor agents.

  19. Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products (United States)

    Borisov, Dmitry A; Vil’, Vera A; Dembitsky, Valery M


    Summary The present review describes the current status of synthetic five and six-membered cyclic peroxides such as 1,2-dioxolanes, 1,2,4-trioxolanes (ozonides), 1,2-dioxanes, 1,2-dioxenes, 1,2,4-trioxanes, and 1,2,4,5-tetraoxanes. The literature from 2000 onwards is surveyed to provide an update on synthesis of cyclic peroxides. The indicated period of time is, on the whole, characterized by the development of new efficient and scale-up methods for the preparation of these cyclic compounds. It was shown that cyclic peroxides remain unchanged throughout the course of a wide range of fundamental organic reactions. Due to these properties, the molecular structures can be greatly modified to give peroxide ring-retaining products. The chemistry of cyclic peroxides has attracted considerable attention, because these compounds are used in medicine for the design of antimalarial, antihelminthic, and antitumor agents. PMID:24454562

  20. Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products. (United States)

    Terent'ev, Alexander O; Borisov, Dmitry A; Vil', Vera A; Dembitsky, Valery M


    The present review describes the current status of synthetic five and six-membered cyclic peroxides such as 1,2-dioxolanes, 1,2,4-trioxolanes (ozonides), 1,2-dioxanes, 1,2-dioxenes, 1,2,4-trioxanes, and 1,2,4,5-tetraoxanes. The literature from 2000 onwards is surveyed to provide an update on synthesis of cyclic peroxides. The indicated period of time is, on the whole, characterized by the development of new efficient and scale-up methods for the preparation of these cyclic compounds. It was shown that cyclic peroxides remain unchanged throughout the course of a wide range of fundamental organic reactions. Due to these properties, the molecular structures can be greatly modified to give peroxide ring-retaining products. The chemistry of cyclic peroxides has attracted considerable attention, because these compounds are used in medicine for the design of antimalarial, antihelminthic, and antitumor agents.

  1. Selective Synthesis of Molecular Borromean Rings: Engineering of Supramolecular Topology via Coordination-Driven Self-Assembly. (United States)

    Kim, Taegeun; Singh, Nem; Oh, Jihun; Kim, Eun-Hee; Jung, Jaehoon; Kim, Hyunuk; Chi, Ki-Whan


    Molecular Borromean rings (BRs) is one of the rare topology among interlocked molecules. Template-free synthesis of BRs via coordination-driven self-assembly of tetracene-based Ru(II) acceptor and ditopic pyridyl donors is reported. NMR and single-crystal XRD analysis observed sequential transformation of a fully characterized monomeric rectangle to molecular BRs and vice versa. Crystal structure of BRs revealed that the particular topology was enforced by the appropriate geometry of the metallacycle and multiple parallel-displaced π-π interactions between the donor and tetracene moiety of the acceptor. Computational studies based on density functional theory also supported the formation of BRs through dispersive intermolecular interactions in solution.

  2. Synthesis of the EF-ring of ciguatoxin 3C based on the [2,3]-Wittig rearrangement and ring-closing olefin metathesis. (United States)

    Goto, Akiyoshi; Fujiwara, Kenshu; Kawai, Ayako; Kawai, Hidetoshi; Suzuki, Takanori


    The EF-ring segment of ciguatoxin 3C, a causative toxin of ciguatera fish poisoning, was synthesized in three major steps: 1,4-addition for the C20O-C27 bond connection, chirality transferring anti selective [2,3]-Wittig rearrangement for the construction of the anti-2-hydroxyalkyl ether part, and ring-closing olefin metathesis for the F-ring formation.

  3. Synthesis of first row transition metal carboxylate complexes by ring opening reactions of cyclic anhydrides

    Indian Academy of Sciences (India)

    Jubaraj Bikash Baruah


    Hydrolytic and solvolytic ring opening reactions of phthalic anhydride, pyromellitic dianhydride and 2,3-pyridine dicarboxylic anhydride in the presence of various transition metal salts with or without a ancillary ligands were studied. The reactions were found to be dependent on stoichiometry of ligand and types of anhydride used. In the case of pyromellitic dianhydride selective ring opening reaction by cobalt(II) ions gave 1,3-benzene dicarboxylate derivatives, whereas use of copper(II) ions gave 1,4-benzene dicarboxylate derivatives. Preference for methanolysis was seen in the case of copper (II) promoted reactions of pyromellitic dianhydride in the presence of 1:1 metal to 1,10-phenanthroline ratio.

  4. Synthesis and action on the central nervous system of mescaline analogues containing piperazine or homopiperazine rings. (United States)

    Majchrzak, M W; Kotełko, A; Guryn, R; Lambert, J B; Szadowska, A; Kowalczyk, K


    Structural juxtaposition of the 3,4,5-trimethoxyphenyl group in the same molecule with a piperazine or homopiperazine ring has been realized in a series of mescaline analogues (I-IV) as part of an investigation into the pharmacological properties of the seven-membered perhydro-1,4-diazepines (homopiperazines). The analogous six-membered piperazines were synthesized and tested as reference substances to determine whether the seven-membered ring conveyed special properties. A variety of pharmacological tests of action on the CNS showed that replacement of the amino group in mescaline by the heterocycles significantly alters the biological activity. In particular, both the piperazine and the homopiperazine derivatives displayed sedative activity to about the same extent.


    Institute of Scientific and Technical Information of China (English)

    QU Rongjun; SUN Changmei; JI Chunnuan; WANG Chunhua; CHENG Guoxiang


    By the reaction of poly(bromoacetyl styrene) (EBPS) with thiaurea (TU), a kind of novel chelating resin with heterocyaclic ring of sulfur and nitrogen, poly[4-(2-amino)thiazoleyl-4-vinylben=ene], was synthesized. Its structure was characterized by FTIR and elemental analysis. The factors which have influence on the reaction such as reaction time, solvents, and molar ratio of reactants were investigated.


    Institute of Scientific and Technical Information of China (English)

    Hong-ming Zhang; Qing-zhong Guo; Tian-lu Chen


    A series of cyclic (arylene phosphonate) oligomers were prepared by reaction of phenylphosphonic dichloride (PPD) with various bisphenols under pseudo-high dilution conditions via interfacial polycondensation. The yield of cyclic (arylenc phosphonate) oligomers is over 85% by using hexadecyltrimethylammonium bromide as phase transfer catalyst (PTC) at 0 ℃. The structures of the cyclic oligomers were confirmed by a combination of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and IR analysis. These cyclic oligomers undergo facile ring-opening polymerization in the melt by using potassium 4,4'-biphenoxide as the initiator to give linear polyphosphonate. Free-radical ring-opening polymerization of cyclic(arylene phosphonate) oligomers containing sulfur linkages was also performed in the melt using 2,2'-dithiobis(benzothiazole) (DTB) as the initiator at 270℃ and the resulting polymer had a Mw of 8 × 103 with a molecular weight distribution of 4. Ring-opening copolymerization of these cyclic oligomers with cyclic carbonate oligomers was also achieved. The average molecular weight of the resulting copolymer is higher than the corresponding homopolymer and the thermal stability of the copolymer is better than the corresponding homopolymer.

  7. Synthesis of Human Milk Oligosaccharides and Regioselective Ring Opening of Oxabicycles

    DEFF Research Database (Denmark)

    Jennum, Camilla Arboe

    the fucose is also attached in the same pot. In addition, pNP-neuraminic acid was synthesized for the purpose to perform activity studies on enzymes. The enzymes were designed to perform sialyl transfer reactions in the synthesis human milk oligosaccharides containing neuraminic acid. OH O HO HO O OH O HO O...

  8. Fatty acid synthesis and pyruvate metabolism pathways remain active in dihydroartemisinin-induced dormant ring stages of Plasmodium falciparum. (United States)

    Chen, Nanhua; LaCrue, Alexis N; Teuscher, Franka; Waters, Norman C; Gatton, Michelle L; Kyle, Dennis E; Cheng, Qin


    Artemisinin (ART)-based combination therapy (ACT) is used as the first-line treatment of uncomplicated falciparum malaria worldwide. However, despite high potency and rapid action, there is a high rate of recrudescence associated with ART monotherapy or ACT long before the recent emergence of ART resistance. ART-induced ring-stage dormancy and recovery have been implicated as possible causes of recrudescence; however, little is known about the characteristics of dormant parasites, including whether dormant parasites are metabolically active. We investigated the transcription of 12 genes encoding key enzymes in various metabolic pathways in P. falciparum during dihydroartemisinin (DHA)-induced dormancy and recovery. Transcription analysis showed an immediate downregulation for 10 genes following exposure to DHA but continued transcription of 2 genes encoding apicoplast and mitochondrial proteins. Transcription of several additional genes encoding apicoplast and mitochondrial proteins, particularly of genes encoding enzymes in pyruvate metabolism and fatty acid synthesis pathways, was also maintained. Additions of inhibitors for biotin acetyl-coenzyme A (CoA) carboxylase and enoyl-acyl carrier reductase of the fatty acid synthesis pathways delayed the recovery of dormant parasites by 6 and 4 days, respectively, following DHA treatment. Our results demonstrate that most metabolic pathways are downregulated in DHA-induced dormant parasites. In contrast, fatty acid and pyruvate metabolic pathways remain active. These findings highlight new targets to interrupt recovery of parasites from ART-induced dormancy and to reduce the rate of recrudescence following ART treatment.

  9. Synthesis of aromatic (13)C/(2)H-α-ketoacid precursors to be used in selective phenylalanine and tyrosine protein labelling. (United States)

    Lichtenecker, R J


    Recent progress in protein NMR spectroscopy revealed aromatic residues to be valuable information sources for performing structure and motion analysis of high molecular weight proteins. However, the applied NMR experiments require tailored isotope labelling patterns in order to regulate spin-relaxation pathways and optimize magnetization transfer. We introduced a methodology to use α-ketoacids as metabolic amino acid precursors in cell-based overexpression of phenylalanine and/or tyrosine labelled proteins in a recent publication, which we have now developed further by providing synthetic routes to access the corresponding side-chain labelled precursors. The target compounds allow for selective introduction of (13)C-(1)H spin systems in a highly deuterated chemical environment and feature alternating (12)C-(13)C-(12)C ring-patterns. The resulting isotope distribution is especially suited to render straightforward (13)C spin relaxation experiments possible, which provide insight into the dynamic properties of the corresponding labelled proteins.

  10. Synthesis of 1-Bromo-3-methoxy-4-propoxy-5-iodobenzene-A Novel Efficient Process for the Synthesis of Brominated Aromatic Compound

    Institute of Scientific and Technical Information of China (English)

    Hong Xin SHI; Hui LIN; Gérard MANDVILLE


    The reaction of aromatic carboxylic acid with oxalyl chloride gives rise to the corres- ponding acid chloride which without purification is treated with the sodium salt of mercapto- pyridine oxide in the presence of 2,2-azo-bisisobutyronitrile (AIBN), radical initiator to give a brominated aromatic compound. After etherification and oxidation, 5-iodovaniline was converted to trisubstituted benzene carboxylic acid which give 1-bromo-3-methoxy-4-propoxy-5-iodo- benzene by this new brominating process with a yield of 74 %.

  11. Amidinate aluminium complexes: synthesis, characterization and ring-opening polymerization of rac-lactide. (United States)

    Qian, Feng; Liu, Keyin; Ma, Haiyan


    A series of aluminium alkyl complexes {PhC(NR')(NR'')}AlR(2) (4a-n, R' = 2,6-(i)Pr(2)C(6)H(3), 2,6-Me(2)C(6)H(3); R'' = aryl groups with various ortho-, para- or meta-substituents, tert-butyl; R = methyl, ethyl) bearing non-symmetrically N-substituted benzamidinate ligands were synthesized via the reaction of trialkylaluminium and the corresponding benzamidine proligands. Complex 5 bearing symmetric amidinate ligand was also obtained for comparison purposes. The X-ray diffraction studies of complexes 4b, 4c and 5 show in each case a distorted tetrahedral geometry around the aluminium center. All the amidinate aluminium complexes were found to catalyze the ring-opening polymerization (ROP) of rac-lactide with moderate activities. The steric and electronic characteristics of the ancillary ligands have a significant influence on the polymerization performance of the corresponding aluminium complexes. The introduction of electron-withdrawing substituents at the ortho-positions of N-phenyl ring of the ligands resulted in an obvious increase in catalytic activity. Complex 4b showed the highest activity among the investigated aluminium complexes due to the high electrophilicity of the metal center induced by the ortho-chloro substituents on the phenyl ring. The existence of ortho-substituents of small steric bulkiness is also beneficial for the increase of activity of these catalysts. However, further increase of steric hindrance of the ligands by introducing bulky ortho-substituents onto the phenyl moieties resulted in a decrease of activity and an increase in the isotactic bias of the obtained polylactides. The broad molecular weight distributions (PDI = 1.13-2.02) of the polymer samples indicated that the ROP of rac-lactide initiated by these complexes was not well-controlled.

  12. Low Catalyst Loadings in Olefin Metathesis: Synthesis of Nitrogen Heterocycles by Ring Closing Metathesis (United States)

    Kuhn, Kevin M.; Champagne, Timothy M.; Hong, Soon Hyeok; Wei, Wen-Hao; Nickel, Andrew; Lee, Choon Woo; Virgil, Scott C.; Grubbs, Robert H.; Pederson, Richard L.


    (eq 1) A series of ruthenium catalysts have been screened under ring closing metathesis (RCM) conditions to produce five-, six-, and seven-membered carbamate-protected cyclic amines. Many of these catalysts demonstrated excellent RCM activity and yields with as low as 500 ppm catalyst loadings. RCM of the five-membered carbamate-series could be run neat, the six-membered carbamate-series could be run at 1.0 M concentrations and the seven-membered carbamate-series worked best at 0.2 M to 0.05 M concentrations. PMID:20141172

  13. Recent applications of ring-closing metathesis in the synthesis of lactams and macrolactams. (United States)

    Hassan, Hani Mutlak A


    Lactams are an important class of compounds owing to their presence in numerous biologically active molecules of natural and unnatural nature. They are also highly versatile intermediates that can be elaborated into interesting compounds for potential use in organic and medicinal chemistry endeavors. In this feature article, the reader will be given a background to olefin metathesis followed by concise discussions (with selected examples) to report recent applications of ring-closing metathesis to form lactams and macrolactams from acyclic diene precursors, an area which continues to deposit attractive applications in the chemical literature en route or in the final step to the target molecules.

  14. Low catalyst loadings in olefin metathesis: synthesis of nitrogen heterocycles by ring-closing metathesis. (United States)

    Kuhn, Kevin M; Champagne, Timothy M; Hong, Soon Hyeok; Wei, Wen-Hao; Nickel, Andrew; Lee, Choon Woo; Virgil, Scott C; Grubbs, Robert H; Pederson, Richard L


    A series of ruthenium catalysts have been screened under ring-closing metathesis (RCM) conditions to produce five-, six-, and seven-membered carbamate-protected cyclic amines. Many of these catalysts demonstrated excellent RCM activity and yields with as low as 500 ppm catalyst loadings. RCM of the five-membered carbamate series could be run neat, the six-membered carbamate series could be run at 1.0 M, and the seven-membered carbamate series worked best at 0.2-0.05 M.

  15. Synthesis of all-hydrocarbon stapled α-helical peptides by ring-closing olefin metathesis. (United States)

    Kim, Young-Woo; Grossmann, Tom N; Verdine, Gregory L


    This protocol provides a detailed procedure for the preparation of stapled α-helical peptides, which have proven their potential as useful molecular probes and as next-generation therapeutics. Two crucial features of this protocol are (i) the construction of peptide substrates containing hindered α-methyl, α-alkenyl amino acids and (ii) the ring-closing olefin metathesis (RCM) of the resulting resin-bound peptide substrates. The stapling systems described in this protocol, namely bridging one or two turns of an α-helix, are highly adaptable to most peptide sequences, resulting in favorable RCM kinetics, helix stabilization and promotion of cellular uptake.

  16. All-digital simple clock synthesis through a glitch-free variable-length ring oscillator


    Pérez Puigdemont, Jordi; Moll Echeto, Francisco de Borja; Calomarde Palomino, Antonio


    This brief presents a simple all-digital variable-length ring oscillator (VLRO) design that is capable of synchronously changing the output frequency while keeping a signal free of glitches or spurious oscillations at the frequency transitions. The correct operation of the proposed VLRO has been experimentally validated on a 90-nm Xilinx Spartan-3E field-programmable gate array, showing the ability to switch between 16 different frequencies (from 24.1 to 321 MHz for the nominal core supply vo...

  17. Synthesis and Biological Activity of New Pyrethroid Acid Oxime-esters Containing Pyrazole Ring

    Institute of Scientific and Technical Information of China (English)

    MA Jun-an; HUANG Run-qiu; FENG Lei; SONG Jian; QIU De-wen


    A series of compounds containing oxime-ester linkage and pyrazole ring(in place of the ester linkage and the alcohol moiety in pyrethroid ester) was designed and synthesized. The structures of all the compounds prepared were confirmed by 1H NMR and MS spectroscopy as well as elemental analyses. The bioassay data of those compounds against tobacco mosaic virus(TMV), cucumber mosaic virus(CMV), potato virus X(PVX) and potato virus Y(PVY) were presented. Among them compound 6i was found to possess significant plant antiviral activities. But all the compounds showed low insecticidal and acaricidal activities.

  18. Synthesis of Some New Mono- and Bis-Polycyclic Aromatic Spiro and Bis-Nonspiro-β-Lactams

    Directory of Open Access Journals (Sweden)

    Edris Ebrahimi


    Full Text Available Some new mono-and bis-polycyclic aromatic spiro-β-lactams and bis-non spiro-polycyclic aromatic β-lactams have been synthesized from imines derived from anthracene-9-carbaldehyde, 2-naphtaldehyde and a ketene derived from 9H-xanthene-9-carboxylic acid and phenoxyacetic acid by a [2+2] cycloaddition reaction. The cycloadducts were characterized by spectral data, including 1H-NMR, 13C-NMR, IR and elemental analyses. The configurations of some of these mono-spiro-β-lactams were established by X-ray crystal analysis.

  19. Aromatic-Aromatic Interactions in Biological System: Structure Activity Relationships

    Energy Technology Data Exchange (ETDEWEB)

    Rajagopal, Appavu; Deepa, Mohan [Molecular Biophysics Unit, Indian Institute of Sciences-Bangalore, Karnataka (India); Govindaraju, Munisamy [Bio-Spatial Technology Research Unit, Department of Environmental Biotechnology, School of Environmental Sciences, Bharathidasan University, Tiruchirappalli, Tamil Nadu (India)


    While, intramolecular hydrogen bonds have attracted the greatest attention in studies of peptide conformations, the recognition that several other weakly polar interactions may be important determinants of folded structure has been growing. Burley and Petsko provided a comprehensive overview of the importance of weakly polar interactions, in shaping protein structures. The interactions between aromatic rings, which are spatially approximate, have attracted special attention. A survey of the proximal aromatic residue pairs in proteins, allowed Burley and Petsko to suggest that, “phenyl ring centroids are separated by a preferential distance of between 4.5 and 7 Å, and dihedral angles approximately 90° are most common”.

  20. The application of catalytic ring-closing olefin metathesis to the synthesis of unsaturated oxygen heterocycles

    Energy Technology Data Exchange (ETDEWEB)

    Fu, G.C.; Grubbs, R.H. [California Institute of Technology, Pasadena, CA (United States)


    The development of general approaches to carbon-carbon bond formation represents an important ongoing challenge for synthetic organic chemists. One efficient method for constructing carbon-carbon double bonds, the transition metal alkylidene-catalyzed olefin metathesis reaction, has been the focus of intense interest in recent years from the standpoint of both mechanism and polymer synthesis, in contrast, use of this transformation in organic synthesis has been limited. As part of a broader program directed toward establishing transition metal alkylidenes as versatile reagents for organic chemistry, the authors report the successful application of catalytic olefin methathesis to the generation of a variety of unsaturated oxygen heterocycles. 13 refs., 1 fig., 1 tab.


    Institute of Scientific and Technical Information of China (English)

    Neng-wen Ding; Wei-lin Sun; Yan Lin; Zhi-quan Shen


    A novel conjugated hyperbranched polymer containing bithiazole rings (PBTADB) was synthesized by polycondensation of 1,3,5-benzenetricarboxaldehyde and 2,2′-diamino-4,4′-bithiazole (DABT).The structure of the hyperbranched polymer was confirmed by FT-IR and 1H-NMR.PBTADB dissolved in organic polar solvents such as DMSO and NMP.Bithiazole rings were introduced to provide bidentate N-donor sites for binding metal ions.The metal complexes were prepared by chelation of the polymer with Co2+ and Sm3+.The magnetic behavior of coordination compounds was measured as a function of magnetic field strength (0-4.8 × l06 A/m) at 5 K and as a function of temperature (5-300 K) at magnetic field strength of 2.4 × 106 A/m.The magnetic hysteresis loops of PBTADB-Sm3+ and PBTADB-Co2+ showed the typical ‘S' shape at 5 K with the Curie-Weiss temperature Tθ =96 K and 41 K respectively.The results show that they exhibit properties of soft ferromagnetic materials.

  2. Synthesis, insecticidal activity, and structure-activity relationship (SAR) of anthranilic diamides analogs containing oxadiazole rings. (United States)

    Li, Yuhao; Zhu, Hongjun; Chen, Kai; Liu, Rui; Khallaf, Abdalla; Zhang, Xiangning; Ni, Jueping


    A series of anthranilic diamides analogs (3–11, 16–24) containing 1,2,4- or 1,3,4-oxadiazole rings were synthesized and characterized by (1)H NMR, MS and elemental analyses. The structure of 3-bromo-N-(2-(3-(4-bromophenyl)-1,2,4-oxadiazol-5-yl)-4-chloro-6-methylphenyl)-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide (18, CCDC-) was determined by X-ray diffraction crystallography. The insecticidal activities against Plutella xylostella and Spodoptera exigua were evaluated. The results showed that most of title compounds displayed good larvicidal activities against P. xylostella, especially compound 3-bromo-N-(4-chloro-2-methyl-6-(5-(methylthio)-1,3,4-oxadiazol-2-yl)phenyl)-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide (6), which displayed 71.43% activity against P. xylostella at 0.4 μg mL(-1) and 33.33% against S. exigua at 1 μg mL(-1). The structure-activity relationship showed that compounds decorated with a 1,3,4-oxadiazole were more potent than compounds decorated with a 1,2,4-oxadiazole, and different substituents attached to the oxadiazole ring also affected the insecticidal activity. This work provides some hints for further structure modification and the enhancement of insecticidal activity.

  3. Diels-Alder addition of some 6-and 5-member ring aromatic compounds on the Si(001)-2×1 surface: dependence of the binding energy on the resonance energy of the aromatic compounds

    Institute of Scientific and Technical Information of China (English)



    [1]Onganer, Y., Saglam, M., Turut, A. et al., High barrier metallic polymer p-type silicon Schottky diodes, Solid State Electron, 1996, 39: 677.[2]Lonergan, M. C., A tunable diode based on an inorganic semiconductor vertical bar conjugated polymer interface, Science,1997, 278: 2103.[3]Wolkow, R. A., Moffatt, D. J., The frustrated motion of benzene on the surface of Si(l11), J. Chem. Phys., 1995,103: 10696.[4]MacPherson, C. D., Leung, K. T., Electron-induced chemistry of pyridine on Si(l 11)7x7 An LEED and TDS study,Surf. Sci., 1995, 324: 202.[5]MacPherson, C. D., Hu, D. Q., Leung, K. T., Room-temperature adsorption of thiophene and related 5-membered cyclicolefins on Si( 111)7x7 by thermal-desorption spectrometry, Surf. Sci., 1992, 276:156.[6]Cao, Y.. Wang, Z., Deng, J. F. et al., Evidence for dangling bond mediated dimerization of furan on the silicon (111 )-(7x7) surface, Angew Chem. Int. Ed., 2000, 39: 2740-2743.[7]Cao, Y., Yong, K. S., Wang, Z. Q. et al., Dry thienylation of the silicon (111)-(7x7) surface, J. Am. Chem. Soc., 2000, 112:1812.[8]Taguchi, Y., Fujisawa, M., Takaoka, T. et al., Adsorbed state of benzene on the Si(100) surface-thermal-desorption and electron-energy loss spectroscopy studies, J. Chem. Phys., 1991,95: 6870.[9]Lopinski, G. P., Fortier, T M., Moffatt, D. J. et al., Multiple bonding geometries and binding state conversion of benzene/Si(100), J. Vac. Sci. Technol., 1998, Al6: 1037.[10]Ellison, M. D., Hamers, R. J., Reactions of substituted aromatic hydrocarbons with the Si(001) surface, J. Vac. Sci.Technol., 2000, Al8: 1965.[11]Qiao, M. H., Cao, Y., Deng, J. F. et al, Formation of covalent Si-N linkages on pyrrole functionalized Si(100)-(2×l),Chem. Phys. Lett., 2000, 325: 508.[12]Konecny, R., Doren, D. J., Cycloaddition reactions of unsaturated hydrocarbons on the Si(100)-(2×1) surface: theoretical predictions, Surf. Sci., 1998, 417: 169.[13]Birkenheuer, U., Gutdeutsch, U., Rosch, N

  4. Aromatic Fused [30] Heteroannulenes with NIR Absorption and NIR Emission: Synthesis, Characterization, and Excited-State Dynamics. (United States)

    Mallick, Abhijit; Oh, Juwon; Kim, Dongho; Rath, Harapriya


    Two hitherto unknown planar aromatic [30] fused heterocyclic macrocycles (, with NIR absorption in free-base form and protonation-induced enhanced NIR emission, have been synthesized from easy to make precursors. The induced correspondence of fusion on the macrocyclic structure, electronic absorption, and emission spectra have been highlighted.

  5. Combinatorial Solid-Phase Synthesis of Aromatic Oligoamides: A Research-Based Laboratory Module for Undergraduate Organic Chemistry (United States)

    Fuller, Amelia A.


    A five-week, research-based experiment suitable for second-semester introductory organic laboratory students is described. Each student designs, prepares, and analyzes a combinatorial array of six aromatic oligoamides. Molecules are prepared on solid phase via a six-step synthetic sequence, and purities and identities are determined by analysis of…

  6. Charge migration in dicationic electrophiles and its application to the synthesis of aza-polycyclic aromatic compounds. (United States)

    Li, Ang; Kindelin, Patrick J; Klumpp, Douglas A


    [reaction: see text] Superacid-promoted reactions of dicationic electrophiles have been studied, and the positive charge centers are found to migrate apart in a predictable manner. Using isotopic labeling the charge migration is found in one system to occur through successive deprotonation-reprotonation steps. The charge migration chemistry is the basis for new general synthetic route to aza-polycyclic aromatic compounds.

  7. Efficient Synthesis of 2—Ethyl—A—ring Analogues of 19—Nor—1α,25—dihydroxy Vitamin D3

    Institute of Scientific and Technical Information of China (English)

    WangQiu-an; ZHAOYu-rui


    The novel 19-nor-1α,25-dihydroxy vitamin D3 analogues possessing an ethyl at the 2-position(4 and 5).were synthesized by coupling 25-hydroxy Windaus-Grundmann ketone derivative 20 with A-ring synthons(15 and 19)respectively.The enantioselective synthesis of substituted bicyclic[3,1,0]hexanes structure A-ring synthons,started from all-cis-3,5-dihydroxy-4-ethyl-1-(methoxycarbonyl)cyclohexane via lipase-catalyzd asymmetrization,was demonstratcd.

  8. Synthesis of novel anticancer agents through opening of spiroacetal ring of diosgenin. (United States)

    Hamid, A A; Hasanain, Mohammad; Singh, Arjun; Bhukya, Balakishan; Omprakash; Vasudev, Prema G; Sarkar, Jayanta; Chanda, Debabrata; Khan, Feroz; Aiyelaagbe, O O; Negi, Arvind S


    Diosgenin has been modified to furostane derivatives after opening the F-spiroacetal ring. The aldehyde group at C26 in derivative 8 was unexpectedly transformed to the ketone 9. The structure of ketone 9 was confirmed by spectroscopy and finally by X-ray crystallography. Five of the diosgenin derivatives showed significant anticancer activity against human cancer cell lines. The most potent molecule of this series i.e. compound 7, inhibited cellular growth by arresting the population at G0/G1 phase of cell division cycle. Cells undergo apoptosis after exposure to the derivative 7 which was evident by increase in sub G0 population in cell cycle analysis. Docking experiments showed caspase-3 and caspase-9 as possible molecular targets for these compounds. This was further validated by cleavage of PARP, a caspase target in apoptotic pathway. Compound 7 was found non-toxic up to 1000mg/kg dose in acute oral toxicity in Swiss albino mice.

  9. Pendant triazole ring assisted mesogen containing side chain liquid crystalline polymethacrylates: Synthesis and characterization

    Indian Academy of Sciences (India)

    T Palani; C Saravanan; P Kannan


    Two series of click chemistry assisted alkoxymethyl-1H-[1,2,3]-triazol-1-yl containing sidechain liquid-crystalline polymethacrylates were synthesized by free radical polymerization technique. Mesogen was linked to backbone through various spacer units. Monomers and polymers were characterized by FT-IR, 1H and 13C-NMR spectral techniques. Thermal stability of polymers was confirmed by thermogravimetric analysis. Mesomorphic property and phase transition temperature of polymers were analysed by differential scanning calorimetry and polarized optical microscopy. Phase transition temperature and mesomorphic property of polymers with respect to insertion of polar alkoxy group on terminal triazole ring and spacer length between backbone and mesogen were investigated. Polymers exhibited grainy like textures under polarized optical microscopy. Spacer length between mesogen and backbone alters phase transition temperature of the polymers.


    Directory of Open Access Journals (Sweden)

    Shu Xiao,


    Full Text Available Cellulose-graft-poly (L-lactide (cellulose-g-PLLA was prepared under homogeneous mild conditions. Ring-opening polymerization (ROP was carried out successfully using 4-dimethylaminopyridine (DMAP as an organic catalyst in an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl. The structure of the polymer was characterized by GPC, 1H NMR, 13C NMR, FT-IR, TGA, WAXD, and AFM. The results indicated that the grafting rate of the polymer reached 4.44, which was higher than that reported in AmimCl with Sn(oct2 as a catalyst. In addition, AFM showed that the polymer in solution could aggregate and self-assemble into an approximately spherical structure, which was different from the rod-like structure of cellulose and round-like polylactic acid particles.

  11. Synthesis, Structure and Properties of Two Photochromic Compounds Containing A Pyrazolone-ring

    Institute of Scientific and Technical Information of China (English)


    Two photochromic compounds with the pyrazolone-ring as the photochromic functional structure, 2-(1'-phenyl-3'-methyl-4'-benzoformyl-pyrazolone-5')-thiosemicarbazone(PMBP-TSC) and 2-(1'-phenyl-3'-methyl-4'-benzoformyl-pyrazolone-5')-S-methylthiosemicarbazone(PMBP-MTSC), were synthesized and characterized by elemental analysis, MS, IR spectra, NMR spectra. The crystal structure of the photocolored product of PMBP-TSC was determined by single crystal XRD analysis. The results show that the photochromic phenomenon is due to the photoisomerization from enol form to keto form. Their photochromic properties were studied by powder-UV reflectance spectra under the irradiation of 200-380 nm light. The first-order rate constants of the photocoloring reaction were found to be 7.80×10-3 s-1 for compound 1A and 1.03×10-3 s-1 for compound 2A.

  12. Synthesis and insecticidal activity of new deoxypodophyllotoxin derivatives modified in the D-ring. (United States)

    Wang, Juanjuan; Yu, Xiang; Zhi, Xiaoyan; Xu, Hui


    In continuation of our program aimed at the discovery of new natural-product-based insecticidal agents, twenty-six deoxypodophyllotoxin derivatives modified in the D-ring were synthesized and evaluated as insecticidal agents against the pre-third-instar larvae of oriental armyworm, Mythimna separata (Walker) in vivo at 1 mg/mL. The configuration of three compounds 3, 4, and IIIi was unambiguously determined by single-crystal X-ray diffraction. It demonstrated that aminolysis of deoxypodophyllotoxin in the presence of pyrrolidine and piperidine could result in complete inversion of the configuration of the carbonyl group at its C-2 position. Five compounds IIa, IIi-k, and IIIh showed the equal or higher insecticidal activity than toosendanin. Especially IIj displayed the most potent insecticidal activity with the final mortality rate of 65.5%.

  13. Reactivity of Tp(Me2) -supported yttrium alkyl complexes toward aromatic N-heterocycles: ring-opening or C-C bond formation directed by C-H activation. (United States)

    Yi, Weiyin; Zhang, Jie; Huang, Shujian; Weng, Linhong; Zhou, Xigeng


    Unusual chemical transformations such as three-component combination and ring-opening of N-heterocycles or formation of a carbon-carbon double bond through multiple C-H activation were observed in the reactions of Tp(Me2) -supported yttrium alkyl complexes with aromatic N-heterocycles. The scorpionate-anchored yttrium dialkyl complex [Tp(Me2) Y(CH2 Ph)2 (THF)] reacted with 1-methylimidazole in 1:2 molar ratio to give a rare hexanuclear 24-membered rare-earth metallomacrocyclic compound [Tp(Me2) Y(μ-N,C-Im)(η(2) -N,C-Im)]6 (1; Im=1-methylimidazolyl) through two kinds of C-H activations at the C2- and C5-positions of the imidazole ring. However, [Tp(Me2) Y(CH2 Ph)2 (THF)] reacted with two equivalents of 1-methylbenzimidazole to afford a C-C coupling/ring-opening/C-C coupling product [Tp(Me2) Y{η(3) -(N,N,N)-N(CH3 )C6 H4 NHCHC(Ph)CN(CH3 )C6 H4 NH}] (2). Further investigations indicated that [Tp(Me2) Y(CH2 Ph)2 (THF)] reacted with benzothiazole in 1:1 or 1:2 molar ratio to produce a C-C coupling/ring-opening product {(Tp(Me2) )Y[μ-η(2) :η(1) -SC6 H4 N(CHCHPh)](THF)}2 (3). Moreover, the mixed Tp(Me2) /Cp yttrium monoalkyl complex [(Tp(Me2) )CpYCH2 Ph(THF)] reacted with two equivalents of 1-methylimidazole in THF at room temperature to afford a trinuclear yttrium complex [Tp(Me2) CpY(μ-N,C-Im)]3 (5), whereas when the above reaction was carried out at 55 °C for two days, two structurally characterized metal complexes [Tp(Me2) Y(Im-Tp(Me2) )] (7; Im-Tp(Me2) =1-methyl-imidazolyl-Tp(Me2) ) and [Cp3 Y(HIm)] (8; HIm=1-methylimidazole) were obtained in 26 and 17 % isolated yields, respectively, accompanied by some unidentified materials. The formation of 7 reveals an uncommon example of construction of a CC bond through multiple C-H activations.

