First Hyperpolarizability Evolutions of Some Extended Sesquifulvalene Compounds

Molecular orbital calculations of some extended sesquifulvalene compounds as O_n with olefins bridge and T_n with thiophenes bridge as well as their corresponding cyclopentadienyl‐iron(II) coordination compounds as IO_n and IT_n at the hybrid density functional theory level demonstrate that the dipole moment depends linearly on the molecular size (n), and the linear polarizability depends linearly on n² as well as the first hyperpolarizability also has a linear dependence on n³.     

Synthesis of aromatic polyesters and polyamides by alternating copolymerizations of 1,4-dicarbonyl-1,4-dihydronaphthalene with bezoquinones and benzoquinone diimines

1,4-Dicarbonyl-1,4-dihydronaphthalene ( 1 ) was synthesized by the dehydrochlorination reaction of 1,4-dihydronaphthalene-1,4-dicarbonyl chloride with triethylamine and obtained as its very dilute solution, but it easily polymerized in the concentration as high as 0.1 mol/L to give its polymer. 1 generated in situ by the dehydrochlorination reaction of 1,4-dihydronaphthalene-1,4-dicarbonyl chloride in a deoxygenated toluene polymerized alternatingly with benzoquinones such as 2-dodecylthio-p-benzoquinone, 2,5-di(tert-butyl)-p-benzoquinone, p-benzoquinone, and 2,3-dichloro-5,6-dicyano-p-benzoquinone, and with benzoquinone diimines such as N,N′-diethoxycarbonyl-p-benzoquinone diimine, N,N′-dibenzoyl-p-benzoquinone diimine, and N,N′-diphenyl-p-benzoquinone diimine to give aromatic polyesters and polyamides, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1929–1936, 1998     

Antioxidant activity and chemical composition of three Tunisian Cistus: Cistus monspeliensisCistus villosus and Cistus libanotis☆

The chemical composition of three rockrose Cistus species, Cistus monspeliensis, Cistus libanotis and Cistus villosus, collected in Tunisia, was studied by HPTLC, focusing on the terpenes and phenols constituents. Diterpenes of Cistus are important as the main constituents of the leaf sticky aromatic resin, known as labdanum, which are highly appreciated in perfumery. Polyphenols in the methanolic extracts of each species were identified, quantified as total and as flavonoids and tannins, and tested for antioxidant activity. Diterpenes were evident in C. libanotis and C. monspeliensis, whereas they were practically absent in C. villosus; C. libanotis had higher phenolic amount, whereas antioxidant activities were important, but different according to the following tests: DPPH radical scavenging, conversion of the Fe^3+/ferricyanide complex and inhibition of β-carotene bleaching. The reported data confirm the validity of utilisation of Cistus sp. in marketed herbal products, as well as the relevant presence of diterpenes in species actually not used for labdanum production.     

Antimicrobial activity of amino acid,imidazole, and sulfonamide derivatives of pyrazolo[3,4-d]pyrimidine

Derivatives of pyrazolo[3,4-d]pyrimidine with amino acid 3a–d , imidazole 4a–d , carbonyl 6–9 , pyrazole 10 , pyrazolone 11 , and sulfonamide 12–17 moieties were synthesized. Structure of the new compounds were established by their elemental analyses and spectral data. Some of the synthesized compounds were tested in vitro for their antimicrobial activity. Compounds 4b, 12 , and 16 were almost as potent as the standard antibiotic Chloramphenicol as positive control. Also, compounds 3b, 3c, 12 , and 16 were nearly as active as Terbinafine as positive control. © 2003 Wiley Periodicals, Inc. 15:57–62, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/.hc10212     

Dimeric Manganese-Catalyzed Hydroalkenylation of Alkynes with a Versatile Silicon-Based Directing Group

Herein, we present a manganese-catalyzed, branched-selective hydroalkenylation of terminal alkynes, under mild conditions through facile installation of a versatile silanol as a removable directing group. With an alkenyl boronic acid as the coupling partner, this reaction produces stereodefined (E,E)-1,3-dienes with high regio-, chemo- and stereoselectivity. The protocol features mild reaction conditions such as room temperature and an air atmosphere, while maintaining excellent functional group compatibility. The resulting 1,3-dienesilanol products serve as versatile building blocks, as the removal of the silanol group allows for the synthesis of both branched terminal 1,3-dienes for downstream coupling reactions, as well as stereoselective construction of linear (E,E)-1,3-dienes and (E,E,E)- or (E,E,Z)-1,3,5-trienes. In addition, a Diels–Alder cycloaddition can smoothly and selectively deliver silicon-containing pentasubstituted cyclohexene derivatives. Mechanistic investigations, in conjunction with DFT calculations, suggest a bimetallic synergistic activation model to account for the observed enhanced catalytic efficiency and good regioselectivity.     

