Anthocyanin identification and composition of wild Vitis spp. accessions by using LC–MS and LC–NMR

The composition and concentration of anthocyanins of grape berry skins were analyzed in order to assess phenotypic variation between four grape wine varieties belonging to 4 different species: Vitis vinifera, Vitis amurensis, Vitis cinerea and Vitis X champinii. High-performance liquid chromatography coupled to mass spectrometry (LC–MS) and NMR spectroscopy (LC–NMR) were used to separate and identify the structure of anthocyanins present in these species. Combination of LC–MS and LC–NMR data resulted in the identification of 33 anthocyanins. In particular, newly reported cis isomers of p-coumaric-derivatives were identified (petunidin-, peonidin- and malvidin-3-(6-p-coumaroyl)-5-diglucoside). In V. cinerea and V. vinifera, anthocyanins were monoglucoside derivatives whereas in V. amurensis and V. X champinii, both mono- and diglucoside derivatives were identified. Malvidin-, delphinidin- and petunidin-derivatives were, respectively, the most abundant components in V. cinerea and V. vinifera, V. amurensis and V. X champinii.     

Three-component synthesis of functionalized five-membered ring lactones under Barbier-like conditions

Five-membered ring lactones have been synthesized using a straightforward three-component reaction among in situ-generated arylzinc reagents, dimethyl itaconate and aromatic aldehydes. This Barbier-like procedure, which is characterized by its simplicity, allows the concise synthesis of a range of highly functionalized 4,5-substituted γ-butyrolactones.     

Non-abelian differentiable gerbes

We study non-abelian differentiable gerbes over stacks using the theory of Lie groupoids. More precisely, we develop the theory of connections on Lie groupoid G-extensions, which we call “connections on gerbes”, and study the induced connections on various associated bundles. We also prove analogues of the Bianchi identities. In particular, we develop a cohomology theory which measures the existence of connections and curvings for G-gerbes over stacks. We also introduce G-central extensions of groupoids, generalizing the standard groupoid S¹-central extensions. As an example, we apply our theory to study the differential geometry of G-gerbes over a manifold.     

Exploring the coordination chemistry of MOF-graphite oxide composites and their applications as adsorbents

Metal-organic frameworks (MOFs), besides being porous materials exhibit a very rich chemistry, which can be used for the synthesis of composites and/or the reactive adsorption of toxic gases. In this study, composites of MOFs (MOF-5, HKUST-1 or MIL-100(Fe)) and a graphitic compound (graphite or graphite oxide, GO) were synthesized and tested for the removal of NH(3), H(2)S and NO(2) under ambient conditions. The materials were characterized before and after exposure to the target gases by X-ray diffraction, thermogravimetric analysis, N(2) sorption measurement and FT-IR spectroscopy. The results indicate that strong chemical bonds exist between the MOF and GO as a result of the coordination between the GO oxygen groups and the MOFs' metallic centers. Depending on the structure of the MOF, such interactions induce the formation of a new pore space in the interface between the carbon layers and the MOF units, which enhances the physical adsorption capacity of the toxic gases. When unsaturated metallic sites are present in the MOFs, the target gases are also adsorbed via coordination to these centers. Further reaction with the framework leads to the formation of complexes. This is accompanied by the collapse of the MOF structure.     

Rhenium complexes bearing phosphole-pyridine chelates: simple molecules with large chiroptical properties

The synthesis and chiroptical properties of chiral rhenium complexes bearing mono- or di-topic phosphole ligands are described.     

Stepping towards highly flexible aptamers: enzymatic recognition studies of unlocked nucleic acid nucleotides

Enzymatic recognition of unlocked nucleic acid (UNA) nucleotides was successfully accomplished. Therminator DNA polymerase was found to be an efficient enzyme in primer extension reactions. Polymerase chain reaction (PCR) amplification of a 81 mer UNA-modified DNA library was efficiently achieved by KOD DNA polymerase.     

Single-molecule SERS detection of C60

Single-molecule Surface-Enhanced Raman Scattering (SERS) detection of buckminsterfullerene (C(60)) is achieved by using different isotopologues of the molecule with a distribution around an average isotopic substitution ((12)C → (13)C) of ~30%. The distribution of different isotopologues creates a broad (~20 cm(-1)) average SERS signal within which single-molecule SERS spectra of individual isotopic realizations of the molecule can be distinguished. The SERS enhancement factors for SM-SERS C(60) events are typically in the range of ~10(8), suggesting a limitation imposed by either photobleaching or surface interactions with the (Ag) metallic colloids to reach the highest SERS hot-spots (which can typically have larger maximum enhancements). SM-SERS signals of isotopically substituted C(60) also show broader peaks (FWHM ≈ 4 cm(-1)) than equivalent signals in natural C(60). The latter feature suggests a contribution to the homogeneous broadening coming from isotopic disorder in the molecule; a feature that can only be observed with the ability to detect single-molecule spectra.     

Dipole of the luminosity distance: a direct measure of H(z)

We show that the dipole of the luminosity distance is a useful observational tool which allows us to determine the Hubble parameter as a function of redshift H(z). We determine the number of supernovae needed to achieve a given precision for H(z) and to distinguish between different models for dark energy. We analyze a sample of nearby supernovae and find a dipole consistent with the cosmic microwave background at a significance of more than 2alpha.     

Iron porphyrin-cyclodextrin supramolecular complex as a functional model of myoglobin in aqueous solution

The 1:1 inclusion complex of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphinato iron(II) (Fe(II)TPPS) and an O-methylated beta-cyclodextrin dimer having a pyridine linker (1) binds dioxygen reversibly in aqueous solution. The O2 adduct was very stable (t(1/2) = 30.1 h) at pH 7.0 and 25 degrees C. ESI-MS and NMR spectroscopic measurements and molecular mechanics (MM) calculations indicated the inclusion of the sulfonatophenyl groups at the 5- and 15-positions of Fe(III)TPPS or Fe(II)TPPS into two cyclodextrin moieties of 1 to form a supramolecular 1:1 complex (hemoCD1 for the Fe(II)TPPS complex), whose iron center is completely covered by two cyclodextrin moieties. Equilibrium measurements and laser flash photolysis provided the affinities ( and ) and rate constants for O2 and CO binding of hemoCD1 (k(O2)(on), k(O2)(off), k(CO)(on), and k(CO)(off)). The CO affinity relative to the O2 affinity of hemoCD1 was abnormally high. Although resonance Raman spectra suggested weak back-bonding of d(pi)(Fe) --> pi(CO) and hence a weak CO-Fe bond, the CO adduct of hemoCD1 was very stable. The hydrophobic CO molecule dissociated from CO-hemoCD1 hardly breaks free from a shallow cleft in hemoCD1 surrounded by an aqueous bulk phase leading to fast rebinding of CO to hemoCD1. Isothermal titration calorimetry furnished the association constant (K(O2)), DeltaH degrees , and DeltaS degrees for O2 association to be (2.71 +/- 0.51) x 10(4) M(-1), -65.2 +/- 4.4 kJ mol(-1), and -133.9 +/- 16.1 J mol(-1) K(-1), respectively. The autoxidation of oxy-hemoCD1 was accelerated by H+ and OH-. The inorganic anions also accelerated the autoxidation of oxy-hemoCD1. The O2-Fe(II) bond is equivalent to the O2.--Fe(III) bond, which is attacked by the inorganic anions or the water molecule to produce met-hemoCD1 and a superoxide anion.