  14. A gene expression study of the activities of aromatic ring-cleavage dioxygenases in Mycobacterium gilvum PYR-GCK to changes in salinity and pH during pyrene degradation.

    Directory of Open Access Journals (Sweden)

    Abimbola Comfort Badejo

    Full Text Available Polycyclic aromatic hydrocarbons (PAHs are toxic pollutants found in the environment which can be removed through the use of physical and biological agents. The rate of PAH biodegradation is affected by environmental conditions of pH, salinity and temperature. Adaptation of the pyrene degrading bacteria, Mycobacterium gilvum PYR-GCK, to fluctuating environmental conditions during pyrene biodegrading activity was studied using the quantitative real time - Polymerase Chain Reaction (qRT-PCR technique. Four aromatic ring-cleavage dioxygenase genes: phdF, phdI, pcaG and pcaH; critical to pyrene biodegradation, were studied in pH states of 5.5, 6.5, 7.5 and NaCl concentrations 0 M, 0.17 M, 0.5 M, 0.6 M, 1 M. First, we conducted a residual pyrene study using gas chromatography and flame ionization technologies. Central to a gene expression study is the use of a valid endogenous reference gene, making its determination our next approach, using the geNorm/NormFinder algorithms. Armed with a valid control gene, rpoB, we applied it to a gene expression study, using the comparative critical threshold (2(ΔΔCT quantification method. The pyrene degrading activity of the strain was strongly functional in all the NaCl concentration states, with the least activity found at 1M (∼70% degraded after 48 hours of cultivation. The transcripts quantification of three genes backed this observation with high expression levels. The gene expression levels also revealed pH 6.5 as optimal for pyrene degradation and weak degradation activity at pH of 5.5, corroborating the residual pyrene analysis. The expression of these genes as proteins has already been studied in our laboratory using proteomics techniques and this validates our current study.

  15. Anéis aromáticos condensados e relação E4/E6: estudo de ácidos húmicos de gleissolos por RMN de 13C no estado sólido utilizando a técnica CP/MAS desacoplamento defasado Condensed aromatic rings and E4/E6 ratio: humic acids in gleysoils studied by NMR CP/MAS13C, and dipolar dephasing

    Directory of Open Access Journals (Sweden)

    Sérgio da Costa Saab


    Full Text Available In this work, seven samples of humic acids extracted from gleysoils were investigated. These studies, using NMR CP/MAS 13C techniques, did not show significant correlation between the E4/E6 ratio and the degree of aromaticity. However, dipolar dephasing (DD measurements of condensed aromatic or substituted carbons showed a negative correlation of 0.94. Also, there was a good correlation between the amount of semiquinone free radicals measured by the EPR technique and condensed aromatic rings measured by NMR CP/MAS 13C with the DD technique. The content of semiquinone free radicals was quantified by EPR spectroscopy and was correlated with the humification (degree of aromaticity of the humic substances. The results indicated that the E4/E6 ratio identifies the degree of aromatic rings condensation. It was also found that the degree of aromaticity, measured by NMR, as frequently presented in the literature (by conventional CP/MAS, underestimates aromatic rings in condensed structures.

  16. Condensed aromatic rings and E{sub 4}/E{sub 6} ratio: humic acids in gleysoils studied by NMR CP/MAS{sup 13}C, and dipolar dephasing; Aneis aromaticos condensados e relacao E{sub 4}/E{sub 6}: estudo de acidos humicos de gleissolos por RMN de {sup 13}C no estado solido utilizando a tecnica CP/MAS desacoplamento defasado

    Energy Technology Data Exchange (ETDEWEB)

    Saab, Sergio da Costa [Universidade Estadual de Ponta Grossa, PR (Brazil). Dept. de Fisica]. E-mail:; Martin-Neto, Ladislau [Empresa Brasileira de Pesquisa Agropecuaria, Sao Carlos, SP (Brazil)


    In this work, seven samples of humic acids extracted from gleysoils were investigated. These studies, using NMR CP/MAS {sup 13}C techniques, did not show significant correlation between the E{sub 4}/E{sub 6} ratio and the degree of aromaticity. However, dipolar dephasing (DD) measurements of condensed aromatic or substituted carbons showed a negative correlation of 0.94. Also, there was a good correlation between the amount of semiquinone free radicals measured by the EPR technique and condensed aromatic rings measured by NMR CP/MAS {sup 13}C with the DD technique. The content of semiquinone free radicals was quantified by EPR spectroscopy and was correlated with the humification (degree of aromaticity) of the humic substances. The results indicated that the E{sub 4}/E{sub 6} ratio identifies the degree of aromatic rings condensation. It was also found that the degree of aromaticity, measured by NMR, as frequently presented in the literature (by conventional CP/MAS), underestimates aromatic rings in condensed structures. (author)

  17. Synthesis of Mixed-ring Zirconocene Complexes Containing Alkenyl Group and Ethylene Polymerization Catalyzed with Them

    Institute of Scientific and Technical Information of China (English)

    钱延龙; 孙俊全; 等


    Four new mixed-ring zirconium complexes,[CH2=CH(CH2)n·C5H4](RC5H4)ZrCl2[n=1,R=CH3OCH2CH2(3);n=2,R=CH3OCH2CH2(4);n=2,R=Me3Si(5);n=2,R=allyl(6)],have been prepared by the reaction of CH2=CH(CH2)nC5H4ZrCl3·DME[n=1(1);n=2(2)] with RC5H4Li.When activated with methylaluminoxane(MAO),the catalytic activities of the above complexes in ethylene polymerization were tested.Complexes 5 and 6 show high activities similar to Cp2ZrCl2.Introduction of methoxyethyl group into Cp-ligand dramatically decreases the catalytic activities of complexes 3 and 4,which can be overcome by increasing the amount of MAO.For complex 5,the dependence of activity and molecular weight(Mη) on the Al/Zr ratio,the polymerization time(tp).polymerization temperature(Tp) and the polymerization solvent volume(V) was investigated.

  18. Synthesis and optimization ring opening of monoepoxide linoleic acid using p-toluenesulfonic acid. (United States)

    Salimon, Jumat; Abdullah, Bashar Mudhaffar; Yusop, Rahimi M; Salih, Nadia; Yousif, Emad


    Biolubricant base oils, 9,12-hydroxy-10,13-oleioxy-12-octadecanoic acid (HYOOA) was synthesized based on the esterification reaction of Monoepoxide linoleic acid 9(12)-10(13)-monoepoxy 12(9)-octadecanoic acid (MEOA) with oleic acid (OA) and catalyzed by p-Toluenesulfonic acid. The optimum conditions for the experiment using D-optimal design to obtain high yield% of 84.61, conversion% of 83.54 and lowest OOC% of 0.05 were predicted at OA/MEOA ratio of 0.2:1 (mol/mol), PTSA/MEOA ratio of 0.4:1 (mol/mol), reaction temperature at 110°C, and reaction time at 4.5 h. The FTIR peaks of HYOOA indicate the disappearance of the absorption band at 820 cm(-1), which belongs to the oxirane ring. (13)C and (1)H NMR spectra analyses confirmed the result of HYOOA with appearance carbon-ester (C = O) chemical shift at 174.1 ppm and at 4.06 ppm for (13)C and (1)H NMR respectively.


    Institute of Scientific and Technical Information of China (English)

    Lin Cheng; Xi-gao Jian


    The direct polymerization of an unsymmetrical kink non-coplanar heterocyclic diarnine (1) with various aromatic bis(trimellitimide)s (2a-e) using triphenyl phosphite and pyridine as condensing agents could generate a series of new aromatic poly(amide imide)s (3a-e) containing the kink non-coplanar phthalazinone heterocyclic units in the polymer main chains with inherent viscosities of 0.58-0.66 dL/g. The polymers are readily soluble in a variety of solvents such as N,Ndimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methy1-2-pyrrolidinone, pyridine and m-cresol and can be cast to form flexible and tough films. The glass transition temperatures of polymers (Ts) are in the range of 301-327℃,and the temperatures for 5% weight loss in nitrogen are in the range of 498-521 ℃.


    Institute of Scientific and Technical Information of China (English)

    Yun-hui Zhao; Fen Wang; Xu-bo Yuan; Gen-hui Xu; Jing Sheng


    Two series of aromatic-aliphatic random copolyesters (PEBTOXS) with diverse diol ratios have been synthesizedby direct melting polycondensation. Two kinds of diols (glycol (EG) and 1,4-butanediol (BD)) are used in combination inorder to adjust crystallization and tensile properties, and three kinds of diacids (dimethyl terephthalate (DMT), diethyloxalate (DEOX), and sebacic acid (SA)) are involved. IH-NMR spectra quantify both composition and structure, and showthat the final contents in copolyesters appropriate to the feed ratio. Average sequence lengths of six polyester units arecalculated based on the analyses of 1H-NMR spectra and copolyester structure. The results reveal that the average sequencelengths of sebacate related units increase with the increasing content of sebacic acid in copolyesters, while those of oxalaterelated units show a slight rise. Decreases of average sequence length are found for all terephthalate units, which may bebecause of the restriction of rigid aromatic units in reactions.

  1. Aziridine- and Azetidine-Pd Catalytic Combinations. Synthesis and Evaluation of the Ligand Ring Size Impact on Suzuki-Miyaura Reaction Issues

    Directory of Open Access Journals (Sweden)

    Hamza Boufroura


    Full Text Available The synthesis of new vicinal diamines based on aziridine and azetidine cores as well as the comparison of their catalytic activities as ligand in the Suzuki-Miyaura coupling reaction are described in this communication. The synthesis of three- and four-membered ring heterocycles substituted by a methylamine pendant arm is detailed from the parent nitrile derivatives. Complexation to palladium under various conditions has been examined affording vicinal diamines or amine-imidate complexes. The efficiency of four new catalytic systems is compared in the preparation of variously substituted biaryls. Aziridine- and azetidine-based catalytic systems allowed Suzuki-Miyaura reactions from aryl halides including chlorides with catalytic loadings until 0.001% at temperatures ranging from 100 °C to r.t. The evolution of the Pd-metallacycle ring strain moving from azetidine to aziridine in combination with a methylamine or an imidate pendant arm impacted the Suzuki-Miyaura reaction issue.

  2. Synthesis of a Near-Infrared Emitting Squaraine Dye in an Undergraduate Organic Laboratory (United States)

    Marks, Patrick; Levine, Mindy


    Squaraines are a class of organic fluorophores that possess unique photophysical properties, including strong near-infrared absorption and emission. The synthesis of many squaraines involves the condensation of an electron-rich aromatic ring with squaric acid. These reactions are generally refluxed overnight in a benzene-butanol solvent mixture.…

  3. One-pot synthesis of novel 2,3-dihydro-1H-indazoles. (United States)

    Breton, Gary W; Lepore, Antonio J


    A copper(I)-mediated one-pot synthesis of 2,3-dihydro-1H-indazole heterocycles has been developed. This synthetic route provides the desired indazoles in moderate to good yields (55%-72%) which are substantially better than those achievable with an alternative two-step reaction sequence. The reaction is tolerant of functionality on the aromatic ring.

  4. Metabolic activation of N-hydroxy arylamines, N-hydroxy heterocyclic amines and ring-hydroxymethyl polycyclic aromatic hydrocarbons by human sulfotransferases

    Energy Technology Data Exchange (ETDEWEB)

    Chou, H.C.


    Arylamines and polycyclic aromatic hydrocarbons (PAHs) are two major classes of chemical carcinogens. N-Hydroxylation of arylamines is regarded to be a necessary process for their mutagenicity and carcinogenicity, while alkyl-hydroxylation is the major metabolic pathway for alkyl-substituted PAHs. Evidence has been presented that sulfation of several N-hydroxy arylamines and hydroxymethyl PAHs is an important pathway leading to the formation of ultimate carcinogens in experiment animals. Sulfation of these chemicals forms putative sulfuric acid ester intermediates that can rearrange to electrophilic nitrenium or carbenium ions capable of forming covalent adducts with important cellular macromolecules. In order to study the metabolic activation by sulfotransferase(s) in various human tissue preparations an in vitro enzymatic assay was established. A metabolic phenotyping method was also developed for thermostable phenolsulfotransferase (TS-PST) in platelet homogenates (correlated with TS-PST activity in other tissues) based on a simple colorimetric assay using 2-naphthol as substrate. By using a PAPS-regenerating system to supply the activated sulfate and calf thymus DNA to trap the reactive metabolites, we found that N-hydroxy derivatives of the carcinogens, 4-aminobiphenyl (4-ABP), 4,4[prime]-methylene-bis(2-chloroaniline) (MOCA), 2-acetylaminofluorene (2-AAF), 2-aminofluorene (2-AF), 2-amino-1-methyl-6-phenylimidazo [4,5-b]pyridine (PhIP), and 2-amino-6-methyldipyrido [1,2-1:3[prime],2[prime]-d]imidazole (Glu-P-1) were metabolically activated by human TS-PST. On the other hand, three methyl-hydroxylated derivatives (7-OH, 12-OH, and 7,12-diOH) of 7, 12-dimethylbenz[a]anthracene (DMBA) were metabolically activated by human steroid sulfotransferase. Human sulfotransferase(s)-mediated activation of 2-amino-3-methylimidazo[4,5-f]quinoline (IQ) or 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) was not observed.


    Institute of Scientific and Technical Information of China (English)

    PAN Caiyuan; WANG Yin


    This paper describes the synthesis and free radical ring- opening polymerization of 2 - methyl-and2 - methyl - 9 - n - butyl ( - 7 - methylene - 1,4, 6 - trioxaspiro (4, 4 ) nonane ). The structures of the two polymers were verified by IR, 1H and 13C NMR spectra. The substituent on 9-position of 7-methylene- trioxaspiro (4, 4 ) nona ne affects the structure of polymer and polymerization activity. The polymerization mechanism is discussed .

  6. Synthesis and biological activities of the respiratory chain inhibitor aurachin D and new ring versus chain analogues

    Directory of Open Access Journals (Sweden)

    Xu-Wen Li


    Full Text Available Aurachins are myxobacterial 3-farnesyl-4(1H-quinolone derived compounds initially described as respiratory chain inhibitors, more specifically as inhibitors of various cytochrome complexes. They are also known as potent antibiotic compounds. We describe herein the first synthesis of aurachin D through a key Conrad–Limpach reaction. The same strategy was used to reach some ring as opposed to chain analogues, allowing for the description of structure–activity relationships. Biological screening of the analogues showed antiparasitic, cytotoxic, antibacterial and antifungal activities, and depletion of the mitochondrial membrane potential. The strongest activity was found on Plasmodium falciparum with a selectivity index of 345, compared to Vero cells, for the natural product and its geranyl analogue. The loss of mitochondrial membrane potential induced by aurachins in human U-2 OS osteosarcoma cells was studied, showing the best activity for aurachin D and a naphthalene analogue, yet without totally explaining the observed cytotoxic activity of the compounds. Finally, a synthetic entry is given to the complete carboheterocyclic core of aurachin H through the N-oxidation/epoxidation of aurachin D and a shorter chain analogue, followed by subsequent biomimetic cyclization.

  7. Bidirectional cross metathesis and ring-closing metathesis/ring opening of a C2-symmetric building block: a strategy for the synthesis of decanolide natural products

    Directory of Open Access Journals (Sweden)

    Bernd Schmidt


    Full Text Available Starting from the conveniently available ex-chiral pool building block (R,R-hexa-1,5-diene-3,4-diol, the ten-membered ring lactones stagonolide E and curvulide A were synthesized using a bidirectional olefin-metathesis functionalization of the terminal double bonds. Key steps are (i a site-selective cross metathesis, (ii a highly diastereoselective extended tethered RCM to furnish a (Z,E-configured dienyl carboxylic acid and (iii a Ru–lipase-catalyzed dynamic kinetic resolution to establish the desired configuration at C9. Ring closure was accomplished by macrolactonization. Curvulide A was synthesized from stagonolide E through Sharpless epoxidation.

  8. Bidirectional cross metathesis and ring-closing metathesis/ring opening of a C 2-symmetric building block: a strategy for the synthesis of decanolide natural products. (United States)

    Schmidt, Bernd; Kunz, Oliver


    Starting from the conveniently available ex-chiral pool building block (R,R)-hexa-1,5-diene-3,4-diol, the ten-membered ring lactones stagonolide E and curvulide A were synthesized using a bidirectional olefin-metathesis functionalization of the terminal double bonds. Key steps are (i) a site-selective cross metathesis, (ii) a highly diastereoselective extended tethered RCM to furnish a (Z,E)-configured dienyl carboxylic acid and (iii) a Ru-lipase-catalyzed dynamic kinetic resolution to establish the desired configuration at C9. Ring closure was accomplished by macrolactonization. Curvulide A was synthesized from stagonolide E through Sharpless epoxidation.

  9. Synthesis, Structure and Antimicrobial Properties of Novel Benzalkonium Chloride Analogues with Pyridine Rings. (United States)

    Brycki, Bogumił; Małecka, Izabela; Koziróg, Anna; Otlewska, Anna


    Quaternary ammonium compounds (QACs) are a group of compounds of great economic significance. They are widely used as emulsifiers, detergents, solubilizers and corrosion inhibitors in household and industrial products. Due to their excellent antimicrobial activity QACs have also gained a special meaning as antimicrobials in hospitals, agriculture and the food industry. The main representatives of the microbiocidal QACs are the benzalkonium chlorides (BACs), which exhibit biocidal activity against most bacteria, fungi, algae and some viruses. However, the misuses of QACs, mainly at sublethal concentrations, can lead to an increasing resistance of microorganisms. One of the ways to avoid this serious problem is the introduction and use of new biocides with modified structures instead of the biocides applied so far. Therefore new BAC analogues P13-P18 with pyridine rings were synthesized. The new compounds were characterized by NMR, FT-IR and ESI-MS methods. PM3 semiempirical calculations of molecular structures and the heats of formation of compounds P13-P18 were also performed. Critical micellization concentrations (CMCs) were determined to characterize the aggregation behavior of the new BAC analogues. The antimicrobial properties of novel QACs were examined by determining their minimal inhibitory concentration (MIC) values against the fungi Aspergillus niger, Candida albicans, Penicillium chrysogenum and bacteria Staphylococcus aureus, Bacillus subtilis, Escherichia coli and Pseudomonas aeruginosa. The MIC values of N,N-dimethyl-N-(4-methylpyridyl)-N-alkylammonium chlorides for fungi range from 0.1 to 12 mM and for bacteria, they range from 0.02 to 6 mM.

  10. Synthesis, Structure and Antimicrobial Properties of Novel Benzalkonium Chloride Analogues with Pyridine Rings

    Directory of Open Access Journals (Sweden)

    Bogumił Brycki


    Full Text Available Quaternary ammonium compounds (QACs are a group of compounds of great economic significance. They are widely used as emulsifiers, detergents, solubilizers and corrosion inhibitors in household and industrial products. Due to their excellent antimicrobial activity QACs have also gained a special meaning as antimicrobials in hospitals, agriculture and the food industry. The main representatives of the microbiocidal QACs are the benzalkonium chlorides (BACs, which exhibit biocidal activity against most bacteria, fungi, algae and some viruses. However, the misuses of QACs, mainly at sublethal concentrations, can lead to an increasing resistance of microorganisms. One of the ways to avoid this serious problem is the introduction and use of new biocides with modified structures instead of the biocides applied so far. Therefore new BAC analogues P13–P18 with pyridine rings were synthesized. The new compounds were characterized by NMR, FT-IR and ESI-MS methods. PM3 semiempirical calculations of molecular structures and the heats of formation of compounds P13–P18 were also performed. Critical micellization concentrations (CMCs were determined to characterize the aggregation behavior of the new BAC analogues. The antimicrobial properties of novel QACs were examined by determining their minimal inhibitory concentration (MIC values against the fungi Aspergillus niger, Candida albicans, Penicillium chrysogenum and bacteria Staphylococcus aureus, Bacillus subtilis, Escherichia coli and Pseudomonas aeruginosa. The MIC values of N,N-dimethyl-N-(4-methylpyridyl-N-alkylammonium chlorides for fungi range from 0.1 to 12 mM and for bacteria, they range from 0.02 to 6 mM.

  11. The role of cytochrome P4501A activity inhibition in three- to five-ringed polycyclic aromatic hydrocarbons embryotoxicity of marine medaka (Oryzias melastigma). (United States)

    Mu, Jing-li; Wang, Xin-hong; Jin, Fei; Wang, Ju-ying; Hong, Hua-sheng


    The mode of action of PAHs that causes fish developmental malformations is unclear. The embryotoxicity of marine medaka (Oryzias melastigma) was investigated after individual exposure to three- to five-ring PAHs Phe, Py, and BaP or co-exposure with α-ANF for 18 days. We found that the relationships between EROD induction and developmental deformities of embryos showed a various pattern under different exposure scenarios of Phe, Py, and BaP, which suggested possibly different modes of action in determining the developmental toxicities. As for co-exposure scenarios of each PAH combined with ANF, it showed potentially synergistic effects. The inhibited CYP1A mediated enzyme activity by ANF after co-exposure did not effectively alleviate developmental toxicity of embryo. It showed potentially synergistic effects after co-exposure of marine fish embryos to CYP1A inhibitors and PAH-type CYP1A inducers. Heart deformities in the early life stages of marine medaka were recommended as a biomarker for indicating the extent of PAH pollution.

  12. Aromaticity of group 14 organometallics: experimental aspects. (United States)

    Lee, Vladimir Ya; Sekiguchi, Akira


    The long story of aromatic compounds has extended over almost two centuries, since the discovery by Faraday of "bicarburet of hydrogen", or C(6)H(6), now called benzene. Since then, the chemistry of aromatic compounds has been developed extensively; this is reflected in the synthesis of novel classes of aromatic derivatives including charged species, nonclassical (Möbius, three-dimensional, homo-, metalla-) aromatics, and fullerenes. The theory of aromaticity has also undergone a spectacular evolution since the first definition of aromaticity by Hückel; the classification of aromaticity now requires the consideration of versatile criteria: energetic, structural, magnetic, among others. In this Review, we discuss the current state of affairs in the chemistry of aromatic compounds of the heavier Group 14 elements, the latest experimental achievements, as well as future prospects in the field.

  13. Bioassay of polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Van Kirk, E.A.


    A positive relationship was found between the photodynamic activity of 24 polycyclic aromatic hydrocarbons versus published results on the mutagenicity, carcinogenicity, and initiation of unscheduled DNA synthesis. Metabolic activation of benzo(a)pyrene resulted in detection of increased mutagenesis in Paramecium tetraurelia as found also in the Ames Salmonella assay. The utility of P. tetraurelia as a biological detector of hazardous polycyclic aromatic hydrocarbons is discussed.

  14. Synthesis of New Bifunctional Bis(oxazolines) and Their Application in the Asymmetric Cyanosilylation of Aromatic Ketones

    Institute of Scientific and Technical Information of China (English)

    LUO,Mei; DU,Da-Ming


    @@ Catalytic asymmetric synthesis of tertiary cyanohydrins by the addition of cyanide to a wide range of ketones has important synthetic utility, since the resulting optically active cyanohydrins are important intermediates for the synthesis of a variety of valuable classes of chiral compounds. The application of oxazoline in asymmetric cyanosilylation has seldom reported in comparation with other reactions.[1] Recently, polymer-supported pyridine-bis(oxazoline) ytterbium complex was reported to catalyze cyanosilylation of benzaldehyde.

  15. New thermally stable polyesters based on 2,5-pyridinedicarbonyl dichloride and aromatic diols: Synthesis and characterization

    Institute of Scientific and Technical Information of China (English)

    Hossein Nasr Isfahani; Khalil Faghihi


    Six new thermally stable polyesters (4a-f) were synthesized through the solution polycondensation reaction of 2,5-pyridine dicarbonyldichloride (2) with six aromatic diols in N,N'-dimethyl acetamide (DMAc) solution and in the presence of pyridine as a base. The polycondensation reactions produce a series of new polyesters (4a-f) in high yields, and inherent viscosity between 0.30 and 0.55 dL/g. The resulting polyesters were characterized by elemental analysis, viscosity measurements, thermal gravimetric analysis (TGA and DTG), solubility test, Fourier transform infrared (FT-IR) spectroscopy and gel permeation chromatography (GPC).

  16. Electron-deficient N-heteroaromatic linkers for the elaboration of large, soluble polycyclic aromatic hydrocarbons and their use in the synthesis of some very large transition metal complexes. (United States)

    Fogel, Yulia; Kastler, Marcel; Wang, Zhaohui; Andrienko, Denis; Bodwell, Graham J; Müllen, Klaus


    The selective oxidation of the perimeter of an extended polycyclic aromatic hydrocarbon (PAH), namely a six-fold tert-butylated tetrabenzo[bc,ef,hi,uv]ovalene, led to the formation of an alpha-diketone. The newly installed carbonyl centers allowed this building block to be converted into the largest known heteroatom-containing PAHs (up to 224 atoms in the aromatic core) by way of the quinoxaline ring condensation reaction. The tert-butyl substituents caused a distortion of the usually planar aromatic frameworks, which hampered the aggregation tendency of the extended aromatic pi-systems and led to extraordinarily high solubilities. All of the systems described here, even the giant phthalocyanine, could thus be purified using standard chromatographic techniques and characterized using typical spectroscopic methods. For the first time, fully resolved 1H NMR spectra of soluble, diamagnetic, 98- and 104-atom-containing aromatic systems are presented. The computed and experimental UV/vis spectra emphasize the dependence of the characteristic alpha-, p-, and beta-bands upon the size of the PAHs. It was also possible to obtain the largest known ligand to yet be complexed around a ruthenium center. A quadrupolar solvatochromic effect was observed when two donating PAH moieties were fused to an accepting quinoxaline center, in which case the photoluminescence spanned a range of about 80 nm. Electrochemical properties of the new nanographenes were investigated using cyclic voltammetry, and this showed quasi-reversible reductions.

  17. "Carbo-aromaticity" and novel carbo-aromatic compounds. (United States)

    Cocq, Kévin; Lepetit, Christine; Maraval, Valérie; Chauvin, Remi


    While the concept of aromaticity is being more and more precisely delineated, the category of "aromatic compounds" is being more and more expanded. This is illustrated by an introductory highlight of the various types of "aromaticity" previously invoked, and by a focus on the recently proposed "aromatic character" of the "two-membered rings" of the acetylene and butatriene molecules. This serves as a general foundation for the definition of "carbo-aromaticity", the relevance of which is surveyed through recent results in the synthetic, physical, and theoretical chemistry of carbo-mers and in particular macrocyclic-polycyclic representatives constituting a natural family of "novel aromatic compounds". With respect to their parent molecules, carbo-mers are constitutionally defined as "carbon-enriched", and can also be functionally regarded as "π-electron-enriched". This is exemplified by recent experimental and theoretical results on functional, aromatic, rigid, σ,π-macrocyclic carbo-benzene archetypes of various substitution patterns, with emphasis on the quadrupolar pattern. For the purpose of comparison, several types of non-aromatic references of carbo-benzenes are then considered, i.e. freely rotating σ,π-acyclic carbo-n-butadienes and flexible σ-cyclic, π-acyclic carbo-cyclohexadienes, and to "pro-aromatic" congeners, i.e. rigid σ,π-macrocyclic carbo-quinoids. It is shown that functional carbo-mers are entering the field of "molecular materials" for properties such as linear or nonlinear optical properties (e.g. dichromism and two-photon absorption) and single molecule conductivity. Since total or partial carbo-mers of aromatic carbon-allotropes of infinite size such as graphene (graphynes and graphdiynes) and graphite ("graphitynes") have long been addressed at the theoretical or conceptual level, recent predictive advances on the electrical, optical and mechanical properties of such carbo-materials are surveyed. Very preliminary experimental results

  18. Synthesis and Exploration of Ladder-Structured Large Aromatic Dianhydrides as Organic Cathodes for Rechargeable Lithium Batteries. (United States)

    Zhang, Qichun; Xie, Jian; Chen, Wangqiao; Wang, Zilong; Kenneth Choo Wei Jie, Choo Wei Jie; Liu, Ming


    Comparing to anode materials in Li-ion batteries, the research on cathode materials is far behind and their capacities are much smaller. Thus, in order to address these issues, we believe that organic conjugated materials could be a solution. In this study, we demonstrate two non-polymeric dianhydrides with large aromatic structures: NDA-4N (naphthalenetetracarboxylicdianhydride with four nitrogen atoms) and PDA-4N (perylenetetracarboxylicdianhydride with four nitrogen atoms). Their electrochemical properties have been investigated between 2.0 and 3.9 V (vs. Li+/Li). Benefiting from multi-electron reactions, NDA-4N and PDA-4N could reversibly achieve 79.7% and 92.3% of their theoretical capacity, respectively. Further cycling reveals that organic compound with a relatively larger aromatic building block could be able to achieve a better stability, as an obvious 36.5% improvement of the capacity retention was obtained when the backbone was switched from naphthalene to perylene. This study proposes an opportunity to achieve promising small-molecule based cathode materials through tailoring organic structures.

  19. Solvothermal synthesis of CdIn2S4 photocatalyst for selective photosynthesis of organic aromatic compounds under visible light. (United States)

    Ling, Cancan; Ye, Xiangju; Zhang, Jinghu; Zhang, Jinfeng; Zhang, Sujuan; Meng, Sugang; Fu, Xianliang; Chen, Shifu


    Ternary chalcogenide semiconductor, cadmium indium sulfide (CdIn2S4), was prepared by a simple solvothermal method using ethylene glycol as a solvent, as well as indium chloride tetrahydrate (InCl3(.)4H2O), cadmium nitrate tetrahydrate [Cd(NO3)2(.)4H2O], and thiacetamide (TAA) as precursors. The resulted sample was subject to a series of characterizations. It is the first time to use CdIn2S4 sample as a visible light-driven photocatalyst for simultaneous selective redox transformation of organic aromatic compounds. The results indicate that the as-synthesized CdIn2S4 photocatalyst not only has excellent photocatalytic performance compared with pure In2S3 and CdS for the selective oxidation of aromatic alcohols in an oxygen environment, but also shows high photocatalytic redox activities under nitrogen atmosphere. A possible mechanism for the photocatalytic redox reaction in the coupled system was proposed. It is hoped that our current work could extend the applications of CdIn2S4 photocatalyst and provide new insights for selective transformations of organic compounds.

  20. Improved synthesis of seven aromatic Baylis-Hillman adducts (BHA): evaluation against Artemia salina Leach. and Leishmania chagasi. (United States)

    Barbosa, Ticiano P; Junior, Cláudio G L; Silva, Fábio P L; Lopes, Horacimone M; Figueiredo, Lucas R F; Sousa, Suervy C O; Batista, Guilherme N; da Silva, Thiago G; Silva, Tania M S; de Oliveira, Márcia R; Vasconcellos, Mário L A A


    We described a very efficient procedure to prepare seven aromatic compounds (1-7), a new class of antileishmanial substances, through Baylis-Hillman reaction (BHR). With one, all the Baylis-Hillman adducts were prepared in quantitative yields by reaction of the corresponding aromatic aldehydes in acrylonitrile at 0 degrees C in only 10-40min reaction time. We present our results about the toxicities of these compounds evaluated on the microcrustaceous Artemia salina Leach. and against promastigote Leishmania chagasi. All substances evaluated in this work have showed high bioactivity. The 3-hydroxy-2-methylene-3-(4-bromopheny)propanenitrile (4) (LC(50)=30.9 microg/mL on A. salina; IC(50)=25.2 microM on L. chagasi) was the most active compound evaluated on A. salina Leach. and on promastigote L. chagasi. The 2-[hydroxy(pyridin-4-yl)methyl]acrylonitrile (7) (LC(50)=30.9 microg/mL on A. salina Leach.; IC(50)=4.8 microg/mL on L. chagasi) was also a very active substance evaluated in this work on promastigote L. chagasi.

  1. Towards novel adsorptive nanomaterials: Synthesis of Co2+Mo6+ LDH for sulfur and aromatic removal from crude petrolatum

    Directory of Open Access Journals (Sweden)

    Mohsen S. Mostafa


    Full Text Available In the present work Co/Mo(CO32−-LDH material of highly energetic surface was prepared by controlled titration of ammonium carbonate and ammonium hydroxide against Co and Mo cations at elevated temperatures, while different analytical techniques were applied to proof the chemical constitution and surface features of the material as XPS (X-ray Photoelectric Spectroscopy in addition to XRF metal analysis, FT-IR, SEM, XRD, DSC-TGA and N2 adsorption–desorption isotherm. The highly energetic surface due to formation of 4+ surface charge in the brucite layer between Co and Mo as confirmed by XPS was practically ensured when the freshly prepared Co2+Mo6+-LDH dried at 60 °C overnight without any activation has been applied as a novel adsorbent for the removal of the undesirable compounds (sulfur and aromatics compounds from crude waxes. Suez crude petrolatum has been used during this study. Depending on the experimental data, we were successful to prepare a new type of LDHs showed high ability for removing the undesirable compounds (sulfur and aromatics from Suez crude petrolatum. Also, in the same trend it removed low melting waxes. This leads to isolation of microcrystalline waxes from petroleum wastes which used as a lubricant, rust preventive, in the manufacture of cosmetics, and in medicine as a protective dressing, emollient, and in a lot of industrial applications.