Formation of polyimides by ?COOH and ?CN reactions

The synthesis of linear polyimides by the addition of dicarboxylic acids to dinitriles has been investigated. Adipic, suberic, m- and p-phenylenediacetic, isophthalic, and p-cyanobenzoic acids as well as adiponitrile, m- and p-phenylenediacetonitrile, and isophthalonitrile were studied. Fairly favorable results, low molecular weight polymers only, were obtained in the reaction of p-phenylenediacetic acid with p-phenylenediacetonitrile. The formation of polyimides seems to be restricted by the solubilities of the reactants and products as well as by the pK values of the starting dicarboxylic acid and of the acid which is formed.     

Fused Indacene Dimers

Polycyclic hydrocarbons consisting of two or more directly fused antiaromatic subunits are rare due to their high reactivity. However, it is important to understand how the interactions between the antiaromatic subunits influence the electronic properties of the fused structure. Herein, we present the synthesis of two fused indacene dimer isomers: s-indaceno[2,1-a]-s-indacene ( s -ID ) and as-indaceno[3,2-b]-as-indacene ( as -ID ), containing two fused antiaromatic s-indacene or as-indacene units, respectively. Their structures were confirmed by X-ray crystallographic analysis. ¹H NMR/ESR measurements and DFT calculations revealed that both s -ID and as -ID have an open-shell singlet ground state. However, while localized antiaromaticity was observed in s -ID , as -ID showed weak global aromaticity. Moreover, as -ID exhibited a larger diradical character and a smaller singlet-triplet gap than s -ID . All the differences can be attributed to their distinct quinoidal substructures.     

Energy-adjusted pseudopotentials for the rare earth elements

Nonrelativistic and quasirelativistic energy-adjusted pseudopotentials and optimized (7s6p5d)/[5s4p3d]-GTO valence basis sets for use in molecular calculations for fixed f-subconfigurations of the rare earth elements, La through Lu, have been generated. Atomic excitation and ionization energies from numerical HF, as well as SCF pseudopotential calculations using the derived basis sets, differ by less than 0.1 eV from numerical HF all-electron results. Corresponding values obtained from CI(SD), CEPA-1, as well as density functional calculations using the quasirelativistic pseudopotentials, are in reasonable agreement with experimental data.     

Development of the Peripheral Functionalization Chemistry of meso-Free Corroles

In contrast to the extensive development of the meso-functionalization of porphyrins, that of corroles had rarely been explored until the development of practical synthetic methods for meso-free corroles in 2015. The ready availability of meso-free corroles opened up meso-functionalization chemistry of corroles, giving rise to successful synthesis of various meso-substituted corroles such as meso-halogen, meso-nitro, meso-amino, meso-oxo, and meso-iminocorroles as well as meso–meso-linked corrole dimers and corrole tapes. In some cases, 2NH corroles exist as stable or transient radical species. The impact of meso-functionalization on the structures, electronic properties, optical characteristics, and aromaticity of corroles are highlighted in this Minireview.     

Stabilization of p-Phenylenebis(N-tert-butylaminoxyl) Relative to p-Benzoquinonediimine N,N′-Dioxide

Steric interactions between methoxy and tert -butyl groups are the reason that 2 only exists as p-phenylenebis(N-tert-butylaminoxyl) B . The p-phenylenebis(N-tert-butylaminoxyl) 1 has the p-quinonediimine N,N′-dioxide structure Q in solution as well as in the crystalline state.     

The isomers of phenalene and their singlet and triplet states: A Hartree–Fock and density functional computational investigation

Each of the isomers of phenalene, 1H-, 2H-, 3aH-, and 9bH-phenalene, as well as the cation, neutral radical, and anion in the phenalenyl system, have been examined at the Hartree–Fock 6-31G(d) and the density functional B3LYP/6-31G(d) levels of theory. The structures and properties of the phenalenes were determined as both singlets and triplets. While the data indicate that both the 9bH- and the 1H-isomer will exist as ground state singlets, the 2H- and 3aH-phenalenes are predicted to exist as ground state triplets; only the synthesis of the 1H-isomer has been reported in the literature. Structurally, 1H- and 2H-phenalene are planar systems, 3aH- and 9bH-phenalene are non-planar systems puckered at the saturated carbon, and the cation, neutral radical, and anion of phenalenyl are planar D_3h systems.     

