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981.
The pure rotational J + 1 ← J transitions, with J = 0, 1, 3-8, of H13CN have been observed in the millimeter- and submillimeter-wave region using the Lamb-dip technique to resolve the hyperfine structure due to H, 13C, and 14N. The present observations allow us to provide for the first time the spin-rotation constant of 13C and the spin-spin interaction constant S12 (between H and 13C) as well as to remarkably improve the quadrupole coupling and spin-rotation constants of 14N. In addition, a good empirical estimation of CI(H), based on ab initio calculations, has also been provided. Furthermore, our frequencies together with previous data permit to determine the most accurate ground state rotational parameters known up to now. 相似文献
982.
983.
984.
985.
Dr. Martín Regueiro‐Figueroa Dr. Aline Nonat Dr. Gabriele A. Rolla Dr. David Esteban‐Gómez Dr. Andrés de Blas Dr. Teresa Rodríguez‐Blas Dr. Loïc J. Charbonnière Prof. Mauro Botta Dr. Carlos Platas‐Iglesias 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(35):11696-11706
Homodinuclear lanthanide complexes (Ln=La, Eu, Gd, Tb, Yb and Lu) derived from a bis‐macrocyclic ligand featuring two 2,2′,2′′‐(1,4,7,10‐tetraazacyclododecane‐1,4,7‐triyl)triacetic acid chelating sites linked by a 2,6‐bis(pyrazol‐1‐yl)pyridine spacer (H2L3) were prepared and characterized. Luminescence lifetime measurements recorded on solutions of the EuIII and TbIII complexes indicate the presence of one inner‐sphere water molecule coordinated to each metal ion in these complexes. The overall luminescence quantum yields were determined (?=0.01 for [Eu2(L3)] and 0.50 for [Tb2(L3)] in 0.01 M TRIS/HCl, pH 7.4; TRIS=tris(hydroxymethyl)aminomethane), pointing to an effective sensitization of the metal ion by the bispyrazolylpyridyl unit of the ligand, especially with Tb. The nuclear magnetic relaxation dispersion (NMRD) profiles recorded for [Gd2(L3)] are characteristic of slowly tumbling systems, showing a low‐field plateau and a broad maximum around 30 MHz. This suggests the occurrence of aggregation of the complexes giving rise to slowly rotating species. A similar behavior is observed for the analogous GdIII complex containing a 4,4′‐dimethyl‐2,2′‐bipyridyl spacer ([Gd2(L1)]). The relaxivity of [Gd2(L3)] recorded at 0.5 T and 298 K (pH 6.9) amounts to 13.7 mM ?1 s?1. The formation of aggregates has been confirmed by dynamic light scattering (DLS) experiments, which provided mean particle sizes of 114 and 38 nm for [Gd2(L1)] and [Gd2(L3)], respectively. TEM images of [Gd2(L3)] indicate the formation of nearly spherical nanosized aggregates with a mean diameter of about 41 nm, together with some nonspherical particles with larger size. 相似文献
986.
Saeid Sadeh Dr. Gabriele Schatte Prof. Dr. Jens Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13408-13417
The enantiomerically pure dibromoferrocene 3 [(Sp,Sp)‐1,1′‐dibromo‐2,2′‐di(isopropyl)ferrocene], equipped with two iPr groups in α positions, was prepared using known “Ugi amine” chemistry. Species 3 was targeted in order to gain access to new [1]ferrocenophanes ([1]FCPs) to be used as monomers for ring‐opening polymerization. The iPr groups on the sandwich unit were introduced to stabilize bridging moieties, as well as to increase solubilities of targeted metallopolymers. The planar chiral dibromide 3 can quantitatively be lithiated at 0 °C [2 equiv nBuLi, hexanes/thf (9:1), 30 min]. Salt‐metathesis reactions with respective element dichloride species gave chiral [1]FCPs with a variety of bridging moieties [ERx=Ga[2‐(Me2NCH2)C6H4] ( 4 a ), SiMe2 ( 4 b ), SntBu2 ( 4 c ), BNiPr2 ( 4 d )]. The new [1]FCPs were fully characterized including single‐crystal X‐ray analysis. The stabilizing iPr groups on the Cp rings increase the thermal stabilities of 4 b – d compared to known [1]FCPs, equipped with the same bridging moieties. All three compounds 4 b – d are volatile and could be isolated by vacuum sublimation. Our new approach to [1]FCPs has the potential to overcome many of the existing difficulties in ferrocenophane chemistry, such as limited stability of starting monomers and low solubilities of resulting polyferrocenes. 相似文献
987.