  2. A regioselective synthesis of benzopinacolones through aerobic dehydrogenative α-arylation of the tertiary sp3 C-H bond of 1,1-diphenylketones with aromatic and heteroaromatic compounds. (United States)

    More, Nagnath Yadav; Jeganmohan, Masilamani


    A regioselective synthesis of symmetrical and unsymmetrical benzopinacolones through aerobic dehydrogenative α-arylation at the tertiary sp(3) C-H bond of substituted 1,1-diphenylketones with aromatic and heteroaromatic compounds, in the presence of K2S2O8 in CF3COOH at room temperature, is described. The reaction is proposed to go via a carbocation intermediate, which could be generated directly from cleavage of the sp(3) C-H bond of 1,1-diphenylketone. Subsequent α-arylation was achieved at the methene sp(3) carbon atom of the substituted ketone. A variety of substituted aromatic and heteroaromatic compounds were compatible with this reaction. In addition, benzopinacolones were converted into sterically hindered, tetrasubstituted alkenes and polycyclic aromatic compounds.

  3. Synthesis of benzyl chlorides and cycloveratrylene macrocycles using benzylic alcohols under homogeneous catalysis by HCl/dioxane

    Directory of Open Access Journals (Sweden)

    Yolanda Marina Vargas-Rodríguez


    Full Text Available The synthesis of benzyl chlorides, cyclic derivatives cyclotriveratrylene and cyclotripiperotrylene were carried out in using the HCl/dioxane system as a catalyst. The reaction proceeded with high selectivity and is sensitive to the number of alkyl and methoxy substituent on the aromatic ring.

  4. Ionic liquid mediated synthesis and molecular docking study of novel aromatic embedded Schiff bases as potent cholinesterase inhibitors. (United States)

    Abd Razik, Basma M; Osman, Hasnah; Basiri, Alireza; Salhin, Abdussalam; Kia, Yalda; Ezzat, Mohammed Oday; Murugaiyah, Vikneswaran


    Novel aromatic embedded Schiff bases have been synthesized in ionic liquid [bmim]Br and evaluated in vitro for their acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) enzymes inhibitory activities. Among the newly synthesized compounds, 5f, 5h and 7j displayed higher AChE enzyme inhibitory activities than standard drug, galanthamine, with IC50 values of 1.88, 2.05 and 2.03μM, respectively. Interestingly, all the compounds except for compound 5c displayed higher BChE inhibitories than standard with IC50 values ranging from 3.49 to 19.86μM. Molecular docking analysis for 5f and 7j possessing the most potent AChE and BChE inhibitory activities, disclosed their binding interaction templates to the active site of AChE and BChE enzymes, respectively.

  5. Synthesis and antimicrobial evaluation of 1,4-disubstituted 1,2,3-triazoles with aromatic ester functionality

    Directory of Open Access Journals (Sweden)

    C.P. Kaushik


    Full Text Available A series of 1,4-disubstituted 1,2,3-triazoles having p-substituted aromatic ester functionality were synthesized via Cu(I catalysed click reaction between p-substituted benzoic acid prop-2-ynyl esters and aralkyl azides. The synthesized triazoles were characterized by IR, 1H NMR, 13C NMR and mass spectral techniques. These compounds were evaluated for their antimicrobial activity against Escherichia coli, Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa, Mycobacterium tuberculosis, Candida albicans, Aspergillus niger and Aspergillus flavus by two fold serial dilution method. Some of the synthesized 1,4-disubstituted 1,2,3-triazoles possess comparable or even better antibacterial, antitubercular and antifungal activities than reference drugs against tested bacterial, mycobacterial and fungal strains, respectively.

  6. Synthesis of Acenaphthyl and Phenanthrene Based Fused-Aromatic Thienopyrazine Co-Polymers for Photovoltaic and Thin Film Transistor Applications

    KAUST Repository

    Mondal, Rajib


    Dithiophene and fluorene co-polymers containing fused aromatic thieno[3,4-b]pyrazine moieties were synthesized for organic thin film transistor (OTFT) and organic photovoltaic (OPV) applications. Suzuki and Stille polycondensation reactions were used for the polymerization. The band gap (Eg) of the polymers was tuned in the range of 1.15-1.6 eV to match the solar spectrum. Density functional theory calculations were carried out to rationalize the low band gaps. These polymers showed field effect mobility (μ) as high as 0.2 cm2/(V.s) with an on/off ratio as high as 106 in OTFT devices. Interestingly, one polymer in this class also showed ambipolar charge transport. Power conversion efficiency (PCE) up to 1.3% was achieved in bulk heterojunction solar cells, indicating that these materials are promising for OPV applications. © 2009 American Chemical Society.


    Institute of Scientific and Technical Information of China (English)

    TANG Liming; HUANG Meiyu; JIANG Yingyan


    A silica-supported carboxymethylcellulose platinum complex (abbreviated as SiO2-CMC-Pt) has been prepared and characterized by XPS. Its catalytic properties for hydrogenation of aromatic compounds were studied. The results showed that this catalyst could catalyze the hydrogenation of phenol, anisol, p-cresol, benzene and toluene to cyclohexanol, cyclohexyl methyl ether, p-methyl cyclohexanol, cyclohexane and methylcyclohexane, respectively in 100% yield at 30℃ and 1 atm. In the hydrogenation of phenol,COO/Pt ratio in SiO2-CMC-Pt has much influence on the initial hydrogenation rate and the selectivity for the intermediate product, cyclohexanone. The highest initial rate and the highest yield of cyclohexanone both occur at COO/Pt ratio of 6. The complex is stable during the reaction and can be used repeatedly.

  8. New series of aromatic/ five-membered heteroaromatic butanesulfonyl hydrazones as potent biological agents: Synthesis, physicochemical and electronic properties (United States)

    Hamurcu, Fatma; Mamaş, Serhat; Ozdemir, Ummuhan Ozmen; Gündüzalp, Ayla Balaban; Senturk, Ozan Sanlı


    The aromatic/five-membered heteroaromatic butanesulfonylhydrazone derivatives; 5-bromosalicylaldehydebutanesulfonylhydrazone(1), 2-hydroxy-1-naphthaldehydebutane sulfonylhydrazone(2), indole-3-carboxaldehydebutanesulfonylhydrazone (3), 2-acetylfuran- carboxyaldehydebutanesulfonylhydrazone(4), 2-acetylthiophenecarboxyaldehydebutane- sulfonylhydrazone(5) and 2-acetyl-5-chlorothiophenecarboxyaldehydebutanesulfonyl hydrazone (6) were synthesized by the reaction of butane sulfonic acid hydrazide with aldehydes/ketones and characterized by using elemental analysis, 1H NMR, 13C NMR and FT-IR technique. Their geometric parameters and electronic properties consist of global reactivity descriptors were also determined by theoretical methods. The electrochemical behavior of the butanesulfonylhydrazones were investigated by using cyclic voltammetry (CV), controlled potential electrolysis and chronoamperometry (CA) techniques. The number of electrons transferred (n), diffusion coefficient (D) and standard heterogeneous rate constants (ks) were determined by electrochemical methods.

  9. Total synthesis and evaluation of vinblastine analogues containing systematic deep-seated modifications in the vindoline subunit ring system: core redesign. (United States)

    Schleicher, Kristin D; Sasaki, Yoshikazu; Tam, Annie; Kato, Daisuke; Duncan, Katharine K; Boger, Dale L


    The total synthesis of a systematic series of vinblastine analogues that contain deep-seated structural modifications to the core ring system of the lower vindoline subunit is described. Complementary to the vindoline 6,5 DE ring system, compounds with 5,5, 6,6, and the reversed 5,6 membered DE ring systems were prepared. Both the natural cis and unnatural trans 6,6-membered ring systems proved accessible, with the latter representing a surprisingly effective class for analogue design. Following Fe(III)-promoted coupling with catharanthine and in situ oxidation to provide the corresponding vinblastine analogues, their evaluation provided unanticipated insights into how the structure of the vindoline subunit contributes to activity. Two potent analogues (81 and 44) possessing two different unprecedented modifications to the vindoline subunit core architecture were discovered that matched the potency of the comparison natural products and both lack the 6,7-double bond whose removal in vinblastine leads to a 100-fold drop in activity.

  10. Gaining Control over Radiolytic Synthesis of Uniform Sub-3-nanometer Palladium Nanoparticles: Use of Aromatic Liquids in the Electron Microscope

    Energy Technology Data Exchange (ETDEWEB)

    Abellan Baeza, Patricia; Parent, Lucas R.; Al Hasan, Naila M.; Park, Chiwoo; Arslan, Ilke; Karim, Ayman M.; Evans, James E.; Browning, Nigel D.


    Synthesizing nanomaterials of uniform shape and size is of critical importance to access and manipulate the novel structure-property relationships arising at the nanoscale. In this work we synthesize Pd nanoparticles with well-controlled size using in situ liquid-stage scanning transmission electron microscopy (STEM) and demonstrate a match between the reaction kinetics and products of the radiolytic and chemical syntheses of size-stabilized Pd nanoparticles. We quantify the effect of electron dose on the nucleation kinetics, and compare these results with in situ small angle X-ray scattering (SAXS) experiments investigating the effect of temperature during chemical synthesis. This work introduces methods for precise control of nanoparticle synthesis in the STEM and provides a means to uncover the fundamental processes behind the size and shape stabilization of nanoparticles.


    Institute of Scientific and Technical Information of China (English)

    Chi-fei Wu


    Porcine pancreas lipase (PPL) and PPL immobilized on narrow distributed micron-sized glass beads were employed successfully for the ring-opening polymerization of 5,5-dimethyl-1,3-dioxan-2-one (DTC) for the first time.Different polymerization conditions such as enzyme concentration and reaction temperature were studied. Immobilized PPL exhibits higher activity than native PPL. Along with the increasing enzyme concentration, the molecular weight of resulting PDTC decreases. PPL immobilized on narrow distributed micron-sized glass beads has outstanding recyclability. For the third recycle time, immobilized PPL exhibits the highest catalytic activity and with high activity even after the fifth recyle time for the synthesis of PDTC. The 1H-NMR spectra indicate that decarboxylation does not occur during the ring-opening polymerization.


    Institute of Scientific and Technical Information of China (English)

    Bo-yong Xue; Kenichi Ogata; Akinori Toyota


    Norbornene derivatives exo,endo-2-[2-(3,5-di-tert-butyl-4-hydroxyphenoxy)-acetoxy]methyl-5-norbornene(M1) and 3,3,5,5-tetramethyl-4-piperidinyl 5-norbornene-exo,endo-2-carboxylate(M2)were synthesized and polymerized by RuCl2(=CHPh)(PCy3)2 to prepare a novel kind of bi-functional polymer bearing sterically hindered phenol (SHP) and hindered amine(HLAS)groups via ring-opening metathesis polymerization(ROMP).The resulting copolymers were characterized by gel permeation chromatography(GPC),'H-NMR and differential scanning calorimetry (DSC).The number average molecular weight(Mn)and functional unit content of the resulting copolymer could be regulated by varying the concentration of catalyst and monomer feed.

  13. Fe(OTf)3 versus Bi(OTf)3 as mild catalysts in epoxide oxidative ring-opening, urea α-diketone condensation, and glycoluril diether synthesis. (United States)

    Mandadapu, Vijaybabu; Wu, Feng; Day, Anthony I


    The salt Fe(OTf)3 has been shown to function as an effective catalyst in three different reactions, epoxide oxidative ring-opening to an α-hydroxy ketone, urea α-diketone condensation to form glycolurils, and glycoluril diether synthesis by formaldehyde condensation. In each of these reactions, Fe(OTf)3 was compared to Bi(OTf)3, a viable alternative catalyst with few or no prior examples of this type. Differences and advantages are highlighted but in most cases yields were generally high, and both catalysts outperformed conventional acid catalyzed methods.

  14. The base-free chemoselective ring opening of epoxides with carboxylic acids using [bmim]Br: a rapid entry into 1,2-diol mono-esters synthesis. (United States)

    Rad, Mohammad Navid Soltani; Behrouz, Somayeh


    A facile and highly convenient base-free protocol for the chemoselective preparation of 1,2-diol mono-esters is described. In this method, the regioselective ring opening of epoxides with carboxylic acids in the presence of [bmim]Br furnishes the corresponding 1,2-diol mono-esters in excellent yields. This method is efficient for various structurally diverse epoxides and carboxylic acids and it can be efficiently applied for the scale up synthesis of 1,2-diol mono-esters in reasonable to good yields. [bmim]Br remarkably influences the reaction progress and acts as both solvent and catalyst in this protocol.

  15. Rapid Synthesis of a Lipocationic Polyester Library via Ring-Opening Polymerization of Functional Valerolactones for Efficacious siRNA Delivery. (United States)

    Hao, Jing; Kos, Petra; Zhou, Kejin; Miller, Jason B; Xue, Lian; Yan, Yunfeng; Xiong, Hu; Elkassih, Sussana; Siegwart, Daniel J


    The ability to control chemical functionality is an exciting feature of modern polymer science that enables precise design of drug delivery systems. Ring-opening polymerization of functional monomers has emerged as a versatile method to prepare clinically translatable degradable polyesters.1 A variety of functional groups have been introduced into lactones; however, the direct polymerization of tertiary amine functionalized cyclic esters has remained elusive. We report a strategy that enabled the rapid synthesis of >130 lipocationic polyesters directly from functional monomers without protecting groups. These polymers are highly effective for siRNA delivery at low doses in vitro and in vivo.

  16. A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion

    Energy Technology Data Exchange (ETDEWEB)

    Transue, Wesley J.; Velian, Alexandra; Nava, Matthew; Martin-Drumel, Marie-Aline; Womack, Caroline C.; Jiang, Jun; Hou, Gao-Lei; Wang, Xue-Bin; McCarthy, Michael C.; Field, Robert W.; Cummins, Christopher C.


    Dibenzo-7-phosphanorbornadiene Ph3PC(H)PA (1, A = C14H10, anthracene) is reported as a molecular precursor to phosphaethyne (HC≡P), produced together with anthracene and triphenylphosphine. HCP generated by thermolysis of 1 has been characterized by molecular beam mass spectrometry (MBMS), laser-induced fluorescence (LIF), microwave spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. In toluene, fragmentation of 1 has been found to proceed with activation parameters of ΔH = 25.5 kcal/mol and ΔS = ₋2.43 e.u., and is accompanied by formation of an orange insoluble precipitate. Results from computational studies of the mechanism of HCP generation are in good agreement with experimental data. This high temperature method of HCP generation has pointed to new reaction chemistry with azide anion to produce the 1,2,3,4-phosphatriazolate anion, HCPN3- , for which structural data have been obtained in a single-crystal Xray diffraction study. Negative ion photoelectron spectroscopy has shown the adiabatic detachment energy for this anion to be 3.555(10) eV. The aromaticity of HCPN3- has been assessed using nucleus-independent chemical shift (NICS), quantum theory of atoms in molecules (QTAIM), and natural bond orbital (NBO) methods.

  17. Synthesis of silver nanoparticles confined in hierarchically porous monolithic silica: a new function in aromatic hydrocarbon separations. (United States)

    Zhu, Yang; Morisato, Kei; Li, Wenyan; Kanamori, Kazuyoshi; Nakanishi, Kazuki


    Silver nanoparticles (Ag NPs) have been homogeneously introduced into hierarchically porous monolithic silica columns with well-defined macropores and SBA-15-type hexagonally ordered mesopores by using ethanol as the mild reductant. Within the cylindrical silica mesopores treated with aminopropyl groups as the host, monocrystalline Ag NPs and nanorods are obtained after being treated in silver nitrate/ethanol solution at room temperature for different durations of reducing time. The loading of Ag NPs in the monolith can be increased to 33 wt % by the repetitive treatment, which also led to the formation of polycrystalline Ag nanorods in the mesopores. Although the bare silica column cannot separate aromatic hydrocarbons, good separation of those molecules by noncharged Ag NPs confined in the porous structure of the monolith has been for the first time demonstrated with the Ag NP-embedded silica column. The NP-embedded monolithic silica would be a powerful separation tool for hydrocarbons with different number, position, and configuration of unsaturated bonds.

  18. Synthesis of a series of aromatic benziporphyrins and heteroanalogues via tripyrrane-like intermediates derived from resorcinol and 2-methylresorcinol. (United States)

    Lash, Timothy D; Miyake, Kae; Xu, Linlin; Ferrence, Gregory M


    Tripyrrane analogues were prepared by reacting resorcinol or 2-methylresorcinol with 2 equiv of an acetoxymethylpyrrole in the presence of p-toluenesulfonic acid and calcium chloride. Following removal of the benzyl ester protective groups, the resorcinol-derived benzitripyrrane was reacted with a pyrrole dialdehyde to give an aromatic hydroxyoxybenziporphyrin. However, furan and thiophene dialdehydes gave highly insoluble products that could not be fully characterized. The methylresorcinol-derived tripyrrane analogue reacted with pyrrole, furan, thiophene, and selenophene dialdehydes to give unstable porphyrinoids that were further oxidized with [bis(trifluoroacetoxy)iodo]benzene to give stable benziporphyrin derivatives. These oxidized benziporphyrins showed strongly diatropic properties by proton NMR spectroscopy where the differences in chemical shifts (Δδ) were >18 ppm in some cases. The selenophene-derived system was further characterized by X-ray crystallography, and these results showed that one of the pyrrole subunits in this crowded structure was tilted by 21° relative to the mean macrocyclic plane. The tripyrrolic system reacted with silver(I) acetate to give the corresponding silver(III) organometallic complex. Regioselective alkylation with methyl or ethyl iodide and potassium carbonate gave diastereomeric mixtures of N-alkyl derivatives, and the N-ethyl substitution products showed highly diastereotopic characteristics.

  19. Electronic structure of heterocyclic ring chain polymers

    NARCIS (Netherlands)

    Brocks, Geert; Tol, Arie


    The band gaps, ionization potentials and electron affinities of conjugated chain polymers comprising heterocyclic aromatic rings are studied systematically as a function of atomic substitutions with N, O and S using first principles density functional calculations.

  20. Synthesis and properties of aromatic polyethers containing poly(ethylene oxide) side chains as polymer electrolytes for lithium ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Vöge, Andrea, E-mail: [Department of Chemistry, University of Patras, 26500 Patras (Greece); Deimede, Valadoula, E-mail: [Department of Chemistry, University of Patras, 26500 Patras (Greece); Paloukis, Fotis; Neophytides, Stylianos G. [Foundation of Research and Technology – Hellas, Institute of Chemical Engineering Sciences (FORTH/ICE-HT), Patras 26504 (Greece); Kallitsis, Joannis K. [Department of Chemistry, University of Patras, 26500 Patras (Greece)


    Polymer electrolytes consisting of polar pyridine units in the backbone and poly(ethylene oxide) (PEO) side chains are designed for possible application in lithium ion batteries. In particular, aromatic polyethers bearing PEO side chains with varying length are synthesized either by copolymerization of the corresponding PEO based diols with different arylfluorides or by modification of dihydroxyl functionalized precursor polymers with poly(ethylene oxide) methyl ether tosylate. The formation of free standing films is dependent on the PEO content, polymers' composition as well as on the different monomers used. The mechanical properties study shows that the glass transition temperature can be controlled by varying the PEO content. Thermal stability is also influenced by the PEO length: the shorter the PEO side chain, the higher the stability. XRD analysis gives information about the desired amorphous character of these polymers, which is independent of the PEO content. Solid polymer electrolytes prepared by blending the PEO-based polymers with lithium salt and PEO 2000 (used as plasticizer) show ambient temperature conductivities in the range of 10{sup −6} S/cm. To further improve conductivity doping of PEO-based polymers in liquid electrolyte (1 M LiPF{sub 6} in EC/DMC 1/1) in some cases results in high conductivities in the range of 10{sup −3} S cm{sup −1} at 80 °C. - Highlights: • Polymer electrolytes bearing PEO side chains of varying lengths were designed. • DMA and TGA show that T{sub g} and T{sub d} can be controlled by varying the PEO content. • XRD confirms polymers amorphous character, independent of the PEO content. • Membranes doped in liquid electrolyte have high conductivities (10{sup −3} S cm{sup −1}, 80 °C)

  1. Highly Contorted 1,2,5-Thiadiazole-Fused Aromatics for Solution-Processed Field-Effect Transistors: Synthesis and Properties. (United States)

    Shi, Xin; Liu, Shuli; Liu, Chunming; Hu, Yueming; Shi, Saihua; Fu, Nina; Zhao, Baomin; Wang, Zhaohui; Huang, Wei


    A straightforward strategy has been used to construct 1,2,5-thiadiazole-fused 12-ring π systems through twofold Stille coupling and subsequent cyclodehydrogenation by utilizing the building blocks of naphthodithiophene and 5,6-substituted benzo[b]-2,1,3-thiadidazole. Molecules 1 a and 1 b, which exhibit highly contorted π surfaces, show a butterfly-shaped conformation according to DFT calculations. Within the molecules, a plane-to-plane angle of 44.8° was found. UV/Vis absorption, thermogravimetric analysis, differential scanning calorimetry, and cyclic voltammetry (CV) were used to study their physical properties. Strong intermolecular interactions of the nonplanar molecules were also observed by concentration-dependent (1) H NMR spectroscopy measurements and thin-film XRD characterization. The low-lying LUMO and high-lying HOMO levels of the molecules are -3.73 and -5.48 eV, respectively, as estimated from CV measurements; this indicates their potential as semiconducting materials for solution-processed organic field-effect transistors (OFETS). A field-effect hole mobility of up to 0.035 cm(2)  V(-1)  s(-1) , a threshold voltage of 6.98 V, and a current on/off ratio of 8.65×10(5) in air for 1 a have been demonstrated with the top-contact bottom-gate field-effect transistor device structures; this represents an important step toward the solution-processed OFET application of contorted aromatics.

  2. Synthesis of enantiomerically pure N-(S)-alpha-methylbenzyl-Beta-aminoalcohols by regio-and steroselective ring opening of epoxides

    Energy Technology Data Exchange (ETDEWEB)

    Anaya de Parrodi, C. [Departamento de Quimica y Biologia. Universidad de las Americas-Puebla, Puebla (Mexico); Juaristi, E. [Departamento de Quimica Centro de Investigaciones y Estudios Avanzados. Instituto Politecnico Nacional, Mexico (Mexico)


    A high yield, stereoselective ring opening of symmetrically substituted epoxides with (S)-alpha-methylbenzylamine to produce enantiomerically pure N-(S)-alpha-methylbenzyl-Beta-aminoalcohols is described. In addition, the regio selective ring opening of (R)-styrene oxide with (S)-alpha -methylbenzylamine and enantiomerically pure secondary amines. (S)-N-benzyl-, (S)-N-isopropyl-. (S)-N-[(2-biphenyl) methyl]-alpha-methylbenzylamine is described. (Author) 16 refs.

  3. Doxorubicin-loaded aromatic imine-contained amphiphilic branched star polymer micelles: synthesis, self-assembly, and drug delivery

    Directory of Open Access Journals (Sweden)

    Qiu L


    Full Text Available Liang Qiu, Chun-Yan Hong, Cai-Yuan Pan Chinese Academy of Sciences Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui, People’s Republic of China Abstract: Redox- and pH-sensitive branched star polymers (BSPs, BP(DMAEMA-co-MAEBA-co-DTDMA(PMAIGPns, have been successively prepared by two steps of reversible addition–fragmentation chain transfer (RAFT polymerization. The first step is RAFT polymerization of 2-(N,N-dimethylaminoethylmethacrylate (DMAEMA and p-(methacryloxyethoxybenzaldehyde (MAEBA in the presence of divinyl monomer, 2,2'-dithiodiethoxyl dimethacrylate (DTDMA. The resultant branched polymers were used as a macro-RAFT agent in the subsequent RAFT polymerization. After hydrolysis of the BSPs to form BP(DMAEMA-co-MAEBA-co-DTDMA(PMAGPns (BSP-H, the anticancer drug doxorubicin (DOX was covalently linked to branched polymer chains by reaction of primary amine of DOX and aldehyde groups in the polymer chains. Their compositions, structures, molecular weights, and molecular weight distributions were respectively characterized by nuclear magnetic resonance spectra and gel permeation chromatography measurements. The DOX-loaded micelles were fabricated by self-assembly of DOX-containing BSPs in water, which were characterized by transmission electron microscopy and dynamic light scattering. Aromatic imine linkage is stable in neutral water, but is acid-labile; controlled release of DOX from the BSP-H-DOX micelles was realized at pH values of 5 and 6, and at higher acidic solution, fast release of DOX was observed. In vitro cytotoxicity experiment results revealed low cytotoxicity of the BSPs and release of DOX from micelles in HepG2 and HeLa cells. Confocal laser fluorescence microscopy observations showed that DOX-loaded micelles have specific interaction with HepG2 cells. Thus, this type of BSP micelle is an efficient drug delivery system

  4. General synthesis of substituted 1,2-dihydropyridines. (United States)

    Tejedor, David; Cotos, Leandro; Méndez-Abt, Gabriela; García-Tellado, Fernando


    A general and practical metal-free protocol for the synthesis of 1,2-dihydropyridines with wide structural/functional diversity at the ring and featuring mono, double, or spiro substitution at the sp(3) position is described. The protocol entails a microwave-assisted domino reaction of a propargyl vinyl ether (secondary or tertiary) and a primary amine (aliphatic or aromatic) in toluene or methanol.

  5. Synthesis and biological evaluation of biaryl analogs of antitubulin compounds

    Directory of Open Access Journals (Sweden)

    Camila Santos Suniga Tozatti


    Full Text Available This paper reports the synthesis of methanones and esters bearing different substitution patterns as spacer groups between aromatic rings. This series of compounds can be considered phenstatin analogs. Two of the newly synthesized compounds, 5a and 5c, strongly inhibited tubulin polymerization and the binding of [³H] colchicine to tubulin, suggesting that, akin to phenstatin and combretastatin A-4, they can bind to tubulin at the colchicine site.

  6. Synthesis and biological evaluation of biaryl analogs of antitubulin compounds

    Energy Technology Data Exchange (ETDEWEB)

    Tozatti, Camila Santos Suniga; Khodyuk, Rejane Goncalves Diniz; Silva, Adriano Olimpio da; Santos, Edson dos Anjos dos; Amaral, Marcos Serrou do; Lima, Denis Pires de, E-mail: [Centro de Ciencias Exatas e Tecnologia, Universidade Federal de Mato Grosso do Sul, Campo Grande, MS (Brazil); Hamel, Ernest [Screening Technologies Branch, Division of Cancer Treatment and Diagnosis, National Cancer Institute at Frederick, MD (United States)


    This paper reports the synthesis of methanones and esters bearing different substitution patterns as spacer groups between aromatic rings. This series of compounds can be considered phenstatin analogs. Two of the newly synthesized compounds, 5a and 5c, strongly inhibited tubulin polymerization and the binding of [{sup 3}H] colchicine to tubulin, suggesting that, akin to phenstatin and combretastatin A-4, they can bind to tubulin at the colchicine site. (author)

  7. Multicenter bond index analysis of influence of metal cations on the aromaticity of aromatic amino acids: Phenylalanine and tyrosine (United States)

    Pakiari, A. H.; Farrokhnia, M.; Azami, S. M.


    In order to provide insight into the influence of metal cations on the aromaticity of amino acids, evaluation of six-center delocalization indices is accomplished in the context of quantum theory of atoms in molecules (QTAIM). Aromaticity of two amino acids, phenylalanine and tyrosine, is investigated as typical amino acids containing aromatic ring in their isolated state and complexed by some metal cations. The results showed that the metal cations affect the most important three connectivities differently. Also, it is shown that the existence of metal cations can increase two-center delocalization in certain parts of the aromatic rings.

  8. Metátese de olefinas aplicada ao fechamento de anéis: uma ferramenta poderosa para a síntese de macrociclos naturais Ring-closing olefin metathesis: a powerful tool for the synthesis of natural macrocycles

    Directory of Open Access Journals (Sweden)

    Anderson Rouge dos Santos


    Full Text Available For a quarter of a century, metathesis has become indispensable for the synthesis of natural and non-natural products, particularly of biologically active compounds. This review illustrates through a maximum of appropriate examples the power and the versatility of the metathesis ring-closure (RCM reaction as a key ring-closure methodology for the synthesis of natural macrocycles. Its high functional group compatibility as well as the possibility of further transformations makes this reaction a powerful tool in the cases where the structural framework and function requirements are difficult to meet.

  9. Luminescent Di- and Trinuclear Boron Complexes Based on Aromatic Iminopyrrolyl Spacer Ligands: Synthesis, Characterization, and Application in OLEDs. (United States)

    Suresh, D; Gomes, Clara S B; Lopes, Patrícia S; Figueira, Cláudia A; Ferreira, Bruno; Gomes, Pedro T; Di Paolo, Roberto E; Maçanita, António L; Duarte, M Teresa; Charas, Ana; Morgado, Jorge; Vila-Viçosa, Diogo; Calhorda, Maria José


    New bis- and tris(iminopyrrole)-functionalized linear (1,2-(HNC4 H3 -C(H)N)2 -C6 H4 (2), 1,3-(HNC4 H3 -C(H)N)2 -C6 H4 (3), 1,4-(HNC4 H3 -C(H)N)2 -C6 H4 (4), 4,4'-(HNC4 H3 -C(H)N)2 -(C6 H4 -C6 H4 ) (5), 1,5-(HNC4 H3 C-(H)N)2 -C10 H6 (6), 2,6-(HNC4 H3 C-(H)N)2 -C10 H6 (7), 2,6-(HNC4 H3 C-(H)N)2 -C14 H8 (8)) and star-shaped (1,3,5-(HNC4 H3 -C(H)N-1,4-C6 H4 )3 -C6 H3 (9)) π-conjugated molecules were synthesized by the condensation reactions of 2-formylpyrrole (1) with several aromatic di- and triamines. The corresponding linear diboron chelate complexes (Ph2 B[1,3-bis(iminopyrrolyl)-phenyl]BPh2 (10), Ph2 B[1,4-bis(iminopyrrolyl)-phenyl]BPh2 (11), Ph2 B[4,4'-bis(iminopyrrolyl)-biphenyl]BPh2 (12), Ph2 B[1,5-bis(iminopyrrolyl)-naphthyl]BPh2 (13), Ph2 B[2,6-bis(iminopyrrolyl)-naphthyl]BPh2 (14), Ph2 B[2,6-bis(iminopyrrolyl)-anthracenyl]BPh2 (15)) and the star-shaped triboron complex ([4',4'',4'''-tris(iminopyrrolyl)-1,3,5-triphenylbenzene](BPh2 )3 (16)) were obtained in moderate to good yields, by the treatment of 3-9 with B(C6 H5 )3 . The ligand precursors are non-emissive, whereas most of their boron complexes are highly fluorescent; their emission color depends on the π-conjugation length. The photophysical properties of the luminescent polyboron compounds were measured, showing good solution fluorescence quantum yields ranging from 0.15 to 0.69. DFT and time-dependent DFT calculations confirmed that molecules 10 and 16 are blue emitters, because only one of the iminopyrrolyl groups becomes planar in the singlet excited state, whereas the second (and third) keeps the same geometry. Compound 13, in which planarity is not achieved in any of the groups, is poorly emissive. In the other examples (11, 12, 14, and 15), the LUMO is stabilized, narrowing the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO), and the two iminopyrrolyl groups become planar, extending the size of the π-system, to

  10. Aromatic graphene (United States)

    Das, D. K.; Sahoo, S.


    In recent years graphene attracts the scientific and engineering communities due to its outstanding electronic, thermal, mechanical and optical properties and many potential applications. Recently, Popov et al. [1] have studied the properties of graphene and proved that it is aromatic but without fragrance. In this paper, we present a theory to prepare graphene with fragrance. This can be used as scented pencils, perfumes, room and car fresheners, cosmetics and many other useful household substances.

  11. From small aromatic molecules to functional nanostructured carbon by pulsed laser-induced photochemical stitching

    Directory of Open Access Journals (Sweden)

    R. R. Gokhale


    Full Text Available A novel route employing UV laser pulses (KrF Excimer, 248 nm to cleave small aromatic molecules and stitch the generated free radicals into functional nanostructured forms of carbon is introduced. The process differs distinctly from any strategies wherein the aromatic rings are broken in the primary process. It is demonstrated that this pulsed laser-induced photochemical stitching (PLPS process when applied to routine laboratory solvents (or toxic chemical wastes when discarded Chlorobenzene and o-Dichlorobenzene yields Carbon Nanospheres (CNSs comprising of graphene-like sheets assembled in onion-like configurations. This room temperature process implemented under normal laboratory conditions is versatile and clearly applicable to the whole family of haloaromatic compounds without and with additions of precursors or other nanomaterials. We further bring out its applicability for synthesis of metal-oxide based carbon nanocomposites.

  12. Dehalogenation of aromatics by nucleophilic aromatic substitution. (United States)

    Sadowsky, Daniel; McNeill, Kristopher; Cramer, Christopher J


    Nucleophilic aromatic substitution has been implicated as a mechanism for both the biotic and abiotic hydrodehalogenation of aromatics. Two mechanisms for the aqueous dehalogenation of aromatics involving nucleophilic aromatic substitution with hydride as a nucleophile are investigated using a validated density functional and continuum solvation protocol. For chlorinated and brominated aromatics, nucleophilic addition ortho to carbon-halogen bonds via an anionic intermediate is predicted to be the preferred mechanism in the majority of cases, while concerted substitution is predicted to be preferred for most fluorinated aromatics. Nucleophilic aromatic substitution reactions with the hydroxide and hydrosulfide anions as nucleophiles are also investigated and compared.

  13. Synthesis and luminescent properties of novel lanthanide(III) beta-diketone complexes with nitrogen p,p'-disubstituted aromatic ligands. (United States)

    Bellusci, Anna; Barberio, Giovanna; Crispini, Alessandra; Ghedini, Mauro; La Deda, Massimo; Pucci, Daniela


    Tris-beta-diketonate lanthanide(III) complexes (Ln = Eu, Er, Yb, Tb), of general formula [Ln(acac)3 L(m)], with chelating ligands such as 4,7-disubstituted-1,10-phenanthrolines and 4,4'-disubstituted-2,2'-bipyridines, have been synthesized and fully characterized. The inductive effects of the para-substituents on the aromatic N-donor ligands have been investigated both in the solid and in the solution states. Single-crystal X-ray structures have been determined for the diethyl 1,10-phenanthroline-4,7-dicarboxylate europium and 4,4'-dimethoxy-2,2'-bipyridine erbium derivatives, revealing a distorted square antiprismatic geometry around the lanthanide atom in both cases. The influence exerted by the p,p'-substituents with respect to the nitrogen coordinating atoms on the Ln-N bond distances is discussed comparing the geometrical parameters with those found for the crystal structures containing the fragments [Ln(III)(phen)] and [Ln(III)(bipy)] obtained from the Cambridge Structural Database. The influence exerted by the electron-attracting groups on the coordination ability of the ligands, that in some cases becomes lack of coordination of the lanthanide ions, has been also detected in solution where the loss of the ligand has been followed by UV-vis spectroscopy. Moreover, the use of relatively long alkoxy chains as substituents on the 1,10-phenanthroline ligand led to the formation of a promesogenic lanthanide complex, whose thermal behavior is encouraging for the synthesis of new lanthanide liquid-crystalline species.

