RESUMO
A series of (13)C-labeled polyaromatic hydrocarbons (PAHs), fluorenols and phenanthrenols were synthesized from commercially available (13)C-labeled starting material giving rise to M + 6 isotopomers. This was accomplished using key palladium-catalyzed cross-coupling and one-carbon homologation strategies. The conditions for these reactions were optimized, and the new chemical routes are efficient in the number of chemical steps, can be scaled to afford gram quantities and occur in good yields based on the (13)C label. These labeled compounds as precursors for more complex PAHs and are useful as internal standards in mass spectrometry and NMR spectroscopy studies for monitoring environmental contamination and biological exposure to PAHs and their metabolites.
Assuntos
Fluorenos/síntese química , Fenantrenos/síntese química , Radioisótopos de Carbono/química , Catálise , Marcação por Isótopo/métodos , Espectrometria de Massas/normas , Paládio/química , Valores de ReferênciaRESUMO
Understanding variation in physiological traits across taxa is a central question in evolutionary biology that has wide-ranging implications in biomedicine, disease ecology, and environmental protection. Sialic acid (Sia), and in particular, 5-N-acetylneuraminic acid (Neu5Ac), is chemically bound to galactose and the underlying glycan via α2-3 or α2-6 glycosidic linkage (i.e., Siaα2-3Galactose or Siaα2-6Galactose), conferring two different cell surface structures that affects cell to cell communication and interactions with foreign agents including microparasites and toxins. As an initial step towards understanding variation of Sia across the class Aves, we collected red blood cells (RBCs or erythrocytes) and measured Sia quantity in 76 species and 340 individuals using HPLC-MS/MS and glycosidic linkage type in 24 species and 105 individuals using hemagglutination assay. Although Sia quantity did not, α2-6 glycosidic linkage did exhibit a discernable phylogenetic pattern as evaluated by a phylogenetic signal (λ) value of 0.7. Sia quantity appeared to be higher in after hatch year birds than hatch year birds (Pâ¯<â¯0.05); moreover, ~80% of the measured Sia across all individuals or species was expressed by ~20% of the individuals or species. Lastly, as expected, we detected a minimal presence of 5-N-glycolylneuraminic acid in the avian RBCs tested. These data provide novel insights and a large baseline dataset for further study on the variability of Sia in the class Aves which might be useful for understanding Sia dependent processes in birds.
Assuntos
Aves/metabolismo , Eritrócitos/metabolismo , Ácidos Siálicos/metabolismo , Animais , Aves/classificação , Eritrócitos/química , Ácidos Siálicos/química , Especificidade da EspécieRESUMO
Oligosaccharides, such as starch, cellulose, and hemicelluloses, are abundant and easily obtainable bio-derived materials that can potentially be used as precursors for fuels and chemical feedstocks. To access the pertinent molecular building blocks (i.e., 5- or 6-carbon containing sugar units) located within these biopolymers and transform them into useful fuel precursors, oligosaccharide depolymerization followed by chain extension is required. This chain extension can readily be performed via a Garcia-Gonzalez-like approach using ß-diketones under mild conditions to provide fuel precursors containing an increased carbon atom content that meets fuel requirements. In a subsequent step, ring opening and hydrodeoxygenation chemistry of these species allows for the preparation of branched alkanes under relatively mild conditions. This approach can be applied to monomeric sugars (glucose and xylose), oligosaccharides (starch), and potentially to hydrolyzed dedicated energy crops to allow the conversion of real biomass into fuel type molecules.
Assuntos
Glucose/química , Hidrocarbonetos/química , Amido/química , Xilose/química , Catálise , Cetonas/química , PolimerizaçãoRESUMO
Triazenes (RN=N-NR'R") are a class of compounds that hold much promise in preparative chemistry as they are reactive groups which are both stable and adaptable to numerous synthetic transformations. Useful to scientists in pharmacology, total synthesis, polymer technology, and the construction of novel ring systems, to name a few areas, triazenes also have a tendency to surprise chemists with new reactions and increasing applicability. This review highlights some of the recent advances and diversity possible with these types of systems.