Ferroelectric and piezoelectric properties of a quenched poly(vinylidene fluoride-trifluoroethylene) copolymer

The ferroelectric and piezoelectric properties of melt-quenched unoriented poly(vinylidene fluoride-trifluoroethylene) (73 : 27) copolymer films as a function of the number of poling cycles have been studied. The investigation revealed that quenched films exhibit a decrease in D-E hysteresis behavior as the number of poling cycles increases when the samples are poled at room temperature. Corresponding decreases in remanent polarization, Pr, as well as small increases in the coercive field, Ec, were observed as the material was subjected to successive poling cycles. The piezoelectric coefficients, d₃₁ and e₃₁, also decreased as the number of poling cycles increased. In addition, a clear reduction in the “apparent” Curie transition temperature between unpoled and poled material was observed. Preliminary evidence indicates that films quenched from the melt to below T_c do not form a stable ferroelectric crystal phase as previously believed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2671–2679, 1997     

The Overall Hyper-Wiener Index

The concept of overall connectivity of a graph G was extended here to the definition of the overall hyper-Wiener index OWW(G) of a graph G, defined as the sum of the hyper-Wiener indexes in all subgraphs of G, as well as the sum of eth-order terms, ^e OWW(G), with e being the number of edges in the subgraph. The potential usefulness of the overall hyper-Wiener index in QSAR/QSPR is evaluated by its correlation with a number of properties of C3-C8 alkanes and cycloalkanes.     

Photochemical reactions. 141st communication. Photochemistry of α,β-unsaturated δ,ϵ-epoxyketones of the ionone series

On n,π*- as well as on π,π*-excitation, the 4,5-epoxy-α-ionones (E)- 1 , (E)- 2 , and (E)- 3 undergo (E)/(Z)-isomerization and subsequent γ-H-abstraction leading to the corresponding 4-hydroxy-β-ionones (E/Z)- 9 , (E/Z)- 13 , and (E/Z)- 17 as primary photoproducts. On photolysis of (E)- 3 , as an additional primary photoproduct, the β,γ-unsaturated σ,?-epoxy ketone 18 was obtained. The other isolated compounds, namely the 2H-pyrans 10A + B and 14A + B as well as the retro γ-ionones 11 and 15A + B , represent known types of products, which are derived from the 4-hydroxy-β-ionones (E/Z)- 9 and (E/Z)- 13 , respectively.     

Ultrafast Spectroscopy of Hydroxy‐Substituted Azobenzenes in Water

Ultrafast UV/Vis pump/probe experiments on ortho‐, meta‐ and para‐hydroxy‐substituted azobenzenes (HO‐ABs), as well as for sulfasalazine, an AB‐based drug, were performed in aqueous solution. For meta‐HO‐AB, AB‐like isomerisation behaviour can be observed, whereas, for ortho‐HO‐AB, fast proton transfer occurs, resulting in an excited keto species. For para‐HO‐AB, considerable keto/enol tautomerism proceeds in the ground state, so after excitation the trans‐keto species isomerises into the cis form. Aided by TD‐DFT calculations, insight is provided into different deactivation pathways for HO‐AB, and reveals the role of hydroxy groups in the photochemistry of ABs, as well as their acetylation regarding sulfasalazine. Hydroxy groups are position‐specific substituents for AB, which allow tuning of the timescale of thermal relaxation, as well as the amount and contribution of the keto species to photochemical processes.     

Addition Reactions of Glycal Esters: Access to Glycosyl Donors of Kdo,d-glycero-d-talo- and d-glycero-d-galacto-2-Octulosonic Acid Residues

ABSTRACT

Addition reactions of O-acetylated glycal esters of Kdo mono-, α-(2→8)- and α-(2→4)- linked Kdo disaccharide derivatives 1a - c with NIS in acetic acid afforded good yields of trans-diaxial as well as minor amounts of trans-diequatorial and cis-configured 2-O-acetyl-3-deoxy-3-iodo derivatives, which were efficiently reduced with Bu₃SnH/AIBN to give the corresponding per-O-acetylated Kdo methyl ester derivatives. Similar reactions of 1a with NBS or NCS furnished the trans-diaxial 2-O-acetyl-3-bromo-3-deoxy- as well as 3-chloro-3-deoxy derivatives as the main products. Reaction of 1a with NBS in aqueous MeCN provided the 2,3-trans-bromohydrin derivative 11c, which upon treatment with DBU in MeCN gave the elimination product 11 and the α-2,3-anhydro derivative 12 as a suitable donor of glycosides with D-glycero-D-talo- or D-glycero-D-galacto configuration, respectively.     