  14. Enzymatic synthesis of 2,5-furandicarboxylic acid-based semi-aromatic polyamides : enzymatic polymerization kinetics, effect of diamine chain length and thermal properties

    NARCIS (Netherlands)

    Jiang, Yi; Maniar, Dina; Woortman, Albert J. J.; Loos, Katja


    2,5-Furandicarboxylic acid (FDCA)-based semi-aromatic polyamides are novel biobased alternatives to petrol-based semi-aromatic polyamides (polyphthalamides), that have a broad commercial interest as engineering thermoplastics and high performance materials. In this study, a series of FDCA-based semi

  15. Synthesis and antiproliferative activity of the ring system [1,2]oxazolo[4,5-g]indole. (United States)

    Barraja, Paola; Caracausi, Libero; Diana, Patrizia; Spanò, Virginia; Montalbano, Alessandra; Carbone, Anna; Parrino, Barbara; Cirrincione, Girolamo


    Brand new ring: A series of 27 derivatives of the new ring system [1,2]oxazolo[4,5-g]indole were conveniently prepared and tested at the NCI for antiproliferative studies. Several of them showed good inhibitory activity toward all tested cell lines, reaching GI50 values generally at the micromolar and sub-micromolar levels and in some cases at nanomolar concentrations. The mean GI50 values, calculated on the full panel, were in the range 0.25-7.08 μM.

  16. Synthesis, spectral characterization and antihaemostatic activity of 1,2,4-triazoles incorporating 1,2,4-triazine rings

    Indian Academy of Sciences (India)

    Ravindra R Kamble; Belgur S Sudha


    A simple and high yielding method for the integration of a 1,2,4-triazole ring with 1,2,4-triazine- 5-one (4a-j) has been developed starting from 3-arylsydnones (1a-d). The structures were proved by their spectral data and screened for antihaemostatic activity.

  17. Synthesis and Luminescent Properties of Two New Triphenylamine-based Compounds with Heterocyclic Ring as Conjugation Bridge

    Institute of Scientific and Technical Information of China (English)

    LI,Qian-Qian; DI,Chong-An; YU,Gui; LIU,Yun-Qi; LI,Zhen; QIN,Jin-Gui


    Two new "D-π-D" type triphenylamine-based compounds with a heterocyclic ring,furan or thiophene,as a conjugation bridge were synthesized through a normal Wittig reaction which exhibited good thermal stability and strong luminescence.The preliminary light-emitting diode results indicate that they are promising candidates for the practical application.

  18. Synthesis of a novel uridine analogue and its use in attempts to form new cyclonucleosides using ring-closing metathesis

    Institute of Scientific and Technical Information of China (English)

    MONDON; Martine; LEN; Christophe


    One novel nucleoside analogue having a hex-5-enyl group and an allyl group in the 5’-C and 3-N position was synthesized regioand diastereoselectively from D-glucose in twelve steps.In order to reach a particular conformation of nucleosides the nucleoside formation of restricted cyclonucleoside analogues was studied via Ring-Closing Metathesis.

  19. Synthesis of thermally stable extra-large pore crystalline materials: a uranyl germanate with 12-ring channels. (United States)

    Lin, Chia-Hui; Chiang, Ray-Kuang; Lii, Kwang-Hwa


    A thermally stable extra-large pore uranyl germanate is synthesized under high-temperature, high-pressure hydrothermal conditions at 585 degrees C and 150 MPa. The structure contains U(6+)O(6) tetragonal bipyramids which are interconnected by digermanate groups to form a 3D framework with 12-ring pore openings.

  20. Assessing Uncertainty of Interspecies Correlation Estimation Models for Aromatic Compounds (United States)

    We developed Interspecies Correlation Estimation (ICE) models for aromatic compounds containing 1 to 4 benzene rings to assess uncertainty in toxicity extrapolation in two data compilation approaches. ICE models are mathematical relationships between surrogate and predicted test ...

  1. Ring blowers. Ring blower

    Energy Technology Data Exchange (ETDEWEB)

    Nakahara, Y.; Okamura, T.; Takahashi, M. (Fuji Electric Co. Ltd., Tokyo (Japan))


    Features, structures and several products of ring blowers were outlined. The ring blower is featured by its medium characteristics because it is higher in air pressure than a turboblower and larger in airflow than a vane blower, and it is applicable flexibly to not only air blasting but various industrial fields such as suction transfer. As several products corresponding to various fields, the followings were outlined: the low noise type with optimum shapes of inlet, outlet and casing cover for reducing noises by 10 dB or more, the heat resistant, water-tight and explosion-proof types suitable for severe environmental conditions, the multi-voltage type for every country served at different voltages, the high air pressure type with two pressure rise stages, and the large airflow type with a wide impeller. In addition, as special use products, the glass fiber reinforced unsatulated polyester ring blower for respiration apparatus, and the variable speed blushless DC motor-driven one for medical beds were outlined. 2 refs., 9 figs., 1 tab.

  2. Synthesis and Resolution of Ring-substituted phenylalanines%苯环取代苯丙氨酸的合成及拆分

    Institute of Scientific and Technical Information of China (English)

    梁远军; 刘克良; 于文胜; 赵玉芬


    Seven racemic aromatic ring modified phenylalanines wer e sy nthesized using aniline derivatives as raw materials. The amino acids were resol ved with α--chymotrypsin or subtilisin. D-and L-amino acids were separ ated from each other. The chemical structures of the amino acids were characteri zed by IR, 1 HNMR, EA and optical rotation. The procedure mentioned here coul d be scaled up for producing the amino acids.%以苯胺类化合物为起始原料,经重氮化、丙烯酸加成、氨解 等反应合成了7种消旋苯环取代苯丙氨酸类氨基酸,并采用α-糜蛋白酶或枯草杆菌蛋白酶 对所有氨基酸进行了拆分,其结构分别通过红外光谱、核磁共振、元素分析、熔点、旋光等 分析得到确证。该法可以较大规模合成此类氨基酸。

  3. Regioselective ring opening of epoxides using NH4SCN/silica sulfuric acid: An efficient approach for the synthesis of β-hydroxy thiocyanate under solvent-free conditions

    Institute of Scientific and Technical Information of China (English)

    Ali R. Kiasat; Maryam Zayadi; Mehdi Fallah Mehrjardi


    Silica sulfuric acid was developed as a stable and efficient heterogeneous catalyst in organic synthesis. This solid acid catalyzed the regioselective ring opening of epoxides by thiocyanate anion to give thiocyanohydrins as key intermediates in agricultural and pharmaceutical chemistry in high yields under solvent-free conditions.

  4. All-optically tunable waveform synthesis by a silicon nanowaveguide ring resonator coupled with a photonic-crystal fiber frequency shifter

    KAUST Repository

    Savvin, Aleksandr D.


    A silicon nanowaveguide ring resonator is combined with a photonic-crystal fiber (PCF) frequency shifter to demonstrate an all-optically tunable synthesis of ultrashort pulse trains, modulated by ultrafast photoinduced free-carrier generation in the silicon resonator. Pump-probe measurements performed with a 50-fs, 625-nm second-harmonic output of a Cr:forsterite laser, used as a carrier-injecting pump, and a 1.50-1.56-μm frequency-tunable 100-fs soliton output of a photonic-crystal fiber, serving as a probe, resolve tunable ultrafast oscillatory features in the silicon nanowaveguide resonator response. © 2010 Elsevier B.V. All rights reserved.

  5. Reproducible Synthesis and High Porosity of mer-Zn(Im)2 (ZIF-10): Exploitation of an Apparent Double-Eight Ring Template. (United States)

    Ramirez, Joseph R; Yang, Haiyang; Kane, Christopher M; Ley, Amanda N; Holman, K Travis


    Reproducible synthesis of the elusive merlinoite (mer) topology of zinc imidazolate (mer-Zn(Im)2, or ZIF-10) has been achieved by employing a simple macrocyclic solute-MeMeCH2-as a kinetic template. The corresponding phase-pure material, mer-MeMeCH2@Zn16(Im)32, is confirmed to be porous and exhibits one of the highest experimental surface areas (1893 m(2)/g, BET) yet reported for any ZIF. The X-ray single crystal structure of mer-MeMeCH2@Zn16(Im)32·xsolvent reveals the role of the macrocyle as an 8-fold hydrogen bond acceptor in templating the requisite double-eight rings (d8r) of the mer framework.

  6. Straightforward synthesis of a novel ring-fused pyrazole-lactam and in vitro cytotoxic activity on cancer cell lines. (United States)

    Bertuzzi, G; Locatelli, E; Colecchia, D; Calandro, P; Bonini, B F; Chandanshive, J Z; Mazzanti, A; Zani, P; Chiariello, M; Comes Franchini, M


    In this paper a straightforward synthesis of a novel pyrazole derivative is reported. Prominent feature of this synthetic process is a 1,3-Dipolar Cycloaddition of a suitable nitrile imine with an activated α,β-unsaturated lactam to afford directly and regioselectively the corresponding ring-fused pyrazole. Having obtained the central core of the synthetic target, a double stepwise functionalization with a "side chain" characterized by a terminal cyclic aliphatic amine was carried out. This molecular structure was designed to interact strongly with typical biological residues, and indeed it showed potent anticancer capability: in vitro cytotoxicity test on five different cancer cell lines showed interesting IC50 values in the range of 15-60 μM for exposure time of 24-72 h, thus resulting comparable with commercially available and nowadays therapeutically exploited anticancer compounds, such as 5-FU and NVP-BEZ235.

  7. Epoxy Coenzyme A Thioester pathways for degradation of aromatic compounds. (United States)

    Ismail, Wael; Gescher, Johannes


    Aromatic compounds (biogenic and anthropogenic) are abundant in the biosphere. Some of them are well-known environmental pollutants. Although the aromatic nucleus is relatively recalcitrant, microorganisms have developed various catabolic routes that enable complete biodegradation of aromatic compounds. The adopted degradation pathways depend on the availability of oxygen. Under oxic conditions, microorganisms utilize oxygen as a cosubstrate to activate and cleave the aromatic ring. In contrast, under anoxic conditions, the aromatic compounds are transformed to coenzyme A (CoA) thioesters followed by energy-consuming reduction of the ring. Eventually, the dearomatized ring is opened via a hydrolytic mechanism. Recently, novel catabolic pathways for the aerobic degradation of aromatic compounds were elucidated that differ significantly from the established catabolic routes. The new pathways were investigated in detail for the aerobic bacterial degradation of benzoate and phenylacetate. In both cases, the pathway is initiated by transforming the substrate to a CoA thioester and all the intermediates are bound by CoA. The subsequent reactions involve epoxidation of the aromatic ring followed by hydrolytic ring cleavage. Here we discuss the novel pathways, with a particular focus on their unique features and occurrence as well as ecological significance.

  8. Synthesis and Biological Evaluation of Novel Benzimidazole Derivatives Bearing a Heterocyclic Ring at 4/5 Position

    Energy Technology Data Exchange (ETDEWEB)

    Wubulikasimu, Reyila; Yang, Yanbing; Xue, Fei; Luo, Xianjin; Shao, Dongping [Shanghai Jiaotong Univ., Shanghai (China); Li, Yuhuan; Gao, Rongmei [Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing (China); Ye, Weidong [Zhejiang Medicine Co. Ltd., Zhejiang (China)


    A series of novel benzimidazole derivatives bearing a heterocyclic ring as oxadiazole (21-32), thiadiazole (33-34), triazole (35-36) were synthesized and evaluated for their activities against Coxsackie virus B3 and B6 in Vero cells. Compounds 21-26, 31-36 with moieties of 2'-pyridyl, 3'-pyridyl and 4'-pyridyl at the 2-position and oxadiazoles, thiadiazole, or triazole substituent at the 4- or 5-position generally displayed activities against CVB3 and CVB6. Especially compound 24 (IC{sub 50} = 1.08 μg/mL, SI = 61.7 against CVB3) was the promising candidate as lead compound for anti-enteroviral drug. It was observed in the incorporation of heterocyclic rings in benzimidazole at the 5-position could enhance their biological activities.

  9. cis-Diastereoselective synthesis of chroman-fused tetralins as B-ring-modified analogues of brazilin

    Directory of Open Access Journals (Sweden)

    Dimpee Gogoi


    Full Text Available We have synthesized a series of cis-6a,7,8,12b-tetrahydro-6H-naphtho[2,1-c]chromen-6a-ols as B-ring-modified analogues of (±-brazilin. A completely regio- and cis-diastereoselective intramolecular Friedel–Crafts epoxy–arene cyclization of 1-tetralone-derived glycidyl ethers catalyzed by Brønsted acids was used as the key step. Our worries concerning the formation of cis–trans product mixtures and their probable conversion to naphthopyran derivatives via dehydration of the tertiary hydroxy group were laid to rest. Additionally, the angular hydroxy group of one of the synthesized products has been reductively removed by a diastereoselective method which should be useful in future for preparing libraries of chroman-fused tetralins with trans-stereochemistry at the ring junction.

  10. cis-Diastereoselective synthesis of chroman-fused tetralins as B-ring-modified analogues of brazilin. (United States)

    Gogoi, Dimpee; Devi, Runjun; Pahari, Pallab; Sarma, Bipul; Das, Sajal Kumar


    We have synthesized a series of cis-6a,7,8,12b-tetrahydro-6H-naphtho[2,1-c]chromen-6a-ols as B-ring-modified analogues of (±)-brazilin. A completely regio- and cis-diastereoselective intramolecular Friedel-Crafts epoxy-arene cyclization of 1-tetralone-derived glycidyl ethers catalyzed by Brønsted acids was used as the key step. Our worries concerning the formation of cis-trans product mixtures and their probable conversion to naphthopyran derivatives via dehydration of the tertiary hydroxy group were laid to rest. Additionally, the angular hydroxy group of one of the synthesized products has been reductively removed by a diastereoselective method which should be useful in future for preparing libraries of chroman-fused tetralins with trans-stereochemistry at the ring junction.

  11. Inhibitory effects of polycyclic aromatic hydrocarbons (PAHs) on photosynthetic performance are not related to their aromaticity. (United States)

    Jajoo, Anjana; Mekala, Nageswara Rao; Tomar, Rupal Singh; Grieco, Michele; Tikkanen, Mikko; Aro, Eva-Mari


    Polycyclic aromatic hydrocarbons (PAHs) are very toxic and highly persistent environmental pollutants which accumulate in soil and affect growth of the plants adversely. This study aims to investigate inhibitory effects of 3 major PAH particularly on photosynthetic processes in Arabidopsis thaliana grown in soil treated with PAH. The 3 PAH chosen differ from each other in aromaticity (number of rings) comprising their structure (2 rings: naphthalene, 3 rings: anthracene and 4 rings: pyrene). Several growth parameters and Chlorophyll a fluorescence was monitored in PAH treated plants. BN-PAGe analysis was done in order to get information about change in the protein conformation. PAH treatment led to increased value of Fo which collaborated with increase in the amount of free LHC as seen through BN-Page analysis. Thus PAH were found to inhibit PS II photochemistry and caused distinct change in pigment composition. However the results led us to infer that 3-ring anthracence is more inhibitory as compared to 2-ring naphthalene and 4-ring pyrene. This indicates that aromaticity of PAH is unrelated to their response on photosynthetic processes.

  12. Application of four-membered ring chalcogenation reagents to the synthesis of new phosphorus-chalcogen heterocycles


    Hua, Guoxiong; Cordes, David Bradford; Slawin, Alexandra Martha Zoya; Woollins, J. Derek


    The authors are grateful to the University of St Andrews for financial support. The reaction of four-membered ring chalcogenation reagents such as Lawesson’s reagent, 2,4-diferrocenyl-1,3,2,4-diathiadiphosphetane 2,4-disulfide (the ferrocene analogy of Lawesson’s reagent) and Woollins’ reagent with alkyl- or aryl-dithiols in refluxing toluene gave a series of five- to seven-membered organo-phosphorus-chalcogen heterocycles in 24% to 87% yields. Five representative X-ray structures confirm ...

  13. Synthesis of hyperbranched copolymers by combining enzymatic ring-opening polymerization and A TRP from a novel bifunctional initiator

    Institute of Scientific and Technical Information of China (English)

    Al Peng; CHEN Liang; HU Dehua; CHEN Yanhua; LI Dongshuang; ZHANG Bao; SHA Ke; WANG Jingyuan


    The hyperbranched aliphatic polyester P(ε-CL) was synthesized by means of Novozyme435-catalyzed ring-opening polymerization (ROP) of BHB (2, 2-bis(hydroxymethyl) butyric acid). The chains ended with hydroxyl of P(ε-CL) were modified by the esterification of α-bromopropionyl bromide to obtain hyperbranched difunctional macroinitiator, which was used in the ATRP of St. CuCI/HMTETA was used as the catalyst system in the reaction of ATRP to acquire the hyperbranched copolymers polystyrene-blockpoly(2,2-bis(hydroxymethyl) butyric acid). The copolymer was confirmed by NMR and GPC.

  14. Vortex rings

    Energy Technology Data Exchange (ETDEWEB)

    Akhmetov, D.G. [Lavrentiev Institute of Hydrodynamics, Novosibirsk (Russian Federation)


    This book presents a comprehensive coverage of the wide field of vortex rings. The book presents the results of systematic experimental investigations, theoretical foundation, as well as the practical applications of vortex rings, such as the extinction of fires at gushing gas and oil wells. All the basic properties of vortex rings as well as their hydrodynamic structures are presented. Special attention is paid to the formation and motion of turbulent vortex rings. (orig.)

  15. Design, Synthesis, EPR-Studies and Conformational Bias of Novel Spin-Labeled DCC-Analogues for the Highly Regioselective Labeling of Aliphatic and Aromatic Carboxylic Acids. (United States)

    Gölz, Jan Philipp; NejatyJahromy, Yaser; Bauer, Mirko; Muhammad, Ashraf; Schnakenburg, Gregor; Grimme, Stefan; Schiemann, Olav; Menche, Dirk


    Novel types of spin-labeled N,N'-dicyclohexylcarbodiimides (DCC) are reported that bear a 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) residue on one side and different aromatic and aliphatic cyclohexyl analogues on the other side of the diimide core. These readily available novel reagents add efficiently to aliphatic and aromatic carboxylic acids, forming two possible spin-labeled amide derivatives with different radical distances of the resulting amide. The addition of aromatic DCC analogues proceeds with excellent selectivity, giving amides where the carboxylic acid is exclusively connected to the aromatic residue, while little or no selectivity was observed for the aliphatic congeners. The usefulness of these adducts in structural studies was demonstrated by EPR (electron paramagnetic resonance) measurements of biradical adducts of biphenyl-4,4'-dicarboxylic acids. These analyses also reveal high degrees of conformational bias for aromatic DCC derivatives, which further underlines the powerfulness of these novel reagents. This observation was further corroborated by quantum chemical calculations, giving a detailed understanding of the structural dynamics, while detailed information on the solid state structure of all novel reagents was obtained by X-ray structure analyses.

  16. Heterocycles 38. Biocatalytic Synthesis of New Heterocyclic Mannich Bases and Derivatives

    Directory of Open Access Journals (Sweden)

    Denisa Leonte


    Full Text Available This paper describes the biocatalytic synthesis of new Mannich bases containing various heterocyclic rings (thiazole, furane, thiophene, pyridine by applying the lipase catalyzed trimolecular condensation of the corresponding heterocyclic aldehydes with acetone and primary aromatic amines, in mild and eco-friendly reaction conditions. The obtained Mannich bases were acylated to their corresponding N-acetyl derivatives. All compounds were characterized by 1H-NMR, 13C-NMR and MS spectrometry.

  17. Lewis acid promoted dual bond formation: facile synthesis of dihydrocoumarins and spiro-tetracyclic dihydrocoumarins. (United States)

    Niharika, Pedireddi; Ramulu, Bokka Venkat; Satyanarayana, Gedu


    Lewis acid (FeCl3) mediated dual bond (C-C and C-O) formation for synthesis of 3,4-dihydrocoumarins is presented. This method has successfully delivered a number of dihydrocoumarins containing dense functionalities on the aromatic ring. Significantly, the present method enabled achieving dihydrocoumarins with tertiary as well as quaternary carbon atoms at the benzylic position. Gratifyingly, the novel spiro-tetracyclic lactones have also been dextrously prepared using this process.

  18. One-Pot Synthesis of Novel 2,3-Dihydro-1H-indazoles

    Directory of Open Access Journals (Sweden)

    Antonio J. Lepore


    Full Text Available A copper(I-mediated one-pot synthesis of 2,3-dihydro-1H-indazole heterocycles has been developed. This synthetic route provides the desired indazoles in moderate to good yields (55%–72% which are substantially better than those achievable with an alternative two-step reaction sequence. The reaction is tolerant of functionality on the aromatic ring.

  19. Nucleophilic fluorination of aromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Satyamurthy, Nagichettiar; Barrio, Jorge R


    Iodylbenzene derivatives substituted with electron donating as well as electron withdrawing groups on the aromatic ring are used as precursors in aromatic nucleophilic substitution reactions. The iodyl group (IO.sub.2) is regiospecifically substituted by nucleophilic fluoride to provide the corresponding fluoroaryl derivatives. No-carrier-added [F-18]fluoride ion derived from anhydrous [F-18](F/Kryptofix, [F-18]CsF or a quaternary ammonium fluoride (e.g., Me.sub.4NF, Et.sub.4NF, n-Bu.sub.4NF, (PhCH.sub.2).sub.4NF) exclusively substitutes the iodyl moiety in these derivatives and provides high specific activity F-18 labeled fluoroaryl analogs. Iodyl derivatives of a benzothiazole analog and 6-iodyl-L-dopa derivatives have been synthesized as precursors and have been used in the preparation of no-carrier-added [F-18]fluorobenzothiazole as well as 6-[F-18]fluoro-L-dopa.

  20. Ring theory

    CERN Document Server

    Rowen, Louis H


    This is an abridged edition of the author's previous two-volume work, Ring Theory, which concentrates on essential material for a general ring theory course while ommitting much of the material intended for ring theory specialists. It has been praised by reviewers:**""As a textbook for graduate students, Ring Theory joins the best....The experts will find several attractive and pleasant features in Ring Theory. The most noteworthy is the inclusion, usually in supplements and appendices, of many useful constructions which are hard to locate outside of the original sources....The audience of non

  1. Fusing porphyrins with polycyclic aromatic hydrocarbons and heterocycles for optoelectronic applications

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, Mark E.; Diev, Viacheslav; Hanson, Kenneth; Forrest, Stephen R.


    A compound that can be used as a donor material in organic photovoltaic devices comprising a non-activated porphyrin fused with one or more non-activated polycyclic aromatic rings or one or more non-activated heterocyclic rings can be obtained by a thermal fusion process. The compounds can include structures of Formula I: ##STR00001## By heating the reaction mixture of non-activated porphyrins with non-activated polycyclic aromatic rings or heterocyclic rings to a fusion temperature and holding for a predetermined time, fusion of one or more polycyclic rings or heterocyclic rings to the non-activated porphyrin core in meso,.beta. fashion is achieved resulting in hybrid structures containing a distorted porphyrin ring with annulated aromatic rings. The porphyrin core can be olygoporphyrins.

  2. Synthesis and biological evaluation with plant cells of new fosmidomycin analogues containing a benzoxazolone or oxazolopyridinone ring. (United States)

    Courtois, Martine; Mincheva, Zoia; Andreu, Françoise; Rideau, Marc; Viaud-Massuard, Marie-Claude


    Fosmidomycin, 3-(N-formyl-N-hydroxyamido) propylphosphonic acid sodium salt, is an efficient inhibitor of 1-deoxy-D-xylulose-5-phosphate (DOXP) reductoisomerase, the second enzyme of the 2C-methyl-D-erythritol-4-phosphate (MEP) pathway notably present in Plasmodium species. We have synthesized a new series of analogues of fosmidomycin, containing a benzoxazolone, benzoxazolethione or oxazolopyridinone ring. As the MEP pathway is involved in the biosynthesis of all isoprenoids, accumulation of ajmalicine in Catharanthus roseus cells was chosen as a marker of monoterpenoid indole alkaloid (MIA) production. None of the twelve studied phosphonic esters 3 and phosphonic acids 4 affected periwinkle cell growth, but some of them (3c, 3e, 3g and 3h) showed a significant inhibition of ajmalicine accumulation: 45-85% at 125 microM. Surprisingly, this effect disappeared by conversion of 3c and 3g into the corresponding acids 4c and 4g, respectively.

  3. Synthesis and Biological Activities of Novel Thiophosphoryl Oximates Containing Thiazole and 1,2,3-Triazole Rings

    Institute of Scientific and Technical Information of China (English)

    ZHU,Xiaofei; SHI,Deqing


    In order to find novel high activity and low toxicity agrochemicals,a series of novel thiophosphoryl oximates containing thiazole and 1,2,3-triazole rings 4 were synthesized by the reactions of 1-{1-[(2-chlorothiazol-5-y1)methyl]-5-methyl-1H-1,2,3-triazol-4-yl}ethanone oxime with various asymmetric thiophosphoryl chlorides.Their structures were confn'med by IR,1H NMR,31P NMR,EI-MS and elemental analyses.The target compounds existed as E-configuration,which was deduced by NMR analysis and by comparison with their pyfidyl analog de-termined by X-ray diffraction.The results of preliminary bioassay indicate that some of title compounds possess moderate insecticidal and fungicidal activities.

  4. cis-Nitenpyram Analogues Bearing Acyloxy Segments Anchored on the Tetrahydropyrimidine Ring: Synthesis,Insecticidal Activities and Molecular Docking Studies

    Institute of Scientific and Technical Information of China (English)

    SUN Chuan-wen; WU Ying; CHEN Yan-xia; NAN Shi-bin; ZHANG Wang-geng


    A series of novel cis-nitenpyram analogues bearing acyloxy segments anchored on the tetrahydropyrimidine ring was designed and synthesized.Preliminary bioassays indicate that all the nitenpyram analogues 3a—3n exhibit good insecticidal activities against Nilaparvata lugens and Aphis medicaginis at 100 mg/L,while analogue 3k affords the best activity in vitro and the lethal concentration 50(LC50) values(0.187,0.214 mg/L) are close to that of nitenpyram.The structure activity relationships(SARs) suggest that their insecticidal potency is influenced by the species of acyloxy segments.The docking results reveal that analogue 3k forms stronger hydrogen-bonding with the nAChR,which explain the structure activity relationships(SARs) observed in vitro and imply that the strategies of our designed nitenpyram analogues are feasible.

  5. (Hetero)aromatics from dienynes, enediynes and enyne-allenes. (United States)

    Raviola, Carlotta; Protti, Stefano; Ravelli, Davide; Fagnoni, Maurizio


    The construction of aromatic rings has become a key objective for organic chemists. While several strategies have been developed for the functionalization of pre-formed aromatic rings, the direct construction of an aromatic core starting from polyunsaturated systems is yet a less explored field. The potential of such reactions in the formation of aromatics increased at a regular pace in the last few years. Nowadays, there are reliable and well-established procedures to prepare polyenic derivatives, such as dienynes, enediynes, enyne-allenes and hetero-analogues. This has stimulated their use in the development of innovative cycloaromatizations. Different examples have recently emerged, suggesting large potential of this strategy in the preparation of (hetero)aromatics. Accordingly, this review highlights the recent advancements in this field and describes the different conditions exploited to trigger the process, including thermal and photochemical activation, as well as the use of transition metal catalysis and the addition of electrophiles/nucleophiles or radical species.

  6. Group 4 metal complexes of Trost's semi-crown ligand: synthesis, structural characterization and studies on the ring-opening polymerization of lactides and ε-caprolactone. (United States)

    Rajashekhar, Bijja; Roymuhury, Sagnik K; Chakraborty, Debashis; Ramkumar, Venkatachalam


    The synthesis of titanium(IV), zirconium(IV) and hafnium(IV) complexes of Trost's semi-crown ligand is described. All complexes were fully characterized by 1H and 13C NMR and mass spectroscopy. The molecular structures of the representative complexes 2, 3 and 4 were determined by single-crystal X-ray diffraction studies. The X-ray diffraction studies reveal that complexes 2, 3 and 4 crystallized in an orthorhombic crystal system. Complexes 2 and 3 have a monomeric structure in the solid state with distorted octahedral geometry around the metal center, whereas complex 4 was found to crystallize in a trimeric structure bridging with an oxygen atom, where the geometry around the titanium is distorted trigonal bipyramidal. The activities and stereoselectivities of these complexes toward the ring-opening polymerization (ROP) of lactides (L-LA and rac-LA) and ε-caprolactone (CL) have been investigated. Complexes 1–4 were found to be efficient single-component initiators for the ring-opening polymerization of cyclic esters and yielded high molecular weight polymers (Mn) with narrow molecular weight distributions (MWD).The microstructure of the resultant polylactides (PLAs) from rac-LA was determined. Complexes 2 and 3 afforded isotactic-enriched PLA (Pm = 0.78–0.71) with narrow MWD (1.07–1.04), on the other hand complexes 1 and 4 produced atactic PLA. Kinetic and post polymerization studies confirm that the polymerization proceeds through the coordination–insertion mechanism.

  7. Contorted polycyclic aromatics. (United States)

    Ball, Melissa; Zhong, Yu; Wu, Ying; Schenck, Christine; Ng, Fay; Steigerwald, Michael; Xiao, Shengxiong; Nuckolls, Colin


    CONSPECTUS: This Account describes a body of research in the design, synthesis, and assembly of molecular materials made from strained polycyclic aromatic molecules. The strain in the molecular subunits severely distorts the aromatic molecules away from planarity. We coined the term "contorted aromatics" to describe this class of molecules. Using these molecules, we demonstrate that the curved pi-surfaces are useful as subunits to make self-assembled electronic materials. We have created and continue to study two broad classes of these "contorted aromatics": discs and ribbons. The figure that accompanies this conspectus displays the three-dimensional surfaces of a selection of these "contorted aromatics". The disc-shaped contorted molecules have well-defined conformations that create concave pi-surfaces. When these disc-shaped molecules are substituted with hydrocarbon side chains, they self-assemble into columnar superstructures. Depending on the hydrocarbon substitution, they form either liquid crystalline films or macroscopic cables. In both cases, the columnar structures are photoconductive and form p-type, hole- transporting materials in field effect transistor devices. This columnar motif is robust, allowing us to form monolayers of these columns attached to the surface of dielectrics such as silicon oxide. We use ultrathin point contacts made from individual single-walled carbon nanotubes that are separated by a few nanometers to probe the electronic properties of short stacks of a few contorted discs. We find that these materials have high mobility and can sense electron-deficient aromatic molecules. The concave surfaces of these disc-shaped contorted molecules form ideal receptors for the molecular recognition and assembly with spherical molecules such as fullerenes. These interfaces resemble ball-and-socket joints, where the fullerene nests itself in the concave surface of the contorted disc. The tightness of the binding between the two partners can be

  8. Planetary Rings

    CERN Document Server

    Tiscareno, Matthew S


    Planetary rings are the only nearby astrophysical disks, and the only disks that have been investigated by spacecraft. Although there are significant differences between rings and other disks, chiefly the large planet/ring mass ratio that greatly enhances the flatness of rings (aspect ratios as small as 1e-7), understanding of disks in general can be enhanced by understanding the dynamical processes observed at close-range and in real-time in planetary rings. We review the known ring systems of the four giant planets, as well as the prospects for ring systems yet to be discovered. We then review planetary rings by type. The main rings of Saturn comprise our system's only dense broad disk and host many phenomena of general application to disks including spiral waves, gap formation, self-gravity wakes, viscous overstability and normal modes, impact clouds, and orbital evolution of embedded moons. Dense narrow rings are the primary natural laboratory for understanding shepherding and self-stability. Narrow dusty...

  9. Effects of polyunsaturated fatty acids on prostaglandin synthesis and cyclooxygenase-mediated DNA adduct formation by heterocyclic aromatic amines in human adenocarcinoma colon cells

    NARCIS (Netherlands)

    Moonen, H.J.J.; Dommels, Y.E.M.; Zwam, M.; Herwijnen, van M.H.M.; Kleinjans, J.C.S.; Alink, G.M.; Kok, de T.M.C.M.


    Dietary heterocyclic aromatic amines (HCA) and polyunsaturated fatty acids (PUFA) are both believed to play a role in colon carcinogenesis, and are both substrate for the enzyme cyclooxygenase (COX). In HCA-7 cells, highly expressing isoform COX-2, we investigated the effects of PUFA on prostaglandi

  10. Synthesis of Aromatic Hyperbranched Polyesters and Modification of Their End-groups%全芳型超支化聚酯的合成及端基改性

    Institute of Scientific and Technical Information of China (English)



    Soluble aromatic hyperbranched polyesters with controlled viscosities have been preparedby melt polycondensation of sililated 5-acetoxyisophathalic acid with sililated p-tert-butyl benzoic acidin various molar ratios. By further reaction with thionyl chloride and propargyl alcohol successively,the endgroups of the crude polyester were transferred into ethynylic groups in 78. 2% yield as calculat-ed by 1H NMR spectra.

  11. Bis-perfluoroalkylation of aromatic compounds with sodium perfluoroalkanesulfinates

    Institute of Scientific and Technical Information of China (English)

    LIU, Jin-Tao(刘金涛); LU, He-Jun(吕贺军)


    Bis-perfluoroalkylation of aromatic compounds such as dimethoxybenzenes (2,4,6), anisole (8), pyridine (10) and quinoline (13) was accomplished by reaction with excess sodium perfluoroalkanesulfinates, RFSO2Na (1), in the presence of Mn(OAc)3·2H2O under mild conditions. The reaction provides a facile method for the synthesis of bis-perfluoroalkylated aromatic compounds.