Assuntos
Antineoplásicos Alquilantes/química , Triazenos/química , Antineoplásicos Alquilantes/farmacologia , Técnicas de Química Combinatória , Triazenos/farmacologiaRESUMO
Manganese acetate was found to catalyze the oxidative delignification of wood with hydrogen peroxide at room temperature. The delignification reaction was monitored by optical and Raman microscopy, and liquid chromatography/mass spectrometry. When exposed to H(2)O(2) and Mn(OAc)(3) in aqueous solution, poplar wood sections were converted into a fine powder-like material which consisted of individual wood cells within 4 days at room temperature and without agitation. Optical and Raman microscopy provided the spatial distribution of cellulose and lignin in the wood structure, and showed the preferential oxidation of lignin-rich middle lamellae. Raman spectra from the solid residue revealed a delignified and cellulose-rich material. Glucose yields following enzymatic hydrolysis were 20-40% higher in poplar sawdust pretreated with Mn(OAc)(3) for 2, 4, and 7 days at room temperature than those in sawdust exposed to water only for identical durations, suggesting the viability of this mild, inexpensive method for pretreatment of lignocellulosic biomass.
Assuntos
Acetatos/química , Peróxido de Hidrogênio/química , Lignina/química , Lignina/isolamento & purificação , Compostos de Manganês/química , Populus/química , Madeira/química , Catálise , Oxirredução , TemperaturaRESUMO
The cyclization of (2-ethynylphenyl)triazenes in ODCB at 200 degrees C gives exclusively cinnolines, whereas addition of CuCl to 1,2-dichloroethane solutions of the triazenes at 50 degrees C results in the sole formation of isoindazoles. DFT calculations and deuterium labeling studies suggest the intermediacy of a 3-dehydrocinnolinium ion, produced through a pericyclic transition state. Calculations and trapping studies strongly implicate a carbene intermediate in isoindazole formation, which proceeds through a pseudocoarctate transition state.
Assuntos
Compostos Heterocíclicos/síntese química , Triazenos/química , Indazóis/química , TermodinâmicaRESUMO
A new route to isoindazoles and cinnolines through the cyclization of (2-alkynylphenyl)triazenes under neutral conditions is presented. The products that result from heating the starting triazenes depend on both the type of alkyne ortho to the triazene functionality and the temperature used. Butadiyne moieties ortho to dialkyltriazenes yield bis-isoindazole dimers when heated to 150 degrees C in MeI. A requirement for cyclization in MeI is that the (2-alkynylphenyl)triazene must contain a suitably electron-withdrawing substituent on the phenyl ring to deactivate the triazene toward methylation-induced decomposition to an iodoarene. Ethynyl moieties ortho to dialkyltriazenes yield both isoindazole dimers as well as 3-formylisoindazoles when subjected to the same conditions. Replacing MeI with 1,2-dichlorobenzene as solvent allows for the general cyclization of (2-ethynylphenyl)dialkyltriazenes. Heating to 170 degrees C results in a mixture of isoindazole and cinnoline products, whereas the cinnolines are produced exclusively in high yield at 200 degrees C. Alternatively, the isoindazoles can be obtained in good to excellent yield by stirring a 1,2-dichloroethane solution of the starting triazene with CuCl overnight at 50 degrees C.