First‐Principles Investigation of Anisotropic Electron and Hole Mobility in Heterocyclic Oligomer Crystals

Based on quantum chemistry calculations combined with the Marcus–Hush electron transfer theory, we investigated the charge‐transport properties of oligothiophenes (nTs) and oligopyrroles (nPs) (n=6, 7, 8) as potential p‐ or n‐type organic semiconductor materials. The results of our calculations indicate that 1) the nPs show intrinsic hole mobilities as high as or even higher than those of nTs, and 2) the vertical ionization potentials (VIPs) of the nPs are about 0.6–0.7 eV smaller than the corresponding VIPs of the nTs. Based on their charge‐transport ability and hole‐injection efficiency, the nPs have potential as p‐type organic semiconducting materials. Furthermore, it was also found that the maximum values of the electron‐transfer mobility for the nTs are larger by one‐to‐two orders of magnitude than the corresponding maximum values of hole‐transfer mobility, which suggests that the nTs have the potential to be developed as promising n‐type organic semiconducting materials owing to their electron mobility.     

LC–MS methods combination for identification and quantification of trans-sinapoylquinic acid regioisomers in green coffee

The present study aims to both identify and quantify trans-sinapoylquinic acid (SiQA) regioisomers in green coffee by combined UHPLC-ESI-QqTOF-MS/MS and UHPLC-ESI-QqQ-MS/MS methods. Among the various mono-acyl chlorogenic acids found in green coffee, SiQA regioisomers are the least studied despite having been indicated as unique phytochemical markers of Coffea canephora (known as Robusta). The lack of commercially available authentic standards has been bypassed by resorting to the advantages offered by high-resolution LC–MS as far as the identification is concerned. SiQA regioisomers have been identified in several samples of Robusta and Coffea arabica (known as Arabica) commercial lots from different geographical origin and, for the first time, in different samples of coffee wild species (Coffea liberica and Coffea pseudozanguebariae). Quantification (total SiQA ranging from 3 to 5 mg/100 g) let to reconsider these chlorogenic acids as unique phytochemical markers of Robusta being present in the same quantity and distribution in C. liberica as well. Gardeniae Fructus samples (fruits of Gardenia jasminoides) have additionally been characterized as this matrix is recognized as one of the few naturally occurring SiQA sources. The SiQA regioisomer content (total SiQA about 80 mg/100 mg) fully supports the proposal to use this matrix as a surrogate standard for further studies.     

Radical polymerization of N-substituted itaconamic esters and itaconamides

Two kinds of itaconamic esters, α-substituted acrylate derivatives (IAE-I) and α-substituted acrylamide derivatives (IAE-II), as well as itaconamides (IAm) were prepared and polymerized with a radical initiator. It has been revealed that N,N-disubstituted IAE-I as an acrylate is more reactive in polymerization than N,N-disubstituted IAE-II as an acrylamide and that N,N′-dialkyl substituted IAm homopolymerizes but N,N,N′,N′;-tetraalkyl substituted one does not. In radical copolymerization with styrene, IAE-I showed a higher polymerization reactivity than IAE-II. The effects of the N-substituents on the polymerization reactivity were discussed on the basis of conformation of the monomers. The polymers obtained were also characterized. © 1994 John Wiley & Sons, Inc.     

Calculation of scattering-patterns of ordered nano- and mesoscale materials

Analytical expressions for the scattering patterns of ordered nano- and mesoscopic materials are derived and compared to measured scattering patterns. Ordered structures comprising spheres (fcc, bcc, hcp, sc, and bct), cylinders (hex and sq), lamellae (lam) and vesicles, as well as bicontinuous cubic structures (Ia3d, Pn3m, and Im3m) are considered. The expressions take into account unit cell dimensions, particle sizes and size distributions, lattice point deviations, finite domain sizes, orientational distributions, core/shell-structures as well a variety of peak shapes. The expressions allow to quantitatively describe, model and even fit measured SAXS and SANS-patterns of ordered or oriented micellar solutions, lyotropic phases, block copolymers, colloidal solutions, nanocomposites, photonic crystals, as well as mesoporous materials.