  12. C-Nucleosides Derived from Simple Aromatic Hydrocarbons. (United States)

    Chaudhuri, Narayan C; Ren, Rex X-F; Kool, Eric T


    We describe the synthesis, structure and DNA incorporation of a class of novel aromatic C-deoxynucleosides in which benzenes and larger polycyclic aromatics serve as DNA base analogs. Novel approaches have been developed for glycosidic bond formation and for epimenzation of the anomeric substitutents to β-configuration, and we describe some of the properties of such compounds in DNA.

  13. Cu-catalyzed arylation of the amino group in the indazole ring: regioselective synthesis of pyrazolo-carbazoles. (United States)

    Anil Kumar, K; Kannaboina, Prakash; Dhaked, Devendra K; Vishwakarma, Ram A; Bharatam, Prasad V; Das, Parthasarathi


    Cu(II)-catalyzed cross-coupling of various aryl boronic acids with 5 and 6-amino indazoles has resulted in (arylamino)-indazoles. These (arylamino)-indazoles have been utilized in synthesizing medicinally important pyrazole-fused carbazoles via Pd(II)-catalyzed cross-dehydrogenative coupling (CDC). This combined N-arylation/C-H arylation strategy has been successfully applied to the regioselective synthesis of polyheterocycles 3,6-dihydropyrazolo[3,4-c]carbazoles and 1,6-dihydro pyrazolo[4,3-c]carbazoles. Quantum chemical analysis has been carried out to understand the regioselectivity and to trace the potential energy surface of the entire reaction upon 5-N-aryl-indazole conversion to the corresponding carbazole.

  14. Synthesis and antitumor activity evaluation of new 2-(4-aminophenyl)benzothiazole derivatives bearing different heterocyclic rings. (United States)

    Yurttaş, Leyla; Tay, Funda; Demirayak, Şeref


    Twenty-five new N-[4-(benzothiazole-2-yl)phenyl]acetamide derivatives bearing different heterocyclic ring systems were synthesized using 2-(4-aminophenyl)benzothiazole structure as a pharmacophoric group. Final compounds were screened for their potential antitumor activity in vitro against approximately 60 human tumor cell lines derived from nine neoplastic diseases at National Cancer Institute, USA. 2-(4-Aminophenyl)benzothiazole structure was prepared by the reaction of 4-aminobenzoic acid and 2-aminothiophenol in polyphosphoric acid using microwave irradiation. After acetylation reaction, amide compounds 2a and 2b were obtained, which were then reacted with 2-mercapto(benz)imidazole/benzothiazole/benzoxazole derivatives in acetone with the presence of potassium carbonate to gain final compounds (3-27). Among all tested compounds, compound 10, namely N-[4-(benzothiazole-2-yl)-3-chlorophenyl]-2-[(benzimidazole-2-yl)thio]acetamide, and compound 16, namely N-[4-(benzothiazole-2-yl)phenyl]-2-[(1,5-diphenyl-1H-imidazole-2-yl)thio]acetamide, were found to be of considerable anticancer activity against some cancer cell lines.

  15. Synthesis of High Performance Cyclic Olefin Polymers (COPs with Ester Group via Ring-Opening Metathesis Polymerization

    Directory of Open Access Journals (Sweden)

    Jing Cui


    Full Text Available Novel ester group functionalized cyclic olefin polymers (COPs with high glass transition temperature, high transparency, good mechanical performance and excellent film forming ability have been achieved in this work via efficient ring-opening metathesis copolymerization of exo-1,4,4a,9,9a,10-hexahydro-9,10(1′,2′-benzeno-l,4-methanoanthracene (HBM and comonomers (5-norbornene-2-yl methylacetate (NMA, 5-norbornene-2-yl methyl 2-ethylhexanoate (NME or 5-norbornene-2-yl methyldodecanoate (NMD utilizing the Grubbs first generation catalyst, Ru(CHPh(Cl2(PCy32 (Cy = cyclohexyl, G1, followed by hydrogenation of double bonds in the main chain. The fully hydrogenated copolymers were characterized by nuclear magnetic resonance, FT-IR spectroscopy analysis, gel permeation chromatography, and thermo gravimetric analysis. Differential scanning calorimetry curves showed that the glass transition temperatures (Tg linearly decreased with the increasing of comonomers content, which was easily controlled by changing feed ratios of HBM and comonomers. Static water contact angles tests indicate that hydrophilicity of copolymers can also be modulated by changing the comonomers incorporation. Additionally, the mechanical performances of copolymers were also investigated.

  16. Ring-shaped silafluorene derivatives as efficient solid-state UV-fluorophores: synthesis, characterization, and photoluminescent properties. (United States)

    Cai, Yuanjing; Samedov, Kerim; Dolinar, Brian S; Albright, Haley; Guzei, Ilia A; Hu, Rongrong; Zhang, Chaocan; West, Robert


    Four ring-shaped silafluorene-containing compounds (1-4) were synthesized and characterized as potentially promising monomers for fluorescent polymers. Their optical properties in solution and solid state (thin film and powder) were studied. These compounds have low quantum yields in solution (Φ(fl)=0.13-0.15) with fluorescence maxima at about 355 nm, but high quantum yields in the solid state (powder, Φ(fl)=0.35-0.54) with fluorescence maxima at about 377 and 488 nm. Influence of the substituents and the number of silafluorene units in 1-4 on their optical properties was investigated. Extensive study of the X-ray crystal structures of 1-4 was undertaken to analyze and qualitatively estimate the role, extent, and influence of silafluorene moieties' interactions on solid-state fluorescent properties. Excited state UV/Vis and theoretical molecular orbital (MO) calculations were performed to explore possible fluorescence mechanisms and differences in quantum yields among these compounds.

  17. Two-dimensionally stacked heterometallic layers hosting a discrete chair dodecameric ring of water clusters: synthesis and structural study. (United States)

    Kenfack Tsobnang, Patrice; Wenger, Emmanuel; Biache, Coralie; Lambi Ngolui, John; Ponou, Siméon; Dahaoui, Slimane; Lecomte, Claude


    The stacked two-dimensional supramolecular compound catena-{Co(amp)3Cr(ox)3·6H2O} (amp = 2-picolylamine, ox = oxalate) has been synthesized from the bimolecular approach using hydrogen bonds. It is built from layers in which both Co(amp)(3+) (D) and Cr(ox)(3-) (A) ions are bonded in a repeating DADADA… pattern along the a and c axes by multiple hydrogen bonds. These layers host a well resolved R12 dodecameric discrete ring of water clusters built by six independent molecules located around the 2c centrosymmetric Wyckoff positions of the P21/n space group in which the compound crystallizes. These clusters are ranged along the [001] direction, occupy 733.5 Å(3) (22.0%) of the unit cell and have a chair conformation via 12 hydrogen bonds. The water molecules of the cluster are linked with stronger hydrogen bonds than those between the cluster and its host, which explains the single continuous step of the dehydration process of the compound.

  18. Synthesis of biodegradable amphiphilic Y-shaped block co-polymers via ring-opening polymerization for drug delivery. (United States)

    Jia, Lin; Yan, Lifeng; Li, Yang


    A series of novel Y-shaped biodegradable block co-polymers of poly(ε-caprolactone) (PCL) and poly(ethyl ethylene phosphate) (PEEP) (PCL-(PEEP)2) were synthesized via ring-opening polymerization (ROP) of EEP with bis-hydroxy-functional ROP initiator (init-PCL-(OH)2). The init-PCL-(OH)2 was synthesized by ROP of CL using 4-hydroxybutyl acrylate (HBA) as initiator and L-tartaric acid as catalyst in bulk, and subsequently the resulting vinyl-terminated PCL was end-capped by acetyl chloride, followed by Michael addition using excess diethanolamine. The Y-shaped co-polymers and their intermediates were characterized by (1)H-, (13)C-, (31)P-NMR, FT-IR and gel-permeation chromatography. The results indicated that the molecular weight of the Y-shaped co-polymers increased with the increasing of the molar ratios of EEP to init-PCL-(OH)2 in the feed, while the PCL chain length was kept constant. The amphiphilic block co-polymers could self-assemble into micelles in aqueous solution, which was demonstrated by dynamic light scattering, (1)H-NMR and atomic force microscopy. A study of controlled release of indomethacin indicated that the amphiphilic block co-polymers could potentially provide novel vehicles for drug delivery.

  19. Oligomeric ferrocene rings (United States)

    Inkpen, Michael S.; Scheerer, Stefan; Linseis, Michael; White, Andrew J. P.; Winter, Rainer F.; Albrecht, Tim; Long, Nicholas J.


    Cyclic oligomers comprising strongly interacting redox-active monomer units represent an unknown, yet highly desirable class of nanoscale materials. Here we describe the synthesis and properties of the first family of molecules belonging to this compound category—differently sized rings comprising only 1,1‧-disubstituted ferrocene units (cyclo[n], n = 5-7, 9). Due to the close proximity and connectivity of centres (covalent Cp-Cp linkages; Cp = cyclopentadienyl) solution voltammograms exhibit well-resolved, separated 1e- waves. Theoretical interrogations into correlations based on ring size and charge state are facilitated using values of the equilibrium potentials of these transitions, as well as their relative spacing. As the interaction free energies between the redox centres scale linearly with overall ring charge and in conjunction with fast intramolecular electron transfer (˜107 s-1), these molecules can be considered as uniformly charged nanorings (diameter ˜1-2 nm).

  20. Green Synthesis of Silver Nanoparticles using Achillea biebersteinii Flower Extract and Its Anti-Angiogenic Properties in the Rat Aortic Ring Model

    Directory of Open Access Journals (Sweden)

    Javad Baharara


    Full Text Available Silver nanoparticles display unique physical and biological properties which have attracted intensive research interest because of their important medical applications. In this study silver nanoparticles (Ab.Ag-NPs were synthesized for biomedical applications using a completely green biosynthetic method using Achillea biebersteinii flowers extract. The structure and properties of Ab.Ag-NPs were investigated using UV-visible spectroscopic techniques, transmission electron microscopy (TEM, zeta potential and energy dispersive X-ray spectrometers (EDS. The UV-visible spectroscopic analysis showed the absorbance peak at 460 nm, which indicates the synthesis of silver nanoparticles. The average particle diameter as determined by TEM was found to be 12 ± 2 nm. The zeta potential analysis indicated that Ab.Ag-NPs have good stability EDX analysis also exhibits presentation of silver element. As angiogenesis is an important phenomenon and as growth factors imbalance in this process causes the acceleration of several diseases including cancer, the anti-angiogenic properties of Ab.Ag-NPs were evaluated using the rat aortic ring model. The results showed that Ab.Ag-NPs (200 μg/mL lead to a 50% reduction in the length and number of vessel-like structures. The synthesized silver nanoparticles from the Achillea biebersteinii flowers extract, which do not involve any harmful chemicals were well-dispersed and stabilized through this green method and showed potential therapeutic benefits against angiogenesis.

  1. Study on Synthesis and Application of a New Substituted Aromatic Tannage%一种新的置换型合成鞣剂的制备与应用

    Institute of Scientific and Technical Information of China (English)

    吕生华; 强西怀; 颜天焰


    A new substiuted synthetic tanning agent was produced by sulfonation reaction andcondensation polymerization with aromatic compounds. Furthermore, the properties as tarning,pretanning and retanning agents was measured. Its principle of synthesis and structuralcharacteristics was also shown.%本文对以芳香族单体为主要原料制备的新的置换型合成鞣剂的应用性能进行了研究,表征了共作为鞣剂、预鞣剂及复鞣剂的性能特征,同时对其制备原理及结构特点也作了必要的说明。


    Institute of Scientific and Technical Information of China (English)

    Gui-long Wu; Jin-gang Liu; Zuo-bang Li; Zi-yi Ge; Lin Fan; Shi-yong Yang


    An aromatic diamine monomer, 4,4'-bis(3-amino-5-trifluoromethyl phenoxy)-biphenyl (TFBPDA), was synthesized via the nucleophilic displacement reaction of 3,5-dinitrobenzotrifluoride and 4,4'-biphenol. The monomer was reacted with various aromatic dianhydrides via the high temperature polycondensation procedure to provide a series of polyimides. The polyimides, PI-1 to PI-4, show good solubility not only in aprotic solvents, such as N-methyl-2-pyrrolidinone and N,N-dimethylacetamide, but also in many common solvents, such as m-cresol, chloroform and cyclopentanone. PI-4, derived from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and TFBPDA, was even soluble in toluene. Moreover, PI films exhibit good thermal stability, outstanding transparency in the visible light region and acceptable mechanical and electrical properties. The excellent combined properties of the polyimides make them as a good candidate for fabricating microelectronics.


    Institute of Scientific and Technical Information of China (English)

    HUANG Zhitang


    This review is a concise survey about the works in our laboratory on the polymerization of aromatic and heterocyclic dinitriles, including the polymerization kinetics and mechanism, synthesis of heterocyclic dinitriles, the structure of polymers, and the correlation between the structures of dinitriles and polymerization rates and thermal performances of polymers.

  4. Tandem Ring-Opening-Ring-Closing Metathesis for Functional Metathesis Catalysts. (United States)

    Nagarkar, Amit A; Yasir, Mohammad; Crochet, Aurelien; Fromm, Katharina M; Kilbinger, Andreas F M


    Use of a tandem ring-opening-ring-closing metathesis (RORCM) strategy for the synthesis of functional metathesis catalysts is reported. Ring opening of 7-substituted norbornenes and subsequent ring-closing metathesis forming a thermodynamically stable 6-membered ring lead to a very efficient synthesis of new catalysts from commercially available Grubbs' catalysts. Hydroxy functionalized Grubbs' first- as well as third-generation catalysts have been synthesized. Mechanistic studies have been performed to elucidate the order of attack of the olefinic bonds. This strategy was also used to synthesize the ruthenium methylidene complex.

  5. Degradation of aromatic compounds in plants grown under aseptic conditions

    Energy Technology Data Exchange (ETDEWEB)

    Mithaishvili, T.; Ugrekhelidze, D.; Tsereteli, B.; Sadunishvili, T.; Kvesitadze, G. [Durmishidze Inst. of Biochemistry and Biotechnology, Academy of Sciences of Georgia, Tbilisi (Georgia); Scalla, R. [Lab. des Xenobiotiques, INRA, Toulouse (France)


    The aim of the work is to investigate the ability of higher plants to absorb and detoxify environmental pollutants - aromatic compounds via aromatic ring cleavage. Transformation of {sup 14}C specifically labelled benzene derivatives, [1-6-{sup 14}C]-nitrobenzene, [1-6-{sup 14}C]-aniline, [1-{sup 14}C]- and [7-{sup 14}C]-benzoic acid, in axenic seedlings of maize (Zea mays L.), kidney bean (Phaseolus vulgaris L.), pea (Pisum sativum L.) and pumpkin (Cucurbita pepo L.) were studied. After penetration in plants, the above xenobiotics are transformed by oxidative or reductive reactions, conjugation with cell endogenous compounds, and binding to biopolymers. The initial stage of oxidative degradation consists in hydroxylation reactions. The aromatic ring can then be cleaved and degraded into organic acids of the Krebs cycle. Ring cleavage is accompanied by {sup 14}CO{sub 2} evolution. Aromatic ring cleavage in plants has thus been demonstrated for different xenobiotics carrying different substitutions on their benzene ring. Conjugation with low molecular peptides is the main pathway of aromatic xenobiotics detoxification. Peptide conjugates are formed both by the initial xenobiotics (except nitrobenzene) and by intermediate transformation products. The chemical nature of the radioactive fragment and the amino acid composition of peptides participating in conjugation were identified. (orig.)

  6. Synthesis and biological activity of two pregnane derivatives with a triazole or imidazole ring at C-21. (United States)

    Silva-Ortiz, Aylin Viviana; Bratoeff, Eugene; Ramírez-Apan, María Teresa; García-Becerra, Rocío; Ordaz-Rosado, David; Noyola-Martínez, Nancy; Castillo-Bocanegra, Rafael; Barrera, David


    Pregnane derivatives are studied as agents for the treatment of different hormone-dependent diseases. The biological importance of these steroids is based on their potential use against cancer. In this study, we report the synthesis, characterization and biological activity of two pregnane derivatives with a triazole (3β-hydroxy-21-(1H-1,2,4-triazol-1-yl)pregna-5,16-dien-20-one; T-OH) or imidazole (3β-hydroxy-21-(1H-imidazol-1-yl)pregna-5,16-dien-20-one; I-OH) moieties at C-21. These derivatives were synthesized from 16-dehydropregnenolone acetate. The activity on cell proliferation of the compounds was measured on three human cancer cells lines: prostate cancer (PC-3), breast cancer (MCF7) and lung cancer (SK-LU-1). The cytotoxic and antiproliferative effects of T-OH and I-OH were assessed by using SBR and XTT methods, respectively. The gene expressions were evaluated by real time PCR. In addition, results were complemented by docking studies and transactivation assays using an expression vector to progesterone and androgen receptor. Results show that the two compounds inhibited the three cell lines proliferation in a dose-dependent manner. Compound I-OH downregulated the gene expression of the cyclins D1 and E1 in PC-3 and MFC7 cells; however, effect upon Ki-67, EAG1, BIM or survivin genes was not observed. Docking studies show poor interaction with the steroid receptors. Nevertheless, the transactivation assays show a weak antagonist effect of I-OH on progesterone receptor but not androgenic or antiandrogenic actions. In conclusion, the synthesized compounds inhibited cell proliferation as well as genes key to cell cycle of PC-3 and MCF7 cell lines. Therefore, these compounds could be considered a good starting point for the development of novel therapeutic alternatives to treat cancer.

  7. Synthesis of Novel μ-Star Copolymers with Poly(N-Octyl Benzamide) and Poly(ε-Caprolactone) Miktoarms through Chain-Growth Condensation Polymerization, Styrenics-Assisted Atom Transfer Radical Coupling, and Ring-Opening Polymerization. (United States)

    Huang, Chih-Feng; Aimi, Junko; Lai, Kuan-Yu


    Star copolymers are known to phase separate on the nanoscale, providing useful self-assembled morphologies. In this study, the authors investigate synthesis and assembly behavior of miktoarm star (μ-star) copolymers. The authors employ a new strategy for the synthesis of unprecedented μ-star copolymers presenting poly(N-octyl benzamide) (PBA) and poly(ε-caprolactone) (PCL) arms: a combination of chain-growth condensation polymerization, styrenics-assisted atom transfer radical coupling, and ring-opening polymerization. Gel permeation chromatography, mass-analyzed laser desorption/ionization mass spectrometry, and (1) H NMR spectroscopy reveal the successful synthesis of a well-defined (PBA11 )2 -(PCL15 )4 μ-star copolymer (Mn,NMR ≈ 12 620; Đ = 1.22). Preliminary examination of the PBA2 PCL4 μ-star copolymer reveals assembled nanofibers having a uniform diameter of ≈20 nm.


    Directory of Open Access Journals (Sweden)

    Rajesh G


    Full Text Available Supra mitral ring is a rare cause for congenital mitral valve obstr uction. The reported incidence of supramitral ring is 0.2-0.4% in general population and 8% in patients with congenital mitral valve disease. The condition is characterized by an abnormal ridge of connective tissue often circumferential in shape ,on the atrial side of the mitral valve encroaching on the orifice of the mitral valve. It may adhere to the leaflets of the valve and restrict their movements. Although a supramitral ring may be rarely nonobstructive, it often results in mitral valve inflow obstruction.

  9. Synthesis, photodynamic activity, and quantitative structure-activity relationship modelling of a series of BODIPYs. (United States)

    Caruso, Enrico; Gariboldi, Marzia; Sangion, Alessandro; Gramatica, Paola; Banfi, Stefano


    Here we report the synthesis of eleven new BODIPYs (14-24) characterized by the presence of an aromatic ring on the 8 (meso) position and of iodine atoms on the pyrrolic 2,6 positions. These molecules, together with twelve BODIPYs already reported by us (1-12), represent a large panel of BODIPYs showing different atoms or groups as substituent of the aromatic moiety. Two physico-chemical features ((1)O2 generation rate and lipophilicity), which can play a fundamental role in the outcome as photosensitizers, have been studied. The in vitro photo-induced cell-killing efficacy of 23 PSs was studied on the SKOV3 cell line treating the cells for 24h in the dark then irradiating for 2h with a green LED device (fluence 25.2J/cm(2)). The cell-killing efficacy was assessed with the MTT test and compared with that one of meso un-substituted compound (13). In order to understand the possible effect of the substituents, a predictive quantitative structure-activity relationship (QSAR) regression model, based on theoretical holistic molecular descriptors, was developed. The results clearly indicate that the presence of an aromatic ring is fundamental for an excellent photodynamic response, whereas the electronic effects and the position of the substituents on the aromatic ring do not influence the photodynamic efficacy.

  10. One-pot synthesis of 4′-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling

    Directory of Open Access Journals (Sweden)

    Roman Yu. Peshkov


    Full Text Available A convenient one-pot approach to alkylcyanobiaryls is described. The method is based on biaryl cross-coupling between the sodium salt of the terephthalonitrile dianion and a neutral aromatic nitrile in liquid ammonia, and successive alkylation of the long-lived anionic intermediate with alkyl bromides. The reaction is compatible with benzonitriles that contain methyl, methoxy and phenyl groups, fluorine atoms, and a 1-cyanonaphthalene residue. The variety of ω-substituted alkyl bromides, including an extra bromine atom, a double bond, cyano and ester groups, as well as a 1,3-dioxane fragment are suitable as alkylation reagents.

  11. A base-mediated self-propagative Lossen rearrangement of hydroxamic acids for the efficient and facile synthesis of aromatic and aliphatic primary amines. (United States)

    Ohtsuka, Naoya; Okuno, Moriaki; Hoshino, Yujiro; Honda, Kiyoshi


    A variety of aromatic and aliphatic hydroxamic acids were converted to the corresponding primary amines via base-mediated rearrangement. This rearrangement could proceed with less than 1 equiv. of K2CO3 in polar solvents under thermal conditions with no external reagents. This rearrangement has several features including no external activating agents needed for promoting the rearrangement, less than one equivalent of a base is sufficient for the reaction, and a clean reaction in which only carbon dioxide is produced as a by-product. A self-propagating mechanism via an isocyanate intermediate is proposed and elementary reaction steps, namely, chain propagation reactions are supported by experiments.

  12. Synthesis and characterization of new polyesters based on 2,5-bis[(4-chloro carboxyanilino)carbonyl]pyridine and aromatic diols

    Institute of Scientific and Technical Information of China (English)

    Khalil; Faghihi


    Six new polyesters 7a-f were synthesized through the solution polycondensation reaction of diacid chloride 5 with six aromatic diols 6a-f in N,N-dimethyl acetamide(DMAc) as solvent in the presence of pyridine as base.The polycondensation reaction produced a series of novel polyester containing pyridyl moiety in the main chain in high yields with inherent viscosities between 0.35 and 0.54 dL/g.The resulted polymers were fully characterized by means of FT-IR spectroscopy,elemental analyses,inherent viscosi...

  13. One-pot synthesis of 4′-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling (United States)

    Peshkov, Roman Yu; Chunyan, Wang; Tretyakov, Evgeny V; Shteingarts, Vitalij D


    Summary A convenient one-pot approach to alkylcyanobiaryls is described. The method is based on biaryl cross-coupling between the sodium salt of the terephthalonitrile dianion and a neutral aromatic nitrile in liquid ammonia, and successive alkylation of the long-lived anionic intermediate with alkyl bromides. The reaction is compatible with benzonitriles that contain methyl, methoxy and phenyl groups, fluorine atoms, and a 1-cyanonaphthalene residue. The variety of ω-substituted alkyl bromides, including an extra bromine atom, a double bond, cyano and ester groups, as well as a 1,3-dioxane fragment are suitable as alkylation reagents. PMID:27559409

  14. Determinantal rings

    CERN Document Server

    Bruns, Winfried


    Determinantal rings and varieties have been a central topic of commutative algebra and algebraic geometry. Their study has attracted many prominent researchers and has motivated the creation of theories which may now be considered part of general commutative ring theory. The book gives a first coherent treatment of the structure of determinantal rings. The main approach is via the theory of algebras with straightening law. This approach suggest (and is simplified by) the simultaneous treatment of the Schubert subvarieties of Grassmannian. Other methods have not been neglected, however. Principal radical systems are discussed in detail, and one section is devoted to each of invariant and representation theory. While the book is primarily a research monograph, it serves also as a reference source and the reader requires only the basics of commutative algebra together with some supplementary material found in the appendix. The text may be useful for seminars following a course in commutative ring theory since a ...

  15. Cave Rings (United States)


    hypothesis, that cave rings are formed in the same manner as coffee rings[3], that is, due to the enhanced deposition at the edges of sessile drops ...ring’ is the deposit formed when a sessile drop of a solution containing dissolved particles, such as coffee or salt, dries. This was investigated by...who expanded on Deegan et al.[3] to find an exact form for the evaporation flux over a sessile drop . It turns out that solving 179 for the flux is

  16. Synthesis and characterization of heat-resistant and soluble poly(amide-imide)s from unsymmetrical dicarboxylic acid containing 2-(triphenyl phosphoranylidene) moiety and various aromatic diamines

    Indian Academy of Sciences (India)

    Seema Agrawal; Anudeep Kumar Narula


    An unsymmetrical and non-coplaner heterocyclic phosphorus containing dicarboxylic acid monomer, (DCA-3) is successfully synthesized with high purity. A series of novel aromatic poly(amide-imide)s having ether or/sulphur or/fluorine or/phosphorus containing phenyl moieties in their backbone are then prepared via a direct phosphorylation polycondensation of synthesized dicarboxylic acid with various aromatic diamines. Chemical structures of DCA-3 as well as resulting polymers are confirmed by FT-IR, NMR spectroscopic techniques and elemental analysis. These polymers are readily soluble in a variety of aprotic polar solvents such as NMP, DMSO, DMAc and DMF, etc. UV spectra showed that all poy(amide-imide)s films exhibit high optical transparency. In addition, the glass transition temperatures (Tg) of these polymers were determined by differential scanning calorimetry and found in the range 271–346°C. Furthermore, thermogravimetric analysis of these polymers showed good thermal stability, 10% weight loss at temperature in excess of 538°C and char yield at 700°C in nitrogen ranging from 68 to 79%. From wide-angle X-ray diffraction experiments, all polymers showed amorphous behaviour.

  17. 1-氨基乙内酰脲芳香醛类席夫碱的有效合成%Synthesis of 1-aminohydantoin aromatic aldehyde Schiff bases

    Institute of Scientific and Technical Information of China (English)

    张逢源; 周惠良; 胡奇林


    以1-氨基乙内酰脲与芳香醛为原料,合成了6种1-氨基乙内酰脲芳香醛类席夫碱,收率为72.6%-89.2%,并对其反应条件进行了优化,得出在回流温度下,1-氨基乙内酰脲与芳香醛的投料摩尔比为1∶1(对苯二甲醛为2∶1)时反应1.5~2h产率最高。通过IR、1 HNMR和元素分析表征了目标化合物的结构。%Six aromatic aldehyde Schiff bases were synthesized from 1-aminohydantoin and aromatic aldehyde. Its yield from 72. 6%-89. 2%and the reactive condition were optimized. The target compounds were identified by IR,1 HNMR and elemental analysis.

  18. Advances in Synthesis and Aromatization of Hantzsch 1,4-Dihydropyridine Derivatives%Hantzsch 1,4-二氢吡啶衍生物的合成及其芳香化研究进展

    Institute of Scientific and Technical Information of China (English)



      综述了Hantzsch 1,4-二氢吡啶衍生物的合成及其芳香化研究进展.Hantzsch 1,4-二氢吡啶衍生物的合成方法有:(1)乙酰乙酸乙酯、芳香醛和氨或伯胺反应;(2)1,3-二酮化合物、芳香醛和氨或伯胺反应;(3)烯胺化合物和芳香醛反应;(4)1,5-二酮与氨反应;(5) a,b-不饱和酮与烯胺或酮和氨反应等.在合成技术上有固相合成和微波辅助合成等.Hantzsch 1,4-二氢吡啶芳香化方法有:光化学反应、电化学反应、脱氢反应、氢转移反应等,本文主要对脱氢反应研究进展进行综述.%  The main methods of synthesis and aromatization of Hantzsch 1,4-dihydropyridine derivatives was reviewed in this paper. The former included the reactions of ethyl acetoacetate and aromaticaldehyde with ammonia or primary amine, the reactions of 1,3-diketone compounds and aromaticaldehyde with ammonia or primary amine, the reactions of enamine compounds with aromaticaldehyde, the reactions of 1,5-diketone with amine, the reactions of a,b-unsaturated ketone with enamine or ketone and amine. The synthetic technologies included solid-phase synthesis and microwave-assistant synthesis. The latter included photochemical reactions, electrochemical reactions, dehydrogenation reactions, hydrogen transfer reactions.

  19. Self-Assembled Templates of Aromatic Pentapeptides for Synthesis of CdS Quantum-Dots to Detect the Trace Amounts of Hg(2+) in Aqueous Solutions. (United States)

    Meng, Min; Dou, Yingying; Xu, Wenlong; Hao, Jingcheng


    Molecular self-assembly has become a popular tool to prepare nanomaterials with potential applications, such as ion-responsive detection of Hg(2+) in aqueous solutions. In this study, FFACD aromatic pentapeptides, whose N-terminuses were protected by carboxyl (Ac-FFACD) or a 9-fluorenylmethoxycarbonyl group (Fmoc-FFACD), were chosen as building blocks to produce nanostructures in solutions. Based on the preliminary determination of the critical aggregation concentration (CAC) of Ac-FFACD and Fmoc-FFACD aromatic pentapeptides in water, the order of magnitude of which is 10(-5) mol·L(-1), self-assembled spiral and networked nanowires can be easily obtained over a range of concentrations. These nanowires were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The self-assembled spiral and networked nanowires were designed to be used as templates for preparing CdS quantum dots (QDs) in-situ at room temperature. The peptide-functionalized, nanowire-encapsulated CdS QDs can be used for rapid, sensitive, and selective detection of trace amounts of mercuric ions (Hg(2+)) in aqueous solutions. This method enables rapid, linear detection (the linear correlation coefficients are 0.9972 of ΔF = 257.09 + 3.58 cHg(2+) for Ac-FFACD and 0.9994 of ΔF = 48.13 + 32.96 cHg(2+) for Fmoc-FFACD) with the Hg(2+) limit of detection at 300.85 ng·L(-1) and 32.09 ng·L(-1) for Ac-FFACD and Fmoc-FFACD, respectively. The supramolecular, self-assembled nanowires, fabricated from the two aromatic pentapeptides and having encapsulated QDs, exhibit superior properties attributable to the large loading capacity and the coordination sites of these peptides with Hg(2+). These structures can serve as novel Hg(2+) sensors and have possible applications for detection of various targets in scientific and engineering systems.

  20. A Novel Aromatic Fluorine-18 Labeling Method Using Iodonium Salts Precursor

    Energy Technology Data Exchange (ETDEWEB)

    Moon, Byung Seok; Lee, Byung Chul; Kim, Sang Eun [Seoul National University College of Medicine, Seoul National University Bundang Hospital, Seongnam (Korea, Republic of)


    As many new drug substances contained various aromatic rings and fluorine attached to an electron rich aromatic ring or on the meta-position, a strategy towards improvement in aromatic fluorination of these compounds is highly desirable. The introduction of fluorine-18 onto aromatic rings showed in the limited condition containing electron withdrawing group (EWG) on the para- or ortho-position to get reasonable radiochemical yield so far. No-carrier added (NCA) [{sup 18}F]fluorenone syntheses by iodonium salts recently reported that has the potential to greatly increase the yield in systems or positions that normally not reactive enough to give sufficient yields in simple model reaction. This review describes the methodological approach towards effective aromatic fluorination by diaryliodonium salts and future prospects in an application of novel PET radiotracer.

  1. Synthesis of a new cyclosporine-based stationary phase and separation behaviors toward aromatic positional isomers by high-performance liquid chromatography. (United States)

    Liu, Wen-na; Fan, Jun; Lin, Chun; Zheng, Sheng-run; Zhang, Wei-guang


    A new cyclosporine-bonded stationary phase has been synthesized through the Staudinger reaction between azido cyclosporine A (CsA) and aminopropyl silica gel and applied in separations of six disubstituted aromatic analytes by high-performance liquid chromatography. For dimethyl phthalate, nitroaniline and chloronitrobenzene, their positional isomers were well-separated on this CsA stationary phase, in which the separation factor for m-/o-dimethyl phthalates was the biggest. For nitrotoluene, dichlorobenzene and benzenediol, the m-/o-isomers were co-eluted. Then, effects of chromatographic conditions (such as types and content of alcoholic modifiers) on separation of nitroaniline positional isomers have been investigated. Retention behaviors of nitroaniline isomers on the column exhibited the strengthening trend along with increasing carbon number of alcohols, from ethanol to 1-propanol, and to 1-butanol. A similar phenomenon was observed by lowering the content of alcohol.

  2. Batch and flow photochemical benzannulations based on the reaction of ynamides and diazo ketones. Application to the synthesis of polycyclic aromatic and heteroaromatic compounds. (United States)

    Willumstad, Thomas P; Haze, Olesya; Mak, Xiao Yin; Lam, Tin Yiu; Wang, Yu-Pu; Danheiser, Rick L


    Highly substituted polycyclic aromatic and heteroaromatic compounds are produced via a two-stage tandem benzannulation/cyclization strategy. The initial benzannulation step proceeds via a pericyclic cascade mechanism triggered by thermal or photochemical Wolff rearrangement of a diazo ketone. The photochemical process can be performed using a continuous flow reactor which facilitates carrying out reactions on a large scale and minimizes the time required for photolysis. Carbomethoxy ynamides as well as more ketenophilic bis-silyl ynamines and N-sulfonyl and N-phosphoryl ynamides serve as the reaction partner in the benzannulation step. In the second stage of the strategy, RCM generates benzofused nitrogen heterocycles, and various heterocyclization processes furnish highly substituted and polycyclic indoles of types that were not available by using the previous cyclobutenone-based version of the tandem strategy.