RESUMO
The mechanistic aspects of the cyclization of (2-ethynylphenyl)triazenes under both thermal and copper-mediated conditions are reported. For cyclization to an isoindazole, a carbene mechanistic pathway is proposed. The carbene intermediate can react with oxygen, dimerize to give an alkene, or be trapped either intermolecularly (using 2,3-dimethyl-2-butene to generate a cyclopropane) or intramolecularly (using a biphenyl moiety at the terminus of the acetylene to form a fluorene). Density-functional theory (DFT) calculations support a pseudocoarctate pathway for this type of cyclization. Thermal cyclization to give a cinnoline from (2-ethynylphenyl)triazenes is proposed to occur through a pericyclic pathway. DFT calculations predict a zwitterionic dehydrocinnolinium intermediate that is supported by deuterium trapping studies as well as cyclizations performed using a 2,2,6,6-tetramethylpiperidine moiety at the 3-position of the triazene.
RESUMO
Stable isotope-labeled N-acyl selones have been constructed in fewer than four steps from readily available starting materials. Site-specific labeling was achieved using the following synthons: bromo[2-(13)C]acetic acid, [(13)C]formic acid, and elemental (77)Se. These labeled selones have been found to provide unique insights into enolate structure and may be useful in the detection and quantitation of remotely disposed chiral centers in compounds in short supply.
Assuntos
Compostos de Selênio/química , Isótopos de Carbono , Isótopos , Espectroscopia de Ressonância Magnética , Estrutura MolecularRESUMO
Our group has used Ti-promoted aldol additions with an oxazolidineselone as the chiral auxiliary with much success. In these reactions, the Se atom in the auxiliary both promotes stereospecific addition as well as reports on, through the use of 77Se NMR spectroscopy, the ratio of diastereomers produced and the geometry of intermediates as the reaction proceeds. Through stable isotope labeling and NMR spectroscopy, we are able to experimentally observe a Ti enolate in solution and gain insight into its structure and reactivity. Results from molecular modeling calculations are also presented for comparison with NMR data.
Assuntos
Compostos Organometálicos/química , Compostos Organosselênicos/química , Oxazóis/química , Titânio/química , Isótopos de Carbono , Marcação por Isótopo , Isótopos , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Conformação Molecular , Compostos Organosselênicos/síntese química , Oxazóis/síntese química , Selênio , Soluções , TermodinâmicaRESUMO
A series of isoindazole-C(60) dyads 4a-c based on pyrazolino[60]fullerene have been prepared by 1,3-dipolar cycloadditions of the nitrile imines, generated in situ from hydrazones 3a-c, to C(60). Molecular orbital calculations for 4b revealed that the electron distribution of the HOMO is located on the isoindazole moiety, while the electron distribution of the LUMO is located on the C(60) moiety. Electrochemical properties of the new dyads 4a-c show a similar electron affinity with respect to C(60). Charge-transfer interactions in the ground state between the isoindazole ring and the fullerene cage are predicted by the molecular orbital calculations and confirmed by electrochemical studies in 4a,b. Steady-state fluorescence emission spectra of dyads 4a-c show that fluorescence intensities in polar benzonitrile solvent decrease with increasing electron-donating ability of the substituent attached on the isoindazole group. This was confirmed by the shortening of fluorescence lifetimes, from which intramolecular charge-separation rates and efficiencies via the excited singlet states of the fullerene moiety were evaluated. The yields of the triplet states in polar solvent decrease with the electron-donating ability, supporting the competitive formation of the charge-separated state with the intersystem crossing from the excited states. Thus, isoindazole[60]fullerene 4b can be considered a molecular switch with an AND logic gate.
RESUMO
The synthesis and study of dehydrobenzoannulene (DBA)-dimethyldihydropyrene (DDP) hybrids as models for the investigation of aromaticity in weakly diatropic systems is reported. Three new monofused DBA-DDP hybrids have been synthesized, and their NMR spectra are discussed with regard to quantifying the aromaticity remaining in multibenzene-fused DBAs. Nucleus-independent chemical shifts, determined at a series of locations for each compound, bond lengths, and (1)H and (13)C NMR chemical shifts were calculated and used to probe the aromaticity of these hybrids. Systems where more than one annulene/DBA is fused to the DDP core have also been obtained, and their potential use in photoinduced isomerization applications is discussed.