  3. Synthesis of 1H-Indol-3-ylpyrazole Derivatives from 1,3,5-Triketones and Arylhydrazines: One-Pot Construction of Pyrazole and Indole Rings

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sung Hwan; Kim, Se Hee; Kim, Ko Hoon; Kim, Jae Nyoung [Chonnam National Univ., Gwangju (Korea, Republic of); Lee, Sang Ku [Immune Modulator Research Center, Daejeon (Korea, Republic of)


    The reaction of 1,3,5-triketones and arylhydrazines provided indolylpyrazole derivatives in a one-pot reaction in good to moderate yields. Both the pyrazole and indole rings were constructed simultaneously with phenylhydrazine, RCOCH{sub 2}CO- moiety for the pyrazole and the remaining -CH{sub 2}COR part for the indole ring.

  4. Topological rings

    CERN Document Server

    Warner, S


    This text brings the reader to the frontiers of current research in topological rings. The exercises illustrate many results and theorems while a comprehensive bibliography is also included. The book is aimed at those readers acquainted with some very basic point-set topology and algebra, as normally presented in semester courses at the beginning graduate level or even at the advanced undergraduate level. Familiarity with Hausdorff, metric, compact and locally compact spaces and basic properties of continuous functions, also with groups, rings, fields, vector spaces and modules, and with Zorn''s Lemma, is also expected.

  5. Synthesis of 1,7-Bis(4-hydroxyphenyl)hepta-4E,6E-dien-3-one

    Institute of Scientific and Technical Information of China (English)

    XU,Guang-Bing; LI,Shao-Bai


    @@ Diarylheptanoids, most of which appearing in the areas of anti-inflammatory, anti-oxidative, super-oxide scavenging and anti-hepatotoxic effects, constitute a distinct group of metabolites of natural plants characterized by two aromatic rings linked by a linear seven aliphatic chain. We have investigated this kind of compounds and made some progress.[1]1,7-Bis(4-hydroxy-phenyl)hepta-4E,6E-dien-3-one (1) was firstly isolated from the seeds of Alpinia blepharocalyx.[2] So far the synthesis of the compound has not been reported yet. Herein, we report the synthesis of compound 1. The synthetic route is outlined in Scheme 1.

  6. Birds and polycyclic aromatic hydrocarbons (United States)

    Albers, P.H.


    Polycyclic aromatic hydrocarbons (PAH) are present throughout the global environment and are produced naturally and by activities of humans. Effects of PAH on birds have been determined by studies employing egg injection, egg immersion, egg shell application, single and multiple oral doses, subcutaneous injection, and chemical analysis of field-collected eggs and tissue. The four-to six-ring aromatic compounds are the most toxic to embryos, young birds, and adult birds. For embryos, effects include death, developmental abnormalities, and a variety of cellular and biochemical responses. For adult and young birds, effects include reduced egg production and hatching, increased clutch or brood abandonment, reduced growth, increased organweights, and a variety of biochemical responses. Trophic level accumulation is unlikely. Environmental exposure to PAH in areas of high human population or habitats affected by recent petroleum spills might be sufficient to adversely affect reproduction. Evidence of long-term effects of elevated concentrations of environmental PAH on bird populations is very limited and the mechanisms of effect are unclear.

  7. Ring interferometry

    CERN Document Server

    Malykin, Grigorii B; Zhurov, Alexei


    This monograph is devoted to the creation of a comprehensive formalism for quantitative description of polarized modes' linear interaction in modern single-mode optic fibers. The theory of random connections between polarized modes, developed in the monograph, allows calculations of the zero shift deviations for a fiber ring interferometer. The monograph addresses also the

  8. Formation and destruction of Polycyclic Aromatic Hydrocarbons (PAHs in the flaring of the biogas collected from an automotive shredded residues landfill

    Directory of Open Access Journals (Sweden)

    Massimo Raboni


    Full Text Available The paper shows the results of the combustion in an enclosed flare of the biogas collected from an automotive shredded residues landfill. The results demonstrate that at 1,000°C and long combustion, several synthesis reactions lead to the formation of 4 to 6 rings of PAHs. This formation also involves the formation of compounds such as benzo(g,h,iperylene, indeno(1,2,3-cdpyrene and dibenzo(a,hanthracene not present in raw biogas. However, the compounds most likely to form in combustion are benzo (a anthracene and benzo (b fluoranthene. The only exception is chrysene which is significantly destroyed. The experience has proved the total lack of formation of PAHs with only 2 and 3 aromatic rings.

  9. Aromater i drikkevand

    DEFF Research Database (Denmark)

    Nyeland, B. A.; Hansen, A. B.

    DMU har den 10. Juni 1997 afholdt en præstationsprøvning: Aromater i drikkevand. Der deltog 21 laboratorier i præstationsprøvningen. Prøvningen omfattede 6 vandige prøver og 6 ampuller indeholdende 6 aromater. Laboratorierne spikede de tilsendte vandprøver med indholdet fra ampullerne...

  10. On SAP-rings


    Zhixiang, Wu


    The rings whose simple right modules are absolutely pure are called right $SAP$-rings. We give a new characterization of right $SAP$ rings, right $V$ rings, and von Neumann regular rings. We also obtain a new decomposition theory of right selfinjective von Neumann regular rings. The relationships between $SAP$-rings, $V$-rings, and von Neumann regular rings are explored. Some recent results obtained by Faith are generalized and the results of Wu-Xia are strengthened.

  11. First Synthesis and Isolation of the E- and Z-Isomers of Some New Schiff Bases. Reactions of 6-Azido-5-Formyl-2-Pyridone with Aromatic Amines

    Directory of Open Access Journals (Sweden)

    Kamal U. Sadek


    Full Text Available Some novel Schiff bases have been prepared by reacting 6-azido-5-formyl-2-pyridone 1 with a series of aromatic amines 2a-f. 5-Arylaminomethylene-6-(E-aryliminopyridones3a-e were obtained by reaction of 1 with 2a-e at room temperature,whereas with 2f, the 6-azido-5-naphthalen-2-yl-iminomethylpyridone derivative 4 wasformed. On the other hand, heating 1 with 2a-d at 140-150°C yielded two sets of isomericproducts, (E-3a-d and (Z-5a-d. Refluxing compounds (Z-3a,c with hydroxyl-amine inmethanol gave the corresponding hydroxyliminopyridones 8a,c. Heating of (E-3a-d withexcess POCl3 at reflux did not give the expected tricyclic compound 9, but rather theisomeric products (Z-5a-d were obtained. The structures of all these products have beencharacterized using IR and 1H- and 13C-NMR spectroscopy.

  12. In situ solvothermal synthesis of metal-organic framework coated fiber for highly sensitive solid-phase microextraction of polycyclic aromatic hydrocarbons. (United States)

    Gao, Jia; Huang, Chuanhui; Lin, Yifen; Tong, Ping; Zhang, Lan


    The present work reported a facile and simple in situ solvothermal growth method for immobilization of metal-organic framework UiO-66 via covalent bonding on amino functional silica fiber for highly sensitive solid-phase microextraction (SPME) of ten polycyclic aromatic hydrocarbons (PAHs) by coupling with gas chromatography-mass spectrometry (GC-MS) analysis. The developed SPME coated fiber has been characterized through SEM, TGA and XRD, confirmed the coating thickness of ∼25μm with high thermal and chemical stability. Under optimized conditions, the obtained method exhibited satisfactory linearity in range of 1.0-5000.0ngL(-1) for all the PAHs. The low detection limits were from 0.28ngL(-1) to 0.60ngL(-1) (S/N=3). The UiO-66 coated fibers showed good repeatability (RSDs less than 8.2%, n=5) and satisfying reproducibility between fiber to fiber (RSDs less than 8.9%, n=5). This method was successfully used for simultaneous determination of ten PAHs from Minjiang water and soil samples with satisfactory recoveries of 87.0-113.6% and 83.8-116.7%, respectively. Experimental results shows that the chemical bonding approach has dramatically improve the stability and lifetime of pure MOFs coating for SPME in sample pretreatment.

  13. Aromatic fumaronitrile core-based donor-linker-acceptor-linker-donor (D-pi-A-pi-D) compounds: synthesis and photophysical properties. (United States)

    Panthi, Krishna; Adhikari, Ravi M; Kinstle, Thomas H


    A new class of aromatic fumaronitrile core-based compounds with different donors and linkers has been synthesized and well characterized. Compounds 1 and 2 have indole and 2-phenylindole groups as electron donors, respectively. Compounds 3 and 4 have a diphenylamino group as the electron donor, and compound 5 has a 3,6-di-tert-butylcarbazole group as an electron donor. These compounds absorb in the blue-to-green region and emit in the blue-to-red region depending on the electron donor, linker, and solvents. The quantum yields of fluorescence of these compounds in solution are measured and found to be moderate, but in solid states, they are high. These compounds display strong emission solvatochromism that is reflected by a large shift in their fluorescence emission maxima on changing the solvents. This change is accompanied by a successive decrease in fluorescence intensity. The fluorescence lifetimes of these compounds are measured in different solvent and found to vary from compounds with solvents, concentration, and excitation energy have been studied. The correlation between the functional group and optical properties has been established to some extent. The ability of these compounds to function as colorimetric and luminescence pH sensors is demonstrated with color changes and luminescence switching upon the addition of trifluoroacetic acid. The potentiality of these compounds for application in optoelectronics has been optically assessed.

  14. Hydroxylation activity of P450 BM-3 mutant F87V towards aromatic compounds and its application to the synthesis of hydroquinone derivatives from phenolic compounds. (United States)

    Sulistyaningdyah, Woro Triarsi; Ogawa, Jun; Li, Qing-Shan; Maeda, Chiharu; Yano, Yuki; Schmid, Rolf D; Shimizu, Sakayu


    Cytochrome P450 BM-3 from Bacillus megaterium is a fatty acid hydroxylase exhibiting selectivity for long-chain substrates (12-20 carbons). Replacement of Phe87 in P450 BM-3 by Val (F87V) greatly increased its activity towards a variety of aromatic and phenolic compounds. The apparent initial reaction rates of F87V as to benzothiophene, indan, 2,6-dichlorophenol, and 2-(benzyloxy)phenol were 227, 204, 129, and 385 nmol min(-1) nmol(-1) P450, which are 220-, 66-, 99-, and 963-fold those of the wild type, respectively. These results indicate that Phe87 plays a critical role in the control of the substrate specificity of P450 BM-3. Furthermore, F87V catalyzed regioselective hydroxylation at the para position of various phenolic compounds. In particular, F87V showed high activity as to the hydroxylation of 2-(benzyloxy)phenol to 2-(benzyloxy)hydroquinone. With F87V as the catalyst, 0.71 mg ml(-1) 2-(benzyloxy)hydroquinone was produced from 1.0 mg ml(-1) 2-(benzyloxy)phenol in 4 h, with a molar yield of 66%.

  15. Biomimetic synthesis of silver nanoparticles using the fish scales of Labeo rohita and their application as catalysts for the reduction of aromatic nitro compounds. (United States)

    Sinha, Tanur; Ahmaruzzaman, M; Sil, A K; Bhattacharjee, Archita


    In this article, a cleaner, greener, cheaper and environment friendly method for the generation of self assembled silver nanoparticles (Ag NPs) applying a simple irradiation technique using the aqueous extract of the fish scales (which is considered as a waste material) of Labeo rohita is described. Gelatin is considered as the major ingredient responsible for the reduction as well as stabilisation of the self assembled Ag NPs. The size and morphology of the individual Ag NPs can be tuned by controlling the various reaction parameters, such as temperature, concentration, and pH. Studies showed that on increasing concentration and pH Ag NPs size decreases, while on increasing temperature, Ag NPs size increases. The present process does not need any external reducing agent, like sodium borohydride or hydrazine or others and gelatin itself can play a dual role: a 'reducing agent' and 'stabilisation agent' for the formation of gelatin-Ag NPs colloidal dispersion. The synthesized Ag NPs were characterised by Ultraviolet-Visible spectroscopy (UV-Vis), Transmission electron microscopy (TEM) and Selected area electron diffraction (SAED) analyses. The synthesized Ag NPs was used to study the catalytic reduction of various aromatic nitro compounds in aqueous and three different micellar media. The hydrophobic and electrostatic interaction between the micelle and the substrate is responsible for the catalytic activity of the nanoparticles in micelle.

  16. Facile synthesis of magnetic carbon nitride nanosheets and its application in magnetic solid phase extraction for polycyclic aromatic hydrocarbons in edible oil samples. (United States)

    Zheng, Hao-Bo; Ding, Jun; Zheng, Shu-Jian; Zhu, Gang-Tian; Yuan, Bi-Feng; Feng, Yu-Qi


    In this study, we proposed a method to fabricate magnetic carbon nitride (CN) nanosheets by simple physical blending. Low-cost CN nanosheets prepared by urea possessed a highly π-conjugated structure; therefore the obtained composites were employed as magnetic solid-phase extraction (MSPE) sorbent for extraction of polycyclic aromatic hydrocarbons (PAHs) in edible oil samples. Moreover, sample pre-treatment time could be carried out within 10 min. Thus, a simple and cheap method for the analysis of PAHs in edible oil samples was established by coupling magnetic CN nanosheets-based MSPE with gas chromatography-mass spectrometry (GC/MS) analysis. Limits of quantitation (LOQs) for eight PAHs ranged from 0.4 to 0.9 ng/g. The intra- and inter-day relative standard deviations (RSDs) were less than 15.0%. The recoveries of PAHs for spiked soybean oil samples ranged from 91.0% to 124.1%, with RSDs of less than 10.2%. Taken together, the proposed method offers a simple and cost-effective option for the convenient analysis of PAHs in oil samples.

  17. Adsorption of aromatic amino acids in a fixed bed column

    Directory of Open Access Journals (Sweden)

    M.A. Cremasco


    Full Text Available Phenylalanine (Phe and tyrosine (Tyr are two of the twenty amino acids in proteins; they are classified as aromatic amino acids, because both have a benzene ring in their structures. These amino acids are important in the synthesis of several biologically active amines, such as beta-endorphin, a neurotransmitter. Amino acids can be separated by ion-exchange chromatography. In this case, it is important that fixed-bed adsorber design adequately predict the breakthrough curve. This work presents a mathematical model for both fluid and porous phases. In the solution proposed for this model the liquid-phase concentration inside the particles is solved analytically and is related to the liquid-phase concentration in the bed using Duhamel's theorem. The solution for liquid-phase concentration in the bed is then solved numerically instead of analytically. The basic mass transfer parameters are from the literature. The results from the model are compared with those obtained experimentally using Phe and Tyr diluted in aqueous solutions in a fixed bed of PVP (poly-4-vinylpyridine resin.

  18. Synthesis of the new ring system bispyrido[4',3':4,5]pyrrolo [1,2-a:1',2'-d]pyrazine and its deaza analogue. (United States)

    Parrino, Barbara; Spanò, Virginia; Carbone, Anna; Barraja, Paola; Diana, Patrizia; Cirrincione, Girolamo; Montalbano, Alessandra


    Derivatives of the new ring systems bispyrido[4',3':4,5]pyrrolo[1,2-a:1',2'-d] pyrazine-6,13-dione and its deaza analogue pyrido[4'',3'':4',5']pyrrolo-[1',2':4,5]pyrazino [1,2-a]indole-6,13-dione were conveniently synthesized through a four-step sequence. Symmetrical derivatives of the former ring system were obtained through self condensation. On the other hand, condensation of 6-azaindole carboxylic acid with indole 2-carboxylic acid afforded the deaza analogue ring system. Derivatives of the title ring system were tested by the National Cancer Institute (Bethesda, MD, USA) and four of them exhibited modest activity against MCF7 (a breast cancer cell line) and/or UO-31 (a renal cancer cell line).

  19. Synthesis of the New Ring System Bispyrido[4',3':4,5]pyrrolo [1,2-a:1',2'-d]pyrazine and Its Deaza Analogue

    Directory of Open Access Journals (Sweden)

    Barbara Parrino


    Full Text Available Derivatives of the new ring systems bispyrido[4',3':4,5]pyrrolo[1,2-a:1',2'-d] pyrazine-6,13-dione and its deaza analogue pyrido[4'',3'':4',5']pyrrolo-[1',2':4,5]pyrazino [1,2-a]indole-6,13-dione were conveniently synthesized through a four-step sequence. Symmetrical derivatives of the former ring system were obtained through self condensation. On the other hand, condensation of 6-azaindole carboxylic acid with indole 2-carboxylic acid afforded the deaza analogue ring system. Derivatives of the title ring system were tested by the National Cancer Institute (Bethesda, MD, USA and four of them exhibited modest activity against MCF7 (a breast cancer cell line and/or UO-31 (a renal cancer cell line.


    Institute of Scientific and Technical Information of China (English)

    Y. Mansoori; S. Shah Sanaei; S.V. Atghia; M.R. Zamanloo; Gh. Imanzadeh


    In this work,the syntheses of new thermally stable poly(amide-imide)s with pendant 2-pyridyl-1,3,4-oxadiazole units in n-butyl methyl imidazolium bromide as reaction media have been reported.A new dicarboxylic acid has been derived from the reaction of diamine,2-(5-(3,5-diaminophenyl)-1,3,4-oxadiazole-2-yl)pyridine (POBD),and trimellitic acid anhydride.Polymers were prepared from the reaction of the diimide-diacid (DIDA) and different aromatic diamines in butyl methyl imidazolium bromide,[bmim][Br],in the presence of triphenyl phosphite (TPP) as condensing agent without needing any extra components.The prepared poly(amide-imide)s were characterized by FTIR,elemental analysis,and through the synthesis of a model compound.The prepared polymers were soluble in polar and aprotic solvents,such as DMF,DMSO,NMP and DMAc.The inherent viscosity of the polymer solutions was in the range of 0.52-1.33 dL/g measured in concentrated H2SO4 at a concentration of 0.125 g/dL at (25 ± 0.5)℃.The results are compared with the results obtained from common direct polycondensation with NMP as solvent.Polymers obtained in ionic liquid showed higher inherent viscosity than that of polymers obtained via classical method in NMP.Thermal properties of the polymers were studied with DSC and TGA methods.

  1. Benzopyrans as selective estrogen receptor beta agonists (SERBAs). Part 3: synthesis of cyclopentanone and cyclohexanone intermediates for C-ring modification. (United States)

    Richardson, Timothy I; Dodge, Jeffrey A; Durst, Gregory L; Pfeifer, Lance A; Shah, Jikesh; Wang, Yong; Durbin, Jim D; Krishnan, Venkatesh; Norman, Bryan H


    Benzopyrans are selective estrogen receptor (ER) beta agonists (SERBAs), which bind the ER subtypes alpha and beta in opposite orientations. Here we describe the syntheses of cyclopentanone and cyclohexanone intermediates for SAR studies of the C-ring on the benzopyran scaffold. Modification of the C-ring disrupts binding to ERalpha, thus improving ERbeta selectivity up to 100-fold. X-ray cocrystal structures confirm previously observed binding modes.

  2. The Synthesis and Characterization of Aromatic Hybrid Anderson-Evans POMs and their Serum Albumin Interactions: The Shift from Polar to Hydrophobic Interactions. (United States)

    Al-Sayed, Emir; Blazevic, Amir; Roller, Alexander; Rompel, Annette


    Four aromatic hybrid Anderson polyoxomolybdates with Fe(3+) or Mn(3+) as the central heteroatom have been synthesized by using a pre-functionalization protocol and characterized by using single-crystal X-ray diffraction, FTIR, ESI-MS, (1) H NMR spectroscopy, and elemental analysis. Structural analysis revealed the formation of (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-FeMo6 -bzn; TBA=tetrabutylammonium, ACN=acetonitrile, bzn=TRIS-benzoic acid alkanolamide, TRISR=(HOCH2 )3 CR)), (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-FeMo6 -cin; cin=TRIS-cinnamic acid alkanolamide), (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-MnMo6 -bzn), and (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-MnMo6 -cin). To make these four compounds applicable in biological systems, an ion exchange was performed that gave the water-soluble (up to 80 mM) sodium salts Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-FeMo6 -bzn), Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-FeMo6 -cin), Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-MnMo6 -bzn), and Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-MnMo6 -cin). The hydrolytic stability of the sodium salts was examined by applying ESI-MS in the pH range of 4 to 9. Sodium dodecylsulfate-polyacrylamide gel electrophoresis (SDS-PAGE) showed that human and bovine serum albumin (HSA and BSA) remain intact in solutions that contain up to 100 equivalents of the sodium salts over more than 4 d at 20 °C. Tryptophan (Trp) fluorescence quenching was applied to study the interactions between the sodium salts and HSA and BSA at pH 5.5 and 7.4. The quenching constants were extracted by using Stern-Volmer analysis, which suggested the formation of a 1:1 POM-protein complex in all samples. It is suggested that the aromatic hybrid POM approaches subdomain IIA of HSA and exhibits hydrophobic interactions with its hydrophobic tails, whereas the Anderson core is stabilized through electrostatic

  3. Unexpectedly Enhanced Solubility of Aromatic Amino Acids and Peptides in an Aqueous Solution of Divalent Transition-Metal Cations (United States)

    Shi, Guosheng; Dang, Yaru; Pan, Tingting; Liu, Xing; Liu, Hui; Li, Shaoxian; Zhang, Lijuan; Zhao, Hongwei; Li, Shaoping; Han, Jiaguang; Tai, Renzhong; Zhu, Yiming; Li, Jichen; Ji, Qing; Mole, R. A.; Yu, Dehong; Fang, Haiping


    We experimentally observed considerable solubility of tryptophan (Trp) in a CuCl2 aqueous solution, which could reach 2-5 times the solubility of Trp in pure water. Theoretical studies show that the strong cation-π interaction between Cu2 + and the aromatic ring in Trp modifies the electronic distribution of the aromatic ring to enhance significantly the water affinity of Trp. Similar solubility enhancement has also been observed for other divalent transition-metal cations (e.g., Zn2 + and Ni2 + ), another aromatic amino acid (phenylalanine), and three aromatic peptides (Trp-Phe, Phe-Phe, and Trp-Ala-Phe).

  4. Calculations of proton chemical shifts in olefins and aromatics

    CERN Document Server

    Escrihuela, M C


    induced reagents on alpha,beta unsaturated ketones has also been investigated in order to deduce molecular structures and to obtain the assignment of the spectra of these molecules. A semi-empirical calculation of the partial atomic charges in organic compounds based on molecular dipole moments (CHARGE3) was developed into a model capable of predicting proton chemical shifts in a wide variety of organic compounds to a reasonable degree of accuracy. The model has been modified to include condensed aromatic hydrocarbons and substituted benzenes, alkenes, halo-monosubstituted benzenes and halo-alkenes. Within the aromatic compounds the influence of the pi electron densities and the ring current have been investigated, along with the alpha, beta and gamma effects. The model gives the first accurate calculation of the proton chemical shifts of condensed aromatic compounds and the proton substituent chemical shifts (SCS) in the benzene ring. For the data set of 55 proton chemical shifts spanning 3 ppm the rms error...

  5. Aromatic oligoamides with a rare ortho-connectivity

    DEFF Research Database (Denmark)

    Hjelmgaard, T.; Nielsen, John


    Even though aromatic oligoamides composed of aromatic amino acids in a "one-way sequence" attract ever increasing research interest, backbones connected through ortho-linked aromatics remain rare. Herein, we present the first synthesis and study of N-alkylated ortho-aminomethyl- benzamides termed...... studies indicated a more restricted rotation about the amide bonds in ortho-arylopeptoids, presumably due to a more congested backbone structure resulting from the ortho-connectivity pattern. Intriguingly, tert-butyl and phenyl side chains offer complete control over the amide conformations; whereas...

  6. Combining the [2,3] Sigmatropic Rearrangement and Ring-Closing Metathesis Strategies for the Synthesis of Spirocyclic Alkaloids. A Short and Efficient Route to (+/-)-Perhydrohistrionicotoxin

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Hagberg, Lars; Poulsen, Anders


    and efficient formal total synthesis of the alkaloid (+/-)-perhydrohistrionicotoxin (2). Thus, (+/-)-depentylperhydrohistrionicotoxin, 1, a known key intermediate for the synthesis of 2, was synthesised from 2,3-epoxycyclohexan-1-one in 10 laboratory operations and ca. 20% overall yield. The synthetic route...

  7. Fused aromatic thienopyrazines: structure, properties and function

    KAUST Repository

    Mondal, Rajib


    Recent development of a fused aromatic thieno[3.4-b]pyrazine system and their application in optoelectronic devices are reviewed. Introduction of a fused aromatic unit followed by side chain engineering, dramatically enhanced the charge carrier mobility in thin film transistor devices and mobilities up to 0.2 cm2/Vs were achieved. The optoelectronic properties of these fused aromatic thienopyrazine polymers (Eg = 1.3 to 1.6 eV, HOMO = -4.9 to -5.2 V) were tuned by introduction of various fused aromatic rings within thienopyrazine. By balancing the fundamental properties of these polymers, both high charge carrier mobilities and moderate PCEs in solar cells were achieved. Further, effects of copolymerizing units are discussed. Low band gap semiconducting polymer (Eg ∼ 1 eV) with high field effect mobility (0.044 cm2/Vs) was obtained using cyclopentadithiophene as copolymerizing unit. Finally, a molecular design approach to enhance the absorption coefficients is discussed, which resulted in improved power conversion efficiency in bulk heterojunction solar cells. © 2010 The Royal Society of Chemistry.

  8. Synthesis and preliminary evaluation of N-acylhydrazone compounds as antibacterial and antifungal agents; Sintese e avaliacao preliminar da atividade antibacteriana e antifungica de derivados N-acilidrazonicos

    Energy Technology Data Exchange (ETDEWEB)

    Cachiba, Thomas Haruo; Carvalho, Bruno Demartini; Carvalho, Diogo Teixeira [Universidade Federal de Alfenas, MG (Brazil). Fac. de Ciencias Farmaceuticas. Dept. de Alimentos e Medicamentos; Cusinato, Marina; Prado, Clara Gaviao; Dias, Amanda Latercia Tranches, E-mail: [Universidade Federal de Alfenas, MG (Brazil). Inst. de Ciencias Biomedicas


    We describe the synthesis and evaluation of N-acylhydrazone compounds bearing different electron-donating groups in one of its aromatic rings, obtained using a four-step synthetic route. IC{sub 50} values against pathogenic fungi and bacteria were determined by serial microdilution. Compounds showed low activity against Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa. By contrast, a derivative with a meta-oriented electron-donating group showed significant activity (IC50) against Candida albicans (17 {mu}M), C. krusei (34 {mu}M) and C. tropicalis (17 {mu}M). Results suggest this is a promising lead-compound for synthesis of potent antifungal agents. (author)

  9. Synthesis and Evaluation of Changes Induced by Solvent and Substituent in Electronic Absorption Spectra of New Azo Disperse Dyes Containig Barbiturate Ring



    Six azo disperse dyes were prepared by diazotizing 4-amino hippuric acid and coupled with barbituric acid and 2-thiobarbituric acid. Then, the products were reacted with aromatic aldehyde, sodium acetate, and acetic anhydride, and oxazolone derivatives were formed. Characterization of the dyes was carried out by using UV-Vis, FT-IR, 1H NMR and 13C NMR, and mass spectroscopic techniques. The solvatochromic behavior of azo disperse dyes was evaluated in various solvents. The effects of substitu...

  10. Construction of carbocyclic ring of indoles using ruthenium-catalyzed ring-closing olefin metathesis. (United States)

    Yoshida, Kazuhiro; Hayashi, Kazushi; Yanagisawa, Akira


    The selective synthesis of substituted indoles was achieved by the ring-closing olefin metathesis (RCM)/elimination sequence or the RCM/tautomerization sequence of functionalized pyrrole precursors. The RCM/elimination sequence was also applied to double ring closure to yield a substituted carbazole.

  11. Synthesis and structural studies of copper(II) complex supported by -ONNO- tetradentate ligand:Efficient catalyst for the ring-opening polymerization of lactide

    Institute of Scientific and Technical Information of China (English)

    Anita Routaray; Nibedita Nath; Somanath Mantri; Tungabidya Maharan; Alekha Kumar Sutar


    The –ONNO– tetradentate Schiff base ligandN,N’-bis(2-hydroxy-3-methoxybenzaldehyde)benzene-1,2-diamine (HMBBD) has been synthesized. The ligand was attached to copper (Cu-HMBBD) in methanol under N2 atmosphere to give a mononuclear complex. The reactivity of this complex in the ring-opening polymerization (ROP) of lactide has been studied. The complex has a square planner geometry, as determined by X-ray diffraction studies. The copper complex is highly active towards the ring-opening polymerization of lactide, and the rate of polymerization is heavily dependent on the initiator used. The copper complex allows controlled ring-opening polymerization, as shown by the linear relationship between the percentage conversion and the number average molecular weight. Based on the literature, a mechanism for the ROP of lactide has been proposed.

  12. Synthesis of Isoiminosugars

    DEFF Research Database (Denmark)

    Hyldtoft, Lene; Godskesen, Michael Anders; Lundt, Inge


    A short synthesis of isoiminosugars have been developed. Bromolactones are diastereoselectively alkylated at C-2 followed by ring closure to the corresponding lactams. Reduction of these then gives isoiminosugars......A short synthesis of isoiminosugars have been developed. Bromolactones are diastereoselectively alkylated at C-2 followed by ring closure to the corresponding lactams. Reduction of these then gives isoiminosugars...

  13. Xenoestrogenic gene expression: structural features of active polycyclic aromatic hydrocarbons. (United States)

    Schultz, T Wayne; Sinks, Glendon D


    Estrogenicity was assessed using the Saccharomyces cerevisiae-based Lac-Z reporter assay and was reported as the logarithm of the inverse of the 50% molar beta-galactosidase activity (log[EC50(-1)]). In an effort to quantify the relationship between molecular structure of polycyclic aromatic hydrocarbons (PAHs) and estrogenic gene expression, a series of PAHs were evaluated. With noted exceptions, the results of these studies indicate that the initial two-dimensional structural warning for estrogenicity, the superpositioning of a hydroxylated aromatic system on the phenolic A-ring of 17-beta-estradiol, can be extended to the PAHs. This two-dimensional-alignment criterion correctly identified estrogenicity of 22 of the 29 PAHs evaluated. Moreover, the estrogenic potency of these compounds was directly related to the size of the hydrophobic backbone. The seven compounds classified incorrectly by this structural feature were either dihydroxylated naphthalenes or aromatic nitrogen-heterocyclic compounds; all such compounds were false positives. Results with dihydroxylated naphthalenes reveal derivatives that were nonestrogenic when superimposed on the phenolic A-ring of 17-beta-estradiol had the second hydroxyl group in the position of the C-ring or were catechol-like in structure. Structural alerts for nitrogen-heterocyclic compounds must take into account the position of the hydroxyl group and the in-ring nitrogen atom; compounds with the hydroxyl group and nitrogen atom involved with the same ring were observed to be nonactive.

  14. [Inhibition of aromatics on ammonia-oxidizing activity of sediment]. (United States)

    Dong, Chun-hong; Hu, Hong-ying; Wei, Dong-bin; Huang, Xia; Qian, Yi


    The inhibition of 24 aromatics on ammonia-oxidizing activity of nitrifying bacteria in sediment was measured. The effects of the kind, number and position of substituted groups on ammonia-oxidizing activity of nitrifying bacteria were discussed. The inhibition of mono-substituted benzenes on ammonia-oxidizing activity of nitrifying bacteria were in order of -OH > -NO2 > -NH2 > -Cl > -CH3 > -H. The position of substituted groups of di-substituted benzenes also affected the inhibition, and the inhibitions of dimethylbenzenes(xylene) were in order of meta-> ortho-> para-. The increase in number of substituted group on benzene-ring enhanced the inhibition of aromatics studied in this study on nitrifying bacteria. There was a linear relationship between inhibition (IC50, mumol.L-1) of aromatics on ammonia-oxidizing activity and total electronegativity (sigma E) of aromatics: lgIC50 = 14.72 - 0.91 sigma E.

  15. New aromatic polyamides and polyimides having an adamantine bulky group



    Producción Científica This paper reports the synthesis and characterization of a new rigid diamine monomer, having a spiro carbon moiety and an adamantane bulky group in its structure; namely spiro-(adamantane-2,9′(2',7'-diamino)-fluorene) (SADAF). After its synthesis, using a straightforward methodology, a novel family of aromatic polyimides (PIs) and polyamides (PAs) has been attained by reaction of SADAF with three aromatic dianhydrides and two diacid chlorides, respectively. Two of the...

  16. Origami rings

    CERN Document Server

    Buhler, Joe; de Launey, Warwick; Graham, Ron


    Motivated by a question in origami, we consider sets of points in the complex plane constructed in the following way. Let $L_\\alpha(p)$ be the line in the complex plane through $p$ with angle $\\alpha$ (with respect to the real axis). Given a fixed collection $U$ of angles, let $\\RU$ be the points that can be obtained by starting with $0$ and $1$, and then recursively adding intersection points of the form $L_\\alpha(p) \\cap L_\\beta(q)$, where $p, q$ have been constructed already, and $\\alpha, \\beta$ are distinct angles in $U$. Our main result is that if $U$ is a group with at least three elements, then $\\RU$ is a subring of the complex plane, i.e., it is closed under complex addition and multiplication. This enables us to answer a specific question about origami folds: if $n \\ge 3$ and the allowable angles are the $n$ equally spaced angles $k\\pi/n$, $0 \\le k < n$, then $\\RU$ is the ring $\\Z[\\zeta_n]$ if $n$ is prime, and the ring $\\Z[1/n,\\zeta_{n}]$ if $n$ is not prime, where $\\zeta_n := \\exp(2\\pi i/n)$ is ...

  17. Nobel Chemistry in the Laboratory: Synthesis of a Ruthenium Catalyst for Ring-Closing Olefin Metathesis--An Experiment for the Advanced Inorganic or Organic Laboratory (United States)

    Greco, George E.


    An experiment for the upper-level undergraduate laboratory is described in which students synthesize a ruthenium olefin metathesis catalyst, then use the catalyst to carry out the ring-closing metathesis of diethyl diallylmalonate. The olefin metathesis reaction was the subject of the 2005 Nobel Prize in chemistry. The catalyst chosen for this…

  18. Green chemistry approaches to the regioselective synthesis of spiro heterobicyclic rings using iodine as a new and efficient catalyst under solvent-free conditions. (United States)

    Prajapati, Dipak; Bhuyan, Debajyoti; Gohain, Mukut; Hu, Wenhao


    Iodine catalyzes the pseudo four-component reaction of an aldehyde, a urea or thiourea, and cyclic 1,3-dicarbonyl compounds under microwave irradiation in a solvent-free condition to yield various σ symmetric spiro heterobicyclic rings in excellent yields.

  19. A new type of self-supported, polymeric Ru-carbene complex for homogeneous catalysis and heterogeneous recovery: synthesis and catalytic activities for ring-closing metathesis. (United States)

    Chen, Shu-Wei; Kim, Ju Hyun; Shin, Hyunik; Lee, Sang-Gi


    A novel 2nd generation Grubbs-type catalyst tethering an isopropoxystyrene has been synthesized and automatically polymerized in solution to form a self-supported polymeric Ru-carbene complex, which catalyzed ring-closing metathesis homogeneously, but was recovered heterogeneously.

  20. Synthesis of imidacloprid derivatives with a chiral alkylated imidazolidine ring and evaluation of their insecticidal activity and affinity to the nicotinic acetylcholine receptor. (United States)

    Nishiwaki, Hisashi; Kuriyama, Mituhiro; Nagaoka, Hikaru; Kato, Akira; Akamatsu, Miki; Yamauchi, Satoshi; Shuto, Yoshihiro


    A series of imidacloprid (IMI) derivatives with an alkylated imidazolidine ring were asymmetrically synthesized to evaluate their insecticidal activity against adult female housefly, Musca domestica, and affinity to the nicotinic acetylcholine receptor of the flies. The bulkier the alkyl group, the lower was the receptor affinity, but the derivatives methylated and ethylated at the R-5-position of the imidazolidine ring were equipotent to the unsubstituted compound. Quantitative structure-activity relationship (QSAR) analysis of the receptor affinity demonstrated that the introduction of a substituent into the imidazolidine ring was fundamentally disadvantageous, but the introduction of a substituent at the R-5-position was permissible in the case of its small size. The binding model of the synthesized derivatives with the receptor supported the QSAR analysis, indicating the existence of space for a short alkyl group around the R-5-position in the ligand-binding site. In addition, positive correlation was observed between the insecticidal activity and receptor affinity, suggesting that the receptor affinity was the primary factor in influencing the insecticidal activity even if the imidazolidine ring was modified.

  1. Metabolism of aromatic compounds by Caulobacter crescentus

    Energy Technology Data Exchange (ETDEWEB)

    Chatterjee, D.K.; Bourquin, A.W.


    Cultures of Caulobacter crescentus were found to grow on a variety of aromatic compounds. Degradation of benzoate, p-hydroxybenzoate, and phenol was found to occur via ..beta..-ketoadipate. The induction of degradative enzymes such as benzoate 1,2-dioxygenase, the ring cleavage enzyme catechol 1,2-dioxygenase, and cis,cis-muconate lactonizing enzyme appeared similar to the control mechanism present in Pseudomonas spp. Both benzoate 1,2-dioxygenase and catechol 1,2-dioxygenase had stringent specificities, as revealed by their action toward substituted benzoates and substituted catechols, respectively.

  2. Development of Enantiospecific Coupling of Secondary and Tertiary Boronic Esters with Aromatic Compounds (United States)


    The stereospecific cross-coupling of secondary boronic esters with sp2 electrophiles (Suzuki–Miyaura reaction) is a long-standing problem in synthesis, but progress has been achieved in specific cases using palladium catalysis. However, related couplings with tertiary boronic esters are not currently achievable. To address this general problem, we have focused on an alternative method exploiting the reactivity of a boronate complex formed between an aryl lithium and a boronic ester. We reasoned that subsequent addition of an oxidant or an electrophile would remove an electron from the aromatic ring or react in a Friedel–Crafts-type manner, respectively, generating a cationic species, which would trigger 1,2-migration of the boron substituent, creating the new C–C bond. Elimination (preceded by further oxidation in the former case) would result in rearomatization giving the coupled product stereospecifically. Initial work was examined with 2-furyllithium. Although the oxidants tested were unsuccessful, electrophiles, particularly NBS, enabled the coupling reaction to occur in good yield with a broad range of secondary and tertiary boronic esters, bearing different steric demands and functional groups (esters, azides, nitriles, alcohols, and ethers). The reaction also worked well with other electron-rich heteroaromatics and 6-membered ring aromatics provided they had donor groups in the meta position. Conditions were also found under which the B(pin)- moiety could be retained in the product, ortho to the boron substituent. This protocol, which created a new C(sp2)–C(sp3) and an adjacent C–B bond, was again applicable to a range of secondary and tertiary boronic esters. In all cases, the coupling reaction occurred with complete stereospecificity. Computational studies verified the competing processes involved and were in close agreement with the experimental observations. PMID:27384259

  3. Development of Enantiospecific Coupling of Secondary and Tertiary Boronic Esters with Aromatic Compounds. (United States)

    Odachowski, Marcin; Bonet, Amadeu; Essafi, Stephanie; Conti-Ramsden, Philip; Harvey, Jeremy N; Leonori, Daniele; Aggarwal, Varinder K


    The stereospecific cross-coupling of secondary boronic esters with sp(2) electrophiles (Suzuki-Miyaura reaction) is a long-standing problem in synthesis, but progress has been achieved in specific cases using palladium catalysis. However, related couplings with tertiary boronic esters are not currently achievable. To address this general problem, we have focused on an alternative method exploiting the reactivity of a boronate complex formed between an aryl lithium and a boronic ester. We reasoned that subsequent addition of an oxidant or an electrophile would remove an electron from the aromatic ring or react in a Friedel-Crafts-type manner, respectively, generating a cationic species, which would trigger 1,2-migration of the boron substituent, creating the new C-C bond. Elimination (preceded by further oxidation in the former case) would result in rearomatization giving the coupled product stereospecifically. Initial work was examined with 2-furyllithium. Although the oxidants tested were unsuccessful, electrophiles, particularly NBS, enabled the coupling reaction to occur in good yield with a broad range of secondary and tertiary boronic esters, bearing different steric demands and functional groups (esters, azides, nitriles, alcohols, and ethers). The reaction also worked well with other electron-rich heteroaromatics and 6-membered ring aromatics provided they had donor groups in the meta position. Conditions were also found under which the B(pin)- moiety could be retained in the product, ortho to the boron substituent. This protocol, which created a new C(sp(2))-C(sp(3)) and an adjacent C-B bond, was again applicable to a range of secondary and tertiary boronic esters. In all cases, the coupling reaction occurred with complete stereospecificity. Computational studies verified the competing processes involved and were in close agreement with the experimental observations.

  4. Synthesis of reported and revised structures of amathamide D and synthesis of convolutamine F, H and lutamide A, C. (United States)

    Khan, Faiz Ahmed; Ahmad, Saeed


    Total synthesis of the published structure of amathamide D is described. Methyl 2,3,4-tribromo-5-hydroxybenzoate was selected as starting compound because it is readily accessible via acid-mediated Grob fragmentation-aromatization reaction of 1,4,5,6-tetrabromo-7,7-dimethoxybicyclo[2.2.1]hept-5-en-2-one. The aforementioned ester was transformed into the reported structure of amathamide D through methylation of a hydroxyl group and conversion of the ester moiety to a β-aminoethyl side chain. The NMR data of the synthetic compound did not conform to the reported natural product structure possessing contiguously positioned β-aminoethyl side chain, a set of three adjacent bromines, and a methyl ether linkage on the phenyl ring. This prompted us to redefine the natural product structure by synthesizing a product whose spectral data exactly matched with the reported data of amathamide D. The convolutamine H, with completely substituted phenyl ring adorned with an extra methyl ether functional group, has also been synthesized by application of Grob fragmentation-aromatization strategy to 3-(benzyloxy)-1,4,5,6-tetrabromo-7,7-dimethoxybicyclo[2.2.1]hept-5-en-2-one. This approach furnished directly methyl 2,3,4-tribromo-5,6-dimethoxybenzoate, which was converted straightforwardly into convolutamine H. Further, synthesis of convolutamine F and lutamide A and C is also described.

  5. Palladium- and copper-mediated N-aryl bond formation reactions for the synthesis of biological active compounds

    Directory of Open Access Journals (Sweden)

    Burkhard Koenig


    Full Text Available N-Arylated aliphatic and aromatic amines are important substituents in many biologically active compounds. In the last few years, transition-metal-mediated N-aryl bond formation has become a standard procedure for the introduction of amines into aromatic systems. While N-arylation of simple aromatic halides by simple amines works with many of the described methods in high yield, the reactions may require detailed optimization if applied to the synthesis of complex molecules with additional functional groups, such as natural products or drugs. We discuss and compare in this review the three main N-arylation methods in their application to the synthesis of biologically active compounds: Palladium-catalysed Buchwald–Hartwig-type reactions, copper-mediated Ullmann-type and Chan–Lam-type N-arylation reactions. The discussed examples show that palladium-catalysed reactions are favoured for large-scale applications and tolerate sterically demanding substituents on the coupling partners better than Chan–Lam reactions. Chan–Lam N-arylations are particularly mild and do not require additional ligands, which facilitates the work-up. However, reaction times can be very long. Ullmann- and Buchwald–Hartwig-type methods have been used in intramolecular reactions, giving access to complex ring structures. All three N-arylation methods have specific advantages and disadvantages that should be considered when selecting the reaction conditions for a desired C–N bond formation in the course of a total synthesis or drug synthesis.

  6. Swern Oxidation of Bicyclo[2.2.1]hept-5-ene-2,3-diol and Its Pyrazine-fused Derivatives: An Improved Synthesis of Bicyclo[2.2.1]hept-5-ene-2,3-dione and An Unexpected Ring-Opening Reaction

    Directory of Open Access Journals (Sweden)

    Sayuri Kobayashi


    Full Text Available An improved synthesis of bicyclo[2.2.1]hept-5-ene-2,3-dione by Swern oxidation of bicyclo[2.2.1]hept-5-ene-2,3-diol, and an unexpected ring-opening reaction by the Swern oxidation of pyrazine-fused congeners are described.

  7. Disordered organic electronic materials based on non-benzenoid 1,6-methano[10]annulene rings (United States)

    Tovar, John D; Streifel, Benjamin C; Peart, Patricia A


    Conjugated polymers and small molecules including the nonplanar aromatic 1,6-methano[10]annulene ring structure along with aromatic subunits, such as diketopyrrolopyrrole, and 2,1,3-benzothiadiazole, substituted with alkyl chains in a "Tail In," "Tail Out," or "No Tail" regiochemistry are disclosed.

  8. Total synthesis of dihydrolysergic acid and dihydrolysergol: development of a divergent synthetic strategy applicable to rapid assembly of D-ring analogs (United States)

    Lee, Kiyoun; Poudel, Yam B.; Glinkerman, Christopher M.; Boger, Dale L.


    The total syntheses of dihydrolysergic acid and dihydrolysergol are detailed based on a Pd(0)-catalyzed intramolecular Larock indole cyclization for the preparation of the embedded tricyclic indole (ABC ring system) and a subsequent powerful inverse electron demand Diels–Alder reaction of 5-carbomethoxy-1,2,3-triazine with a ketone-derived enamine for the introduction of a functionalized pyridine, serving as the precursor for a remarkably diastereoselective reduction to the N-methylpiperidine D-ring. By design, the use of the same ketone-derived enamine and a set of related complementary heterocyclic azadiene [4 + 2] cycloaddition reactions permitted the late stage divergent preparation of a series of alternative heterocyclic derivatives not readily accessible by more conventional approaches. PMID:26273113

  9. Asymmetric Synthesis of Bicyclic Nitrocyclopropanes from Primary Nitro Compounds and Stereoselective Formation of Tetrahydro-2H-cyclopenta[b]furans via Ring Expansion/Cyclization Reaction. (United States)

    Kamimura, Akio; Moriyama, Takaaki; Ito, Yuji; Kawamoto, Takuji; Uno, Hidemitsu


    Optically active bicyclic nitrocyclopropanes are readily prepared from primary chiral nitro compounds, prepared by the conjugate addition of propionaldehyde to a nitro alkene in the presence of proline-derived organocatalysts. The one-step cyclopropanation took place smoothly in a highly stereoselective manner regardless of the stereogenic center adjacent to the allylic unit. Although the allylation reaction catalyzed by BF3·OEt2 provides a mixture of two possible diastereomers, subsequent oxidation of the alcoholic carbon after the formation of nitrocyclopropanes gave diastereomerically pure single products. As a result, separation of the diastereomers during the reaction sequence is unnecessary. Baeyer-Villiger oxidation of the bicyclic nitrocyclopropane ketones followed by enolization resulted in stereoselective formation of a novel cyclopenta[b]furan ring in good yield via ring expansion followed by transannular nucleophilic cyclization.

  10. Synthesis of 4β-acyloxypodophyllotoxin analogs modified in the C and E rings as insecticidal agents against Mythimna separata Walker. (United States)

    Zhi, Xiaoyan; Yu, Xiang; Yang, Chun; Ding, Guodong; Chen, Hui; Xu, Hui


    To discover the new natural-product-based insecticidal agents, four series of sixty novel 4β-acyloxypodophyllotoxin analogs modified in the C and E rings were prepared, and their insecticidal activity was tested against the pre-third-instar larvae of oriental armyworm, Mythimna separata (Walker) in vivo at the concentration of 1 mg/mL. It demonstrated that the position of the dioxo group on the E-ring of 4'-demethylepipodophyllotoxin was regioselectively controlled by the chlorine atom at its C-2' position when 2'-chloro-4'-demethylepipodophyllotoxin was oxidized by sodium periodate. Among all the derivatives, IIIi exhibited the best potent insecticidal activity with the final mortality rate of 63.3%. To alkylacyloxy series, the proper length of the side chain at the C-4 position of Ia-g, IIa-g and IIIa-g was important for their insecticidal activity.

  11. A Convenient Approach to Heterocyclic Building Blocks: Synthesis of Novel Ring Systems Containing a [5,6]Pyrano[2,3-c]pyrazol-4(1H-one Moiety

    Directory of Open Access Journals (Sweden)

    Wolfgang Holzer


    Full Text Available Starting from commercially available educts, a straightforward synthetic route to new heterocyclic building blocks is exemplified with the one- or two-step synthesis of tri-, tetra-, or pentacyclic ring systems. Representatives of the following novel ring systems are prepared from 3-methyl-1-phenyl-2-pyrazolin-5-one and the corresponding o-halo-arenecarbonyl chloride using calcium hydroxide in refluxing 1,4-dioxane: pyrimidino[4',5':5,6]pyrano[2,3-c]pyrazol-4(1H-one, thieno[3',2':5,6]pyrano[2,3c]pyrazol- 4-(1H-one, thieno[3',4':5,6]pyrano[2,3-c]pyrazol-4(1H-one, thieno[3'',2'':4',5']thieno[2',3':5,6]-pyrano[2,3-c]pyrazol-4(1H-one, [1,3]dioxolo[5',6'][1]benzothieno[2',3':5,6]pyrano-[2,3-c]- pyrazol-4(1H-one, pyridazino[4',3':5,6]pyrano[2,3-c]pyrazol-4(1H-one and pyrazolo-[4'',3'':5',6']pyrido[3',4':5,6]pyrano[2,3-c]pyrazol-4(1H-one. While the latter two ring systems are directly obtained due to a spontaneous intramolecular substitution reaction, in the other reactions uncyclised 4-aroylpyrazol-5-ols are produced, which are cyclised into the target heterocycles in a subsequent synthetic step (i.e. treatment with NaH in DMF. Detailed NMR spectroscopic investigations (1H-, 13C-, 15N- with the obtained compounds were undertaken to unambiguously prove the new structures.

  12. Thermodiffusion of polycyclic aromatic hydrocarbons in binary mixtures (United States)

    Hashmi, Sara M.; Senthilnathan, Sid; Firoozabadi, Abbas


    Thermodiffusion in liquid mixtures may explain some counter-intuitive but naturally occurring phenomena such as hydrocarbon reservoirs with heavier component(s) stratified on top of lighter ones. However, beyond benchmark systems, systematic measurements of thermodiffusion in binary organic mixtures are lacking. We use an optical beam deflection apparatus to simultaneously probe Fickian and thermal diffusion in binary solution mixtures of polycyclic aromatic hydrocarbons dissolved in alkanes, and measure both Fickian diffusion D and the Soret coefficient ST, and then obtain the thermodiffusion coefficient DT. In a series of nine binary mixtures, we vary both the size of the aromatic compound from two to four rings, as well as the length of the alkane chain from 6 to 16 carbons. To probe the effect of increasing ring size, we include a 6-ringed aromatic compound, coronene, and toluene as a solvent, due to the insolubility of coronene in alkanes. Our results suggest that Fickian diffusion increases with the inverse of solvent viscosity and also with decreasing molecular weight of the solute. While both of these trends match our intuition, the behavior of ST and DT is more complicated. We find that ST and DT increase with the solute molecular weight when the solvent is held fixed and that the impact of solute ring size is higher in shorter chain alkane solvents.

  13. Recent Studies on the Aromaticity and Antiaromaticity of Planar Cyclooctatetraene

    Directory of Open Access Journals (Sweden)

    Masahiko Iyoda


    Full Text Available Cyclooctatetraene (COT, the first 4nπ-electron system to be studied, adopts an inherently nonplanar tub-shaped geometry of D2d symmetry with alternating single and double bonds, and hence behaves as a nonaromatic polyene rather than an antiaromatic compound. Recently, however, considerable 8π-antiaromatic paratropicity has been shown to be generated in planar COT rings even with the bond alternated D4h structure. In this review, we highlight recent theoretical and experimental studies on the antiaromaticity of hypothetical and actual planar COT. In addition, theoretically predicted triplet aromaticity and stacked aromaticity of planar COT are also briefly described.

  14. Singly N-fused Möbius aromatic [28]hexaphyrins( (United States)

    Higashino, Tomohiro; Inoue, Mitsunori; Osuka, Atsuhiro


    A singly N-fused [28]hexaphyrin was isolated and metalated with Pd(OAc)2 to give a conformationally twisted Pd(II) complex that displays distinct Möbius aromatic properties such as a strong ring current and an absorption spectrum characteristic of an aromatic porphyrinoid.

  15. A bis(heptafulvenyl)-dicyanoethylene thermoswitch with two sites for ring closure

    DEFF Research Database (Denmark)

    Broman, Søren Lindbæk; Petersen, Anne Ugleholdt; Tortzen, Christian;


    Suitably functionalized vinylheptafulvenes (VHFs) act as thermoswitches undergoing ring closure to the corresponding dihydroazulenes (DHAs). Here we present the synthesis of a new such thermoswitch incorporating two heptafulvene rings on a dicyanoethylene unit. The synthetic protocol explores both...

  16. Mercaptolysis of the E/F Rings of Steroidal Sapogenins: A Concise Synthesis of Δ20(22)-Furostene-26-thioethers

    Institute of Scientific and Technical Information of China (English)

    田伟生; 关慧平; 潘鑫复


    Lewis acid catalyzed mercaptolysls of steroidal sapogenins was reinvestigated. Besides obtaining the reported 26-thioacetals 5 under milder conditions, a new type of compounds Δ20(22)-furostene-26-thioethers 6 were also synthesized through the mercaptolysis of steroidal sapogenlns, which can be used to the synthesis of the steroidal molecule with side chains.

  17. Contribution of methyl group to secondary organic aerosol formation from aromatic hydrocarbon photooxidation (United States)

    Li, Lijie; Qi, Li; Cocker, David R.


    The complete atmospheric oxidation pathways leading to secondary organic aerosol remain elusive for aromatic compounds including the role of methyl substitutes on oxidation. This study investigates the contribution of methyl group to Secondary Organic Aerosol (SOA) formation during the photooxidation of aromatic hydrocarbons under low NOx condition by applying methyl carbon labeled aromatic hydrocarbons ((13C2) m-xylene and (13C2) p-xylene). Particle and gas phase oxidation products are analyzed by a series of mass spectrometers (HR-TOF-AMS, PTR-MS and SIFT-MS). The methyl group carbon containing oxidation products partition to the particle-phase at a lower rate than the carbons originating from the aromatic ring as a result of ring opening reactions. Further, the methyl carbon in the original aromatic structure is at least 7 times less likely to be oxidized when forming products that partition to SOA than the aromatic ring carbon. Therefore, oxidation of the methyl group in xylenes exerts little impact on SOA formation in current study. This study provides supporting evidence for a recent finding - a similarity in the SOA formation and composition from aromatic hydrocarbons regardless of the alkyl substitutes.

  18. Prime rings with PI rings of constants

    CERN Document Server

    Kharchenko, V K; Rodríguez-Romo, S


    It is shown that if the ring of constants of a restricted differential Lie algebra with a quasi-Frobenius inner part satisfies a polynomial identity (PI) then the original prime ring has a generalized polynomial identitiy (GPI). If additionally the ring of constants is semiprime then the original ring is PI. The case of a non-quasi-Frobenius inner part is also considered.

  19. Synthesis of nisin AB dicarba analogs using ring-closing metathesis: influence of sp(3) versus sp(2) hybridization of the α-carbon atom of residues dehydrobutyrine-2 and dehydroalanine-5 on the lipid II binding affinity. (United States)

    Slootweg, Jack C; van Herwerden, Eric F; van Doremalen, Mark F M; Breukink, Eefjan; Liskamp, Rob M J; Rijkers, Dirk T S


    Herein the synthesis of two nisin AB dicarba analogs is described, focusing on amino acid modifications at positions 2 and 5. The nisin mimics were synthesized by a combination of solid phase synthesis of the linear peptides, followed by macrocyclization via ring-closing metathesis and fragment assembly by means of solution phase chemistry. The two N-terminal nisin AB-fragment mimics contain either the native dehydrobutyrine (Dhb)/dehydroalanine (Dha) amino acid residues or alanine at position 2 and 5, respectively. The native dehydrobutyrine at position 2 and dehydroalanine at position 5 were introduced as their precursors, namely threonine and serine, respectively, and subsequent dehydration was carried out by EDCI/CuCl as the condensing agent. Both AB-fragment mimics were analyzed in a lipid II binding assay and it was found that the Ala2/Ala5 AB-mimic (2) showed a reduced activity, while the Dhb2/Dha5 AB-mimic (3) was as active as the native AB-fragment (1).

  20. The Effect of n vs. iso Isomerization on the Thermophysical Properties of Aromatic and Non-aromatic Ionic Liquids (United States)

    Rodrigues, Ana S.M.C.; Almeida, Hugo F. D.; Freire, Mara G.; Lopes-da-Silva, José A.; Coutinho, João A. P.; Santos, Luís M. N. B. F.


    This work explores the n vs. iso isomerization effects on the physicochemical properties of different families of ionic liquids (ILs) with variable aromaticity and ring size. This study comprises the experimental measurements, in a wide temperature range, of the ILs’ thermal behavior, heat capacities, densities, refractive indices, surface tensions, and viscosities. The results here reported show that the presence of the iso-alkyl group leads to an increase of the temperature of the glass transition, Tg. The iso-pyrrolidinium (5 atoms ring cation core) and iso-piperidinium (6 atoms ring cation core) ILs present a strong differentiation in the enthalpy and entropy of melting. Non-aromatic ILs have higher molar heat capacities due to the increase of the atomic contribution, whereas it was not found any significant differentiation between the n and iso-alkyl isomers. A small increase of the surface tension was observed for the non-aromatic ILs, which could be related to their higher cohesive energy of the bulk, while the lower surface entropy observed for the iso isomers indicates a structural resemblance between the IL bulk and surface. The significant differentiation between ILs with a 5 and 6 atoms ring cation in the n-alkyl series (where 5 atoms ring cations have higher surface entropy) is an indication of a more efficient arrangement of the non-polar region at the surface in ILs with smaller cation cores. The ILs constituted by non-aromatic piperidinium cation, and iso-alkyl isomers were found to be the most viscous among the studied ILs due to their higher energy barriers for shear stress. PMID:27682333

  1. The Effect of n vs. iso Isomerization on the Thermophysical Properties of Aromatic and Non-aromatic Ionic Liquids. (United States)

    Rodrigues, Ana S M C; Almeida, Hugo F D; Freire, Mara G; Lopes-da-Silva, José A; Coutinho, João A P; Santos, Luís M N B F


    This work explores the n vs. iso isomerization effects on the physicochemical properties of different families of ionic liquids (ILs) with variable aromaticity and ring size. This study comprises the experimental measurements, in a wide temperature range, of the ILs' thermal behavior, heat capacities, densities, refractive indices, surface tensions, and viscosities. The results here reported show that the presence of the iso-alkyl group leads to an increase of the temperature of the glass transition, Tg. The iso-pyrrolidinium (5 atoms ring cation core) and iso-piperidinium (6 atoms ring cation core) ILs present a strong differentiation in the enthalpy and entropy of melting. Non-aromatic ILs have higher molar heat capacities due to the increase of the atomic contribution, whereas it was not found any significant differentiation between the n and iso-alkyl isomers. A small increase of the surface tension was observed for the non-aromatic ILs, which could be related to their higher cohesive energy of the bulk, while the lower surface entropy observed for the iso isomers indicates a structural resemblance between the IL bulk and surface. The significant differentiation between ILs with a 5 and 6 atoms ring cation in the n-alkyl series (where 5 atoms ring cations have higher surface entropy) is an indication of a more efficient arrangement of the non-polar region at the surface in ILs with smaller cation cores. The ILs constituted by non-aromatic piperidinium cation, and iso-alkyl isomers were found to be the most viscous among the studied ILs due to their higher energy barriers for shear stress.

  2. Radical theory of rings

    CERN Document Server

    Gardner, JW


    Radical Theory of Rings distills the most noteworthy present-day theoretical topics, gives a unified account of the classical structure theorems for rings, and deepens understanding of key aspects of ring theory via ring and radical constructions. Assimilating radical theory's evolution in the decades since the last major work on rings and radicals was published, the authors deal with some distinctive features of the radical theory of nonassociative rings, associative rings with involution, and near-rings. Written in clear algebraic terms by globally acknowledged authorities, the presentation

  3. Aromatization of n-octane over Pd/C catalysts

    KAUST Repository

    Yin, Mengchen


    Gas-phase aromatization of n-octane was investigated using Pd/C catalyst. The objectives were to: (1) determine the effects of temperature (400-600 °C), weight hourly space velocity (WHSV) (0.8-∞), and hydrogen to hydrocarbon molar ratio (MR) (0-6) on conversion, selectivity, and yield (2) compare the activity of Pd/C with Pt/C and Pt/KL catalysts and (3) test the suitability of Pd/C for aromatization of different alkanes including n-hexane, n-heptane, and n-octane. Pd/C exhibited the best aromatization performance, including 54.4% conversion and 31.5% aromatics yield at 500 °C, WHSV = 2 h-1, and a MR of 2. The Pd/C catalyst had higher selectivity towards the preferred aromatics including ethylbenzene and xylenes, whereas Pt/KL had higher selectivity towards benzene and toluene. The results were somewhat consistent with adsorbed n-octane cyclization proceeding mainly through the six-membered ring closure mechanism. In addition, Pd/C was also capable of catalyzing aromatization of n-hexane and n-heptane. © 2012 Elsevier Ltd. All rights reserved.

  4. Synchronized aromaticity as an enthalpic driving force for the aromatic Cope rearrangement. (United States)

    Babinski, David J; Bao, Xiaoguang; El Arba, Marie; Chen, Bo; Hrovat, David A; Borden, Weston Thatcher; Frantz, Doug E


    We report herein experimental and theoretical evidence for an aromatic Cope rearrangement. Along with several successful examples, our data include the first isolation and full characterization of the putative intermediate that is formed immediately after the initial [3,3] sigmatropic rearrangement. Calculations at the B3LYP/6-31G(d) level of theory predict reaction energy barriers in the range 22-23 kcal/mol for the [3,3]-rearrangement consistent with the exceptionally mild reaction conditions for these reactions. The experimental and computational results support a significant enthalpic contribution of the concomitant pyrazole ring formation that serves as both a kinetic and thermodynamic driving force for the aromatic Cope rearrangement.

  5. Synthesis of Azanucleosides through Regioselective Ring-Opening of Epoxides Catalyzed by Sulphated Zirconia under Microwave and Solvent-Free Conditions

    Directory of Open Access Journals (Sweden)

    Guillermo E. Negrón-Silva


    Full Text Available New azanucleosides were obtained using sulphated zirconia (ZS as catalyst in the nucleophilic oxirane ring opening reaction of 1-allyl-3-(oxiran-2-ylmethyl pyrimidine-2,4(1H,3H-dione and 1-allyl-5-methyl-3-(oxiran-2-ylmethyl-pyrimidine-2,4(1H,3H-dione, with (S-prolinol. The new templates were obtained with good yields following a route which exploits the reactivity of epoxides in the presence of sulphated zirconia as catalyst. The key step was carried out using microwave and solvent-free conditions and proceeds with high selectivity.

  6. Synthesis and plant-growth regulatory activities of novel imine derivatives containing 1H-1,2,4-triazole and thiazole rings

    Institute of Scientific and Technical Information of China (English)


    Eleven new imine derivatives 6 containing 1H-1,2,4-triazole and thiazole rings were synthesized by the condensation of 5-((1H- 1,2,4-triazol-1-yl)methyl)-4-tert-butylthiazol-2-amine with various substituted benzaldehydes.The structures of the title compounds were characterized by ~1H NMR,MS and elemental analysis.The plant-growth regulatory activities of these compounds were evaluated.The primary bioassay results indicated that these target compounds exhibited promising plant-growth regulatory activities...

  7. Redox Switching of Orthoquinone-Containing Aromatic Compounds with Hydrogen and Oxygen Gas. (United States)

    Urakawa, Kazuki; Sumimoto, Michinori; Arisawa, Mitsuhiro; Matsuda, Masaki; Ishikawa, Hayato


    Unique redox switching of orthoquinone-containing pentacyclic aromatic compounds with molecular hydrogen and oxygen in the presence of a palladium nanoparticle catalyst (SAPd) is disclosed. These molecules were predicted by in silico screening before synthesis. Efficient protocols for the synthesis of orthoquinone-containing aromatic compounds by palladium-mediated homocoupling and the benzoin condensation reaction were developed. Clear switching between orthoquinone and aromatic hydroquinone compounds was observed on the basis of their photoluminescence properties. Furthermore, the twist strain of the orthoquinone moiety could induce dramatic changes in color and emission.

  8. Synthesis and characterization of azo benzothiazole chromophore based liquid crystal macromers: Effects of substituents on benzothiazole ring and terminal group on mesomorphic, thermal and optical properties

    Energy Technology Data Exchange (ETDEWEB)

    Karim, Md. Rabiul [Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Sheikh, Md. Rezaul Karim, E-mail: [Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Salleh, Noordini M.; Yahya, Rosiyah; Hassan, Aziz [Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Hoque, Md. Asadul [Department of Materials Science and Engineering, University of Rajshahi, Rajshahi 6205 (Bangladesh); Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-25, Nagatsuta-Cho, Midori-Ku, Yokohama 226-8503 (Japan)


    A series of azo benzothiazole chromophore based liquid crystalline compounds having different substituents at the sixth position on benzothiazole moiety with methacrylate terminal group were synthesized and characterized by FTIR, {sup 1}H and {sup 13}C NMR. TGA investigations showed synthesized compounds were thermally stable. POM and DSC studies revealed that all the compounds showed liquid crystal behaviors. SAXS analysis exposed that all the investigated compounds exhibited lamellar structure. Compound with H at the sixth position on the benzothiazole ring revealed only smectic liquid crystal phase whereas compounds with CH{sub 3}, OCH{sub 3} and OC{sub 2}H{sub 5} groups showed both nematic and smectic liquid crystal phases. The formation of mesophases as well as temperature ranges of mesophases was greatly influenced by the sixth position electron pushing substituent on benzothiazole ring as well as terminal methacrylate group. The absorption maxima (λ{sub max}) of UV–vis spectra were bathochromically shifted with the replacement of sixth position hydrogen atom by the electron donating groups on benzothiazole chromophore. Macromer with OCH{sub 3} substituent exhibited highest fluorescence emission than other compounds. - Highlights: • Benzothiazole based liquid crystalline macromers were synthesized and characterized. • Sixth position substituents of benzothiazole influenced the mesophase properties. • Terminal methacrylate group also influenced the mesophase formation. • The absorption maxima were red shifted by the electron pushing groups. • OCH{sub 3} at 6th position of benzothiazole exhibited highest fluorescence emission.

  9. Synthesis, cytotoxicity, anti-oxidative and anti-inflammatory activity of chalcones and influence of A-ring modifications on the pharmacological effect. (United States)

    Vogel, Susanne; Barbic, Matej; Jürgenliemk, Guido; Heilmann, Jörg


    Besides 2',4'-dihydroxy-4,6'-dimethoxy-3'-prenylchalcone (1) and 4-acetoxy-2',4'-dihydroxy-6'-methoxy-3'-prenylchalkon (2), both phase II metabolites of xanthohumol in rats, also a principally new chalcone 3'-coumaroyl-2',4,4'-trihydroxy-6'-methoxychalcone (3), structurally derived from helichrysetin (4) by introducing a second coumaroyl substructure at C-3' was synthesized. Furthermore new chalcones were synthesized by combination of the B-Ring fragments of helichrysetin, xanthohumol, xanthohumol C and xanthohumol H with ferulic or caffeic acid moieties in Ring A. Compound 3 showed the highest cytotoxic activity against HeLa cells with an IC50 value of 7.3+/-0.4 microM. Anti-oxidative effects were determined in the ORAC assay and revealed very strong activity for 3 and 3-methoxyhelichrysetin (6) exhibiting 7.7+/-0.3 and 6.0+/-1.3 Trolox equivalents, respectively. The anti-inflammatory activity of all compounds was measured in an in vitro ICAM-1 assay with human microvascular endothelial cells (HMEC-1) and compared with the activity of other structurally related chalcones. The results showed increasing anti-inflammatory activity for the new synthetic chalcones exhibiting a caffeoyl substructure with 3-hydroxyhelichrysetin (5) and 3-hydroxyxanthohumol H (14) being the most active. At 10 microM the TNFalpha induced expression of ICAM-1 was significantly reduced to 65.8 and 69.6% of control, respectively.


    Institute of Scientific and Technical Information of China (English)

    Cheng-pei Wu; Shi-jun Zheng; Cai-yuan Pan; Toshiyuki Uryu


    New highly stereoregular 2, 3-di-O-(p-azidobenzyl)-(1→5)-α-D-ribofuranan was synthesized by selective ring-opening polymerization of 1, 4-anhydro-2, 3-di-O-(p-azidobenzyl)-α-D-ribopyranose(ADABR) using phosphorus pentafluoride or tin tetrachloride as catalyst at low temperature in dichloromethane. The monomer was obtained by the reaction of p-bromomethyl-phenyleneazide with 1, 4-anhydro-α-D-ribose in DMF. The structure of poly(ADABR) was identified by specific rotation and 13CNMR spectroscopy. Acid chloride-AgCl4 complex catalyst such as CH2=C(CH3)C+OClO4- used in the polymerization resulted in polymers with mixed structures, i.e. (1→5)-α-D-ribofuranosidic and (1→4)-β-Dribopyranosidic units. However, with C6H5C+OClO4- as catalyst, pure (1→5)-α-D-ribofuranan was obtained.The effects of catalyst, polymerization temperature and time on polymer stereoregularity were examined, and the mechanism of the ring-opening polymerization was discussed.

  11. Synthesis of Novel 3-Aryl Isoindolinone Derivatives

    Institute of Scientific and Technical Information of China (English)

    HU Chen-ming; ZHENG Lian-you; PEI Ya-zhong; BAI Xu


    A library of novel 3-aryl isoindolinone derivatives with aromatic amino acid derivative fragments was designed and synthesized.Two synthetic routes were employed to construct 3-aryl isoindolinone ring system for different amino acid derivatives.

  12. Synthesis and characterization of optically active and organosoluble poly(amide-imide)s containing imidazole rings as pendent groups by direct polycondensation

    Institute of Scientific and Technical Information of China (English)

    KHALIL; Faghihi; MEISAM; Shabanian


    Six new optically active poly(amide-imide)s(PAIs) 6a-f were prepared by direct polycondensation reaction of N-trimelli-tylimido-L-histidine 4 as a chiral diacid with various aromatic diamines 5a-f.Triphenyl phosphite(TPP)/pyridine(Py) in the presence of calcium chloride(CaCl2) and N-methyl-2-pyrrolidone(NMP) were successfully applied to direct polycondensation reaction.The resulting new polymers were in good yields,and had inherent viscosities ranging between 0.29 and 0.41 dL g-1 and were detected with elemental analysis,FTIR,1H-NMR spectroscopy,specific rotation and differential scanning calorimeter(DSC),thermogravimetric analysis(TGA),and derivative of thermaogravimetry(DTG).Imidazole pendent groups of the polymer chains disturb interchain and intrachain interactions and make these PAIs readily soluble in polar aprotic solvents such as N,N-dimethylacetamide(DMAc),N,N-dimethylformamide(DMF),dimethylsulfoxide(DMSO),NMP and solvents such as sulfuric acid.Thermogravimetric analysis indicated that the residual weight percents of polymers at 600 °C were between 56.47% and 68.76%,which show their thermal stability.

  13. Stirling engine piston ring (United States)

    Howarth, Roy B.


    A piston ring design for a Stirling engine wherein the contact pressure between the piston and the cylinder is maintained at a uniform level, independent of engine conditions through a balancing of the pressure exerted upon the ring's surface and thereby allowing the contact pressure on the ring to be predetermined through the use of a preloaded expander ring.

  14. Birth Control Ring (United States)

    ... Loss Surgery? A Week of Healthy Breakfasts Shyness Birth Control Ring KidsHealth > For Teens > Birth Control Ring A A A What's in this article? ... español Anillo vaginal anticonceptivo What Is It? The birth control ring is a soft, flexible, doughnut-shaped ring ...

  15. Actin Rings of Power. (United States)

    Schwayer, Cornelia; Sikora, Mateusz; Slováková, Jana; Kardos, Roland; Heisenberg, Carl-Philipp


    Circular or ring-like actin structures play important roles in various developmental and physiological processes. Commonly, these rings are composed of actin filaments and myosin motors (actomyosin) that, upon activation, trigger ring constriction. Actomyosin ring constriction, in turn, has been implicated in key cellular processes ranging from cytokinesis to wound closure. Non-constricting actin ring-like structures also form at cell-cell contacts, where they exert a stabilizing function. Here, we review recent studies on the formation and function of actin ring-like structures in various morphogenetic processes, shedding light on how those different rings have been adapted to fulfill their specific roles.

  16. Alternative loop rings

    CERN Document Server

    Goodaire, EG; Polcino Milies, C


    For the past ten years, alternative loop rings have intrigued mathematicians from a wide cross-section of modern algebra. As a consequence, the theory of alternative loop rings has grown tremendously. One of the main developments is the complete characterization of loops which have an alternative but not associative, loop ring. Furthermore, there is a very close relationship between the algebraic structures of loop rings and of group rings over 2-groups. Another major topic of research is the study of the unit loop of the integral loop ring. Here the interaction between loop rings and group ri

  17. Efficient Route to Deuterated Aromatics by the Deamination of Anilines. (United States)

    Burglova, Kristyna; Okorochenkov, Sergei; Hlavac, Jan


    One-step replacement of NH2 groups in ring-substituted anilines by deuterium is reported. Approaches comprising both solid-phase and solution-phase syntheses can be used on a large variety of substrates. The method uses diazotization in a mixture of water and either dichloromethane or chloroform, which serve as a source of hydrogen. This protocol can be used as a general method for fast and easy incorporation of deuterium into an aromatic system using deuterated chloroform.

  18. New Palladium-Catalyzed Domino Reaction with Intramolecular Ring Closure of an N-(2-Chloro-3-heteroaryl) arylamide: First Synthesis of Oxazolo[4,5-b] pyrazines

    DEFF Research Database (Denmark)

    Demmer, Charles S.; Hansen, Jacob C.; Kehler, Jan;


    lipophilicity and target interaction points are often desired. In this respect, the oxazolo[4,5-b]pyrazine is an attractive heterocyclic scaffold as it possesses increased water solubility as well as two additional hydrogen bonding acceptors. We here report a new Pd(II)-catalyzed domino reaction comprising...... is required for the domino reaction to proceed. The robustness of the methodology is confirmed by the synthesis of 23 2-substituted oxazolo[4,5-b]pyrazine analogues in good-to-high yields and containing both electron-withdrawing as well as electron-donating substituents on the reacting arylamide....

  19. The formation of polycyclic aromatic hydrocarbons in evolved circumstellar environments

    CERN Document Server

    Cherchneff, Isabelle


    The formation of Polycyclic Aromatic Hydrocarbons in the circumstellar outflows of evolved stars is reviewed, with an emphasis on carbon stars on the Asymptotic Giant Branch. Evidence for PAHs present in their winds is provided by meteoritic studies and recent observations of the Unidentified Infrared bands. We detail the chemical processes leading to the closure of the first aromatic ring as well as the growth mechanisms leading to amorphous carbon grains. Existing studies on PAH formation in evolved stellar envelopes are reviewed and new results for the modelling of the inner wind of the archetype carbon star IRC+10216 are presented. Benzene, C6H6, forms close to the star, as well as water, H2O, as a result of non-equilibrium chemistry induced by the periodic passage of shocks. The growth process of aromatic rings may thus resemble that active in sooting flames due to the presence of radicals like hydroxyl, OH. Finally, we discuss possible formation processes for PAHs and aromatic compounds in the hydrogen-...

  20. New insights into aromatic pathways of carbachlorins and carbaporphyrins based on calculations of magnetically induced current densities. (United States)

    Benkyi, Isaac; Fliegl, Heike; Valiev, Rashid R; Sundholm, Dage


    Magnetically induced current densities have been calculated and analyzed for a number of synthesized carbachlorins and carbaporphyrins using density functional theory and the gauge including magnetically induced current (GIMIC) method. Aromatic properties have been determined by using accurate numerical integration of the current flow yielding reliable current strengths and pathways that are related to the degree of aromaticity and the aromatic character of the studied molecules. All investigated compounds are found to be aromatic. However, the obtained aromatic pathways differ from those previously deduced from spectroscopic data and magnetic shielding calculations. For all studied compounds, the ring current divides into an outer and an inner branch at each pyrrolic subring, showing that all π-electrons of the pyrrolic rings take part in the delocalization pathway. The calculations do not support the common notion that the main share of the current takes the inner route at the pyrrolic rings without an inner hydrogen and follows an 18π aromatic pathway. The aromatic pathways of the investigated carbaporphyrins and carbachlorins are very similar, since the current strength via the Cβ[double bond, length as m-dash]Cβ' bond of the cyclopentadienyl ring of the carbaporphyrins is almost as weak as the current density passing the corresponding saturated Cβ-Cβ' bond of the carbachlorins.

  1. 新型锗中心多孔芳香材料的设计合成和表征%Designed Synthesis and Characterization of Novel Germanium Centered Porous Aromatic Frameworks (Ge-PAFs)

    Institute of Scientific and Technical Information of China (English)

    元野; 闫卓君; 任浩; 刘青英; 朱广山; 孙福兴


    采用四(4-溴苯基)锗烷作为基块,以1,4-苯二硼酸和4,4'-联苯基二硼酸作为桥联,合成了两种锗中心的多孔芳香材料(Ge-PAFs).通过FTIR,MAS NMR,TGA,PXRD,SEM,TEM及N2吸附对该化合物的结构及性质进行表征.Ge-PAF-1和Ge-PAF-2具有优良的热稳定性(420℃失重5%)及化学稳定性.另外,该材料成功地在聚合物中引入锗元素为其在半导体等方面的应用提供了可能[1].%A novel series of germanium centered porous aromatic frameworks (Ge-PAFs) based on tetrakis(4-bromophenyl)germane as building units and 1,4-benzenediboronic acid or 4,4'-biphenyldiboronic acid as linkers were synthesized. These materials were characterized by Fourier transform infrared spectroscopy (FT-IR), 13C solid-state NMR, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TEM), and N2 gas sorption. FTIR spectroscopy is useful in probing the structure of Ge-PAFs networks. From the disappearance of the intense B--OH bands (at 3370 cm^-1) and the C--Br bands (at 482 cm^-1) in the FT-IR spectra, the formation of the product can be preliminarily confirmed. The solid-state 13C CP/MAS NMR spectra of Ge-PAFs indicate that a group of signals with a chemical shift in the range of J 120--145 could be observed. They are related to aromatic carbon atoms in the framework-building phenylene groups. Both the FTIR and 13C CP/MAS NMR analyses show no obvious signals assigned to the halogen or boronic acid end groups, testifying that an almost com- plete coupling reaction has taken place. PXRD was carried out to investigate the crystallinity of Ge-PAFs, which indicate the amorphous texture. No long-range frameworks could be due to distortion and interpenetration of the phenyl rings. SEM im- ages showed that Ge-PAF-1 and Ge-PAF-2 afforded a spherical morphology. Simultaneously, TEM revealed that

  2. Metal complexes with 2,3-bis(diphenylphosphino)-1,4-diazadiene ligands: synthesis, structures, and an intramolecular metal-mediated [4 + 2] cycloaddition employing a benzene ring as a dienophile. (United States)

    Walther, Dirk; Liesicke, Stefan; Böttcher, Lars; Fischer, Reinald; Görls, Helmar; Vaughan, Gavin


    2,3-Bis(diphenylphosphino)-1,4-diazadienes RN=C(PPh2)-C(PPh2)=NR (1a, R = 4-tolyl; 1b, R = 4-tert-butylphenyl; 1c, R = mesityl) were used as novel ligands for transition metals. The metal complexes [(1c)Mo(CO)4] (2a), [(1c)[Mo(CO)4]2] (2b), [(1a)Cu(Cl)(PPh3)] (3), and [(1b)[(NiBr2(THF))]2] (4) were characterized by elemental analysis, MS, and 31P[1H], 1H, and 13C NMR spectra (except the paramagnetic complex 4). Additionally, the molecular structure of the complexes in the solid state was determined by single-crystal X-ray diffraction. In 2a and 2b the chelating ligand coordinates via the N,P donor set, whereas in 3 the chelating ligand coordinates via the two P atoms. 4 contains a square-planar (P,P)NiBr2 moiety on the one side of the bridging ligand 1b. On the opposite side the 1,2-dimine unit bonds to another Ni center having octahedral geometry. The bulkier ligand 1c reacts to form the mononuclear compound 5. X-ray diffraction analysis of single crystals shows that 5 contains a quinoxaline derivative with a cyclohexa-1,3-diene ring in the peripheral position. Furthermore, it contains a bis(diphenylphosphino)-ethylene unit coordinating the NiBr2. This arrangement is the result of an intramolecular [4 + 2] cycloaddition between the 1,2-diimine unit (as diheterodiene) and the benzene ring of the 4-tolyl-N substituent (as dieneophile). The same type of ring-closing reaction followed by a tautomerization reaction to form the mononuclear compound 6 occurred by dissolution of the binuclear complex 4 in methanol. This reaction can be used as a simple method for the synthesis of novel 1,2-bis(diarylphosphanyl)ethylenes containing a quinoxaline backbone.

  3. A New Pathway to Synthesize Cyclomercurated Ferrocenylimines Containing Heterocyclic Ring

    Institute of Scientific and Technical Information of China (English)


    The cyclomercurated ferrocenylimines containing heterocyclic ring were prepared by the condensation of cyclomercuration of acylferrocene with the appropriate heterocyclic amine. This procedure provides an efficient method for the synthesis of cyclomerucurated ferroceny- limines containing heterocyclic ring which are difficultly synthesized by the conventional method. The reaction mechanism is proposed.

  4. Synthetic applications of gold-catalyzed ring expansions

    Directory of Open Access Journals (Sweden)

    Cristina Nevado


    Full Text Available The development of new methodologies catalyzed by late transition metals involving cycloisomerizations of strained rings can open new venues for the synthesis of structurally complex molecules with interesting biological activities. Herein we summarize, from both a synthetic as well as a mechanistic point of view, the most recent developments in gold-catalyzed ring expansions.

  5. The reduction ring-opening reaction of imidazoline

    Institute of Scientific and Technical Information of China (English)

    史真; 李诤; 白银娟


    A new reduction ring-opening reaction of 2-imidazoline with sodium borohydride is reported, and the effect of reaction condition on the yield, reaction mechanism and the use of the new reaction in synthesis of ethylenediamine derivatives are discussed. A new method for the preparation of unsymmetrical substituted ethylenediamine via the reduction ring-opening reaction of imidazoline is provided.

  6. On JB-Rings

    Institute of Scientific and Technical Information of China (English)

    Huanyin CHEN


    A ring R is a QB-ring provided that aR + bR = R with a, b ∈ R implies that there exists a y ∈ R such that a+by ∈ R-1q. It is said that a ring R is a JB-ring provided that R/J(R) is a QB-ring, where J(R) is the Jacobson radical of R. In this paper, various necessary and sufficient conditions, under which a ring is a JB-ring, are established. It is proved that JB-rings can be characterized by pseudo-similarity. Furthermore, the author proves that R is a J B-ring iff so is R/J(R)2.

  7. Polyurethane Foams with Pyrimidine Rings

    Directory of Open Access Journals (Sweden)

    Kania Ewelina


    Full Text Available Oligoetherols based on pyrimidine ring were obtained upon reaction of barbituric acid with glycidol and alkylene carbonates. These oligoetherols were then used to obtain polyurethane foams in the reaction of oligoetherols with isocyanates and water. The protocol of foam synthesis was optimized by the choice of proper kind of oligoetherol and synthetic composition. The thermal resistance was studied by dynamic and static methods with concomitant monitoring of compressive strength. The polyurethane foams have similar physical properties as the classic ones except their enhanced thermal resistance. They stand long-time heating even at 200°C. Moreover thermal exposition of foams results generally in increase of their compressive strength.

  8. One-pot synthesis of linear- and three-arm star-tetrablock quarterpolymers via sequential metal-free ring-opening polymerization using a "catalyst switch" strategy

    KAUST Repository

    Zhao, Junpeng


    A "catalyst switch" strategy has been used to sequentially polymerize four different heterocyclic monomers. In the first step, epoxides (1,2-butylene oxide and ethylene oxide) were successively polymerized from a monohydroxy or trihydroxy initiator in the presence of a strong phosphazene base promoter (t-BuP4). Then, an excess of diphenyl phosphate (DPP) was introduced, followed by addition and polymerization of a cyclic carbonate (trimethylene carbonate) and a cyclic ester (δ-valerolactone or ε-caprolactone). DPP acted as both neutralizer of the phosphazenium alkoxide (polyether chain end) and activator of the cyclic carbonate/ester. Using this method, linear- and star-tetrablock quarterpolymers were prepared in one pot. This work is emphasizing the strength of the previously developed catalyst switch strategy for the facile metal-free synthesis of complex macromolecular architectures. © 2014 Wiley Periodicals, Inc.

  9. Synthesis and characterization of photoluminescent hybrids of poly( ɛ-caprolactone)-grafted-polyhedral oligosilsesquioxane by using a combination of ring-opening polymerization and click chemistry (United States)

    Cao, Xuan Thang; Showkat, Ali Md; Bach, Long Giang; Jeong, Yeon Tae; Kim, Jong Soo; Lim, Kwon Taek; Gal, Yeong-Soon


    Photoluminescent hybrids of poly( ɛ-caprolactone) (PCL), polyhedral oligosilsesquioxane (POSS) and terbium ions (Tb3+) were synthesized by using a combination of ring-opening polymerization (ROP), click chemistry and coordination chemistry. Initially, acetylene functionalized PCL (alkyne-PCL-COOH) was prepared by using ROP of ɛ-caprolactone with propargyl alcohol, and azide-substituted POSS (POSS-N3) was prepared by using the reaction of chloropropyl-heptaisobutyl-substituted POSS with NaN3. The click reaction between alkyne-PCL-COOH and POSS-N3 afforded POSS-g-PCL, which was subsequently coordinated with Tb3+ ions in the presence of 1,10-phenanthroline to produce POSS-g-PCL-Tb3+-Phen. The structures and compositions of the hybrids were investigated by using 1H nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FT-IR), Field emission scanning electron microscope (FE-SEM), Transmission electron microscopy (TEM), and Thermogravimetric analysis (TGA). The optical properties of POSS-g-PCL-Tb3+-Phen complexes were characterized by using photoluminescence spectroscopy, which showed four high emission bands centered at 489, 545, 584, and 620 nm with excitation at 330 nm. The emission spectra of the europium-ion-coordinated hybrids, POSS-g-PCL-Eu3+-Phen, had four high-intensity peaks, 594, 617, 652 and 686 nm, for an excitation wavelength of 352 nm.

  10. Enolate chelating N-heterocyclic carbene complexes of Fe(Ⅱ): Synthesis, structure and their catalytic activity for ring-opening polymerization of ε-caprolactone

    Institute of Scientific and Technical Information of China (English)


    The reaction of anhydrous FeBr2 with two equivalents of anionic N-heterocyclic carbene (NaL1 and NaL2), which are generated in situ by the reaction of the corresponding salt [4-R-C6H4COCH2{CH- (NCHCHNiPr)}Br] (R = OCH3, H2L1Br, 1; R = F, H2L2Br, 2) with two equivalents of NaN(SiMe3)2, affords bis-ligand Fe(Ⅱ) complexes of L21Fe (3) and L22Fe (4) in high yield, respectively. Attempt to synthesize mono-ligand Fe(Ⅱ) bromide by the 1:1 molar ratio of NaL to FeBr2 is unsuccessful, and the same complexes of 3 and 4 were obtained. Both 3 and 4 have been depicted by elemental analysis and X-ray structure determination. Preliminary studies show that both 3 and 4 can be used as single-component catalyst for the ring-opening polymerization of ε-caprolactone, and the catalytic activity of 3 is higher than that of 4.

  11. Synthesis of Aluminum Complexes Bearing 8-Anilide-5,6,7-trihydroquinoline Ligands: Highly Active Catalyst Precursors for Ring-Opening Polymerization of Cyclic Esters

    Directory of Open Access Journals (Sweden)

    Shaofeng Liu


    Full Text Available The stoichiometric reactions of 8-(2,6-R1-4-R2-anilide-5,6,7-trihydroquinoline (LH with AlR3 (R = Me or Et afforded the aluminum complexes LAlR2 (Al1–Al5,Al1: R1 = iPr, R2 = H, R = Me; Al2: R1 = Me, R2 = H, R = Me; Al3: R1 = H, R2 = H, R = Me; Al4: R1 = Me, R2 = Me, R = Me; Al5: R1 = Me, R2 = Me, R = Et in high yields. All aluminum complexes were characterized by NMR spectroscopy and elemental analysis. The molecular structures of complexes Al4 and Al5 were determined by single-crystal X-ray diffractions and revealed a distorted tetrahedral geometry at aluminum. In the presence of BnOH, complexes Al1–Al5 efficiently initiated the ring-opening homopolymerization of ε-caprolactone (ε-CL and rac-lactide (rac-LA, respectively, in a living/controlled manner.

  12. Amphiphilic block copolymers bearing six-membered ortho ester ring in side chains as potential drug carriers: synthesis, characterization, and in vivo toxicity evaluation. (United States)

    Luo, Shi; Tao, Yangyang; Tang, Rupei; Wang, Rui; Ji, Weihang; Wang, Chun; Zhao, Youliang


    A new type of amphiphilic block copolymers, poly(ethylene glycol)-block-poly(2-methyl-acrylicacid 2-methoxy-5-methyl-[1,3]dioxin-5-ylmethyl ester) (PEG-b-PMME), bearing acid-labile six-membered ortho ester rings in side chains was synthesized by reversible addition-fragmentation chain-transfer polymerization, and the influence of chain length of the hydrophobic PMME block on micelle properties was investigated. The PEG-b-PMME micelles were stable in aqueous buffer at physiological pH with a low critical micelle concentration. Nile Red as a model drug was encapsulated into the micelles to explore the release profiles. The Nile Red-loaded polymeric micelles showed rapid release of Nile Red in weakly acidic environments (pH 5) but slow release under physiological condition (pH 7.4), due to different hydrolysis rate of ortho ester side chains of PEG-b-PMME. The Paclitaxel (PTX)-loaded micelles retained potency in killing lung cancer cells (A549), compared with the free PTX. No obvious toxicity was found in vitro and in vivo after intraperitoneal injection of the micelles, which confirms that the PEG-b-PMME micelles with unique acid-labile characteristic have great potential as nano-scaled carriers for drug delivery.

  13. Controlled synthesis, optical properties and cytotoxicity studies of CdSe-poly(lactic acid) multifunctional nanocomposites by ring-opening polymerization. (United States)

    Islam, Md Rafiqul; Bach, Long Giang; Vo, Thanh-Sang; Lee, Doh C; Lim, Kwon Taek


    A facile synthetic route has been developed for the covalent grafting of biocompatible poly(lactic acid) (PLA) onto CdSe Quantum Dots (QDs) using surface initiated ring opening polymerization (ROP) to afford CdSe-g-PLA nanocomposites. At first, 2-mercaptoethanol (ME) capped CdSe QDs were synthesized through a wet chemical process. The surface initiated ROP of lactide was accomplished with Sn(Oct)2 to give CdSe-g-PLA nanocomposites having surface hydroxyl functionality. FT-IR data suggested that a robust covalent bond was formed between ME capped CdSe QDs and polymer moieties. The grafting density of PLA on CdSe QDs was found to be moderate as measured by TGA analysis. The CdSe QDs were well dispersed in CdSe-g-PLA nanocomposites matrices as captured by TEM. The cubic phase crystal structure of CdSe QDs in the nanocomposites was determined by XRD. The optical properties of the CdSe-g-PLA nanocomposites were investigated by UV-vis and photoluminescence spectroscopy which suggested their potentialities as optical materials in biomedical application. Cell viability studies revealed that the biocompatibility of CdSe QDs was improved upon PLA immobilization.

  14. Synthesis and quantitative structure-activity relationship (QSAR) study of novel 4-acyloxypodophyllotoxin derivatives modified in the A and C rings as insecticidal agents. (United States)

    He, Shuzhen; Shao, Yonghua; Fan, Lingling; Che, Zhiping; Xu, Hui; Zhi, Xiaoyan; Wang, Juanjuan; Yao, Xiaojun; Qu, Huan


    In continuation of our program aimed at the discovery and development of natural-product-based insecticidal agents, we have synthesized three series of novel 4-acyloxy compounds derived from podophyllotoxin modified in the A and C rings, which is isolated as the main secondary metabolite from the roots and rhizomes of Podophyllum hexandrum . Their insecticidal activity was preliminarily evaluated against the pre-third-instar larvae of Mythimna separata in vivo. Compound 9g displayed the best promising insecticidal activity. It revealed that cleavage of the 6,7-methylenedioxy group of podophyllotoxin will lead to a less active compound and that the C-4 position of podophyllotoxin was the important modification location. A quantitative structure-activity relationship (QSAR) model was developed by genetic algorithm combined with multiple linear regression (GA-MLR). For this model, the squared correlation coefficient (R(2)) is 0.914, the leave-one-out cross-validation correlation coefficient (Q(2)(LOO)) is 0.881, and the root-mean-square error (RMSE) is 0.024. Five descriptors, BEHm2, Mor14v, Wap, G1v, and RDF020e, are likely to influence the biological activity of these compounds. Among them, two important ones are BEHm2 and Mor14v. This study will pave the way for further design, structural modification, and development of podophyllotoxin derivatives as insecticidal agents.

  15. Synthesis and biological activity of sulfur compounds showing structural analogy with combretastatin A-4

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Edson dos A. dos; Prado, Paulo C.; Carvalho, Wanderley R. de; Lima, Ricardo V. de; Beatriz, Adilson; Lima, Denis P. de, E-mail: [Universidade Federal de Mato Grosso do Sul (UFMS), Campo Grande, MS (Brazil). Departamento de Quimica; Hamel, Ernest [Screening Technologies Branch, Developmental Therapeutics Program, Division of Cancer Treatment and Diagnosis, National Cancer Institute at Frederick, National Institutes of Health, Frederick, MD (United States); Dyba, Marzena A. [Basic Science Program , SAIC-Frederick, Inc., Structural Biophysics Laboratory National Cancer Institute, Frederick, MD (United States); Albuquerque, Sergio [Universidade de Sao Paulo (USP), Ribeirao Preto, SP (Brazil). Faculdade de Ciencias Farmaceuticas


    We extended our previous exploration of sulfur bridges as bioisosteric replacements for atoms forming the bridge between the aromatic rings of combretastatin A-4. Employing coupling reactions between 5-iodo-1,2,3-trimethoxybenzene and substituted thiols, followed by oxidation to sulfones with m-CPBA, different locations for attaching the sulfur atom to ring A through the synthesis of nine compounds were examined. Antitubulin activity was performed with electrophoretically homogenous bovine brain tubulin, and activity occurred with the 1,2,3-trimethoxy-4-[(4-methoxyphenyl)thio]benzene (12), while the other compounds were inactive. The compounds were also tested for leishmanicidal activity using promastigote forms of Leishmania braziliensis (MHOM/BR175/M2904),and the greatest activity was observed with 1,2,3-trimethoxy-4-(phenylthio)benzene (10) and 1,2,3-trimethoxy-4-[(4-methoxyphenyl) sulfinyl]benzene (15). (author)

  16. Synthesis of novel 5-alkyl/aryl/heteroaryl substituted diethyl 3,4-dihydro-2H-pyrrole-4,4-dicarboxylates by aziridine ring expansion of 2-[(aziridin-1-yl-1-alkyl/aryl/heteroaryl-methylene]malonic acid diethyl esters

    Directory of Open Access Journals (Sweden)

    U. K. Syam Kumar


    Full Text Available A novel synthetic methodology has been developed for the synthesis of diethyl 5-alkyl/aryl/heteroaryl substituted 3,4-dihydro-2H-pyrrole-4,4-dicarboxylates (also called 2-substituted pyrroline-4,5-dihydro-3,3-dicarboxylic acid diethyl esters by iodide ion induced ring expansion of 2-[(aziridin-1-yl-1-alkyl/aryl/heteroaryl-methylene]malonic acid diethyl esters in very good to excellent yields under mild reaction conditions. The electronic and steric impact of the substituents on the kinetics of ring expansion of N-vinyl aziridines to pyrrolines has been studied. Various diversely substituted novel pyrroline derivatives have been synthesized by this methodology and the products can be used as key intermediates in the synthesis of substituted pyrrolines, pyrroles and pyrrolidines.

  17. Aromatic Character Studies on Divalent 3, 5 and 7-membered Rings C2H2M,C4H4M and C6H6M(M=C,Si,Ge,Sn and Pb)via Nucleus-independent Chemical Shifts (NICS) Calculation%通过核独立化学位移(NICS)计算研究二价三、五、七元环C2H2M,C4H4M and C6H6M(M=C,Si,Ge,Sn and Pb)的芳香族特性

    Institute of Scientific and Technical Information of China (English)

    Vessally E; Nikoorazm M; Ramazani A


    The aromatic character of divalent three, five and seven-membered rings C2H2M,C4H4 and C6H6M(M=C,Si, Ge, Sn and Pb) is investigated through magnetic and geometric criteria by Density Functional Theory (DFT) method using 6-311++G (3df,2p) basis set of the GAUSSIAN 98 program. The result of Nucleus-independent Chemical Shifts (NICS) (0.5) calculations show an aromatic character for singlet state of C2H2M,(M=C, Si, Ge, Sn and Sn) and nonaromatic character for triplet states of C2H2M (except M =Ge and Pb). NICS (0.5) calculations show nonaromatic character for the singlet state of C4H4C and antiaromatic character for C4H4M (M=Si, Ge, Sn and Pb). In contrast, NICS (0.5) calculations indicate antiaromatic character for the triplet state of C4H4C and nonaromatic character to C4H4M (M=Si, Ge, Sn and Pb). NICS (0.5) calculations show a slightly homoaromatic character for the singlet state of C6H6M and anti-aromatic character for triplet state of C6H6M.

  18. On semi ring bornologies (United States)

    Imran, A. N.; Rakhimov, I. S.; Husain, Sh. K. Said


    Our main focus in this work is to introduce new structure bornological semi rings. This generalizes the theory of algebraic semi rings from the algebraic setting to the framework of bornological sets. We give basic properties for this new structure. As well as, We study the fundamental construction of bornological semi ring as product, inductive limits and projective limits and their extensions on bornological semi ring. Additionally, we introduce the category of bornological semi rings and study product and pullback (fiber product) in the category of bornological semi rings.

  19. Medium-Ring Nitrogen Heterocycles through Migratory Ring Expansion of Metalated Ureas. (United States)

    Hall, Jessica E; Matlock, Johnathan V; Ward, John W; Gray, Katharine V; Clayden, Jonathan


    Simple benzo-fused nitrogen heterocycles (indolines, tetrahydroquinolines, and their homologues) undergo migratory ring expansion through deprotonation of their benzylic urea derivatives with lithium diisopropylamide (LDA) in the presence of N,N'-dimethylpropylideneurea (DMPU). The products of the reactions are benzodiazepines, benzodiazocines, and their homologues, with ring sizes of 8-12. The reactions tolerate a range of substituent patterns and types, and may exhibit enantiospecificity or diastereoselectivity. Considerable complexity is rapidly generated in an efficient synthesis of these otherwise difficult-to-obtain medium-ring nitrogen heterocycles.

  20. Application of Ionic Liquids with Carboxyl and Aromatic Ring Conjugated Anions in Dye-Sensitized Solar Cells%阴离子为羧酸根和芳环共轭的离子液体在染料敏化太阳能电池中的应用

    Institute of Scientific and Technical Information of China (English)

    王海; 徐雪青; 史继富; 徐刚


      提出了利用p-π共轭效应设计离子液体的方法, p-π共轭效应可以有效分散阴离子的负电荷,降低离子液体中阴阳离子之间的库仑引力,以得到低粘度的离子液体.所设计的离子液体为1-乙基-3-甲基咪唑苯甲酸(EMIB)和1-乙基-3-甲基咪唑异烟酸(EMIIN)(它们的阴离子中羧酸根和芳环为p-π共轭结构),这两种离子液体都达到了较低的粘度(EMIB为42 mPa·s, EMIIN为27 mPa·s).进一步将这两种离子液体做成电解质,应用在染料敏化太阳能电池中,通过优化电解质的组成, EMIB基电解质达到了1.43 mS·cm-1的电导率和1.45×10-7 cm2·s-1的I-3的扩散系数,而EMIIN基电解质的电导率和I-3扩散系数分别为1.63 mS·cm-1和2.01×10-7 cm2·s-1,后者电导性能的提高主要和EMIIN粘度较低有关系.进一步将这两种电解质组装成电池,在300 W·m-2的光强下测得EMIB基电池和EMIIN基电池的效率分别为2.85%和4.30%.%A method of utilizing p-π conjugation effects for obtaining low-viscosity ionic liquids is presented. p-π conjugation effectively disperses anionic charge and reduces Coulombic interactions. Ionic liquids prepared in this study were 1-ethyl-3-methylimidazolium benzoate (EMIB) and 1-ethyl-3-methylimidazolium isonicotinate (EMIIN). They have carboxyl and aromatic ring p-π conjugated anions, and achieve low viscosities of 42 and 27 mPa·s, respectively. EMIB and EMIIN were employed as electrolytes, which were used to construct dye-sensitized solar cel s (DSCs). After optimizing the composition, the ionic conductivity and tri odide ionic diffusion constant for the EMIB-based electrolyte were 1.43 mS·cm-1 and 1.45 × 10-7 cm2·s-1, respectively. For the EMIIN-based electrolyte, the ionic conductivity and tri odide ionic diffusion constant were 1.63 mS·cm-1 and 2.01×10-7 cm2·s-1, respectively. These were higher than the corresponding values for the EMIB-based electrolyte because of EMIINʹs lower