Dr. Gabriele Di Carlo Dr. Alessio Orbelli Biroli Prof. Maddalena Pizzotti Dr. Francesca Tessore Dr. Vanira Trifiletti Dr. Riccardo Ruffo Prof. Alessandro Abbotto Dr. Anna Amat Dr. Filippo De Angelis Prof. Patrizia R. Mussini 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(32):10723-10740
A facile and fast approach, based on microwave‐enhanced Sonogashira coupling, has been employed to obtain in good yields both mono‐ and, for the first time, disubstituted push–pull ZnII porphyrinates bearing a variety of ethynylphenyl moieties at the β‐pyrrolic position(s). Furthermore, a comparative experimental, electrochemical, and theoretical investigation has been carried out on these β‐mono‐ or disubstituted ZnII porphyrinates and meso‐disubstituted push–pull ZnII porphyrinates. We have obtained evidence that, although the HOMO–LUMO energy gap of the meso‐substituted push–pull dyes is lower, so that charge transfer along the push–pull system therein is easier, the β‐mono‐ or disubstituted push–pull porphyrinic dyes show comparable or better efficiencies when acting as sensitizers in DSSCs. This behavior is apparently not attributable to more intense B and Q bands, but rather to more facile charge injection. This is suggested by the DFT electron distribution in a model of a β‐monosubstituted porphyrinic dye interacting with a TiO2 surface and by the positive effect of the β substitution on the incident photon‐to‐current conversion efficiency (IPCE) spectra, which show a significant intensity over a broad wavelength range (350–650 nm). In contrast, meso‐substitution produces IPCE spectra with two less intense and well‐separated peaks. The positive effect exerted by a cyanoacrylic acid group attached to the ethynylphenyl substituent has been analyzed by a photophysical and theoretical approach. This provided supporting evidence of a contribution from charge‐transfer transitions to both the B and Q bands, thus producing, through conjugation, excited electrons close to the carboxylic anchoring group. Finally, the straightforward and effective synthetic procedures developed, as well as the efficiencies observed by photoelectrochemical measurements, make the described β‐monosubstituted ZnII porphyrinates extremely promising sensitizers for use in DSSCs. 相似文献
988.
Dr. Markus Horn Dr. Ludwig H. Schappele Dr. Gabriele Lang‐Wittkowski Prof. Dr. Herbert Mayr Dr. Armin R. Ofial 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(1):249-263
Rates of hydride transfer from several hydride donors to benzhydrylium ions have been measured at 20 °C and used for the determination of empirical nucleophilicity parameters N and sN according to the linear free energy relationship log k20 °C=sN(N+E). Comparison of the rate constants of hydride abstraction by tritylium ions with those calculated from the reactivity parameters sN, N, and E showed fair agreement. Therefore, it was possible to convert the large number of literature data on hydride abstraction by tritylium ions into N and sN parameters for the corresponding hydride donors, and construct a reactivity scale for hydride donors covering more than 20 orders of magnitude. 相似文献
989.
Graziano Baccolini Carla Boga Gabriele Micheletti 《Phosphorus, sulfur, and silicon and the related elements》2013,188(11):2303-2315
In this article, we present a study about the non-enzymatic hydrolysis of phosphoenolpyruvate (PEP) by following the reaction course through 31P NMR spectroscopy. We have demonstrated that PEP in water exists mainly as a very stable cyclic pentacoordinate phosphorus compound in equilibrium with other cyclic forms. This explains the PEP stability in water. In contrast, after addition of an alcohol to a PEP aqueous solution, other very unstable cyclic pentacoordinated intermediates are formed, which immediately collapse, giving a feasible phosphorylation of the alcohol. It is known that cyclic pentacoordinated phosphorus intermediates are favored over the corresponding acyclic intermediates by a factor of 106–108, and this preference, found also in this study, might be the “driver mechanism” able to overcome the clutter of abiotic chemistry, thus permitting formation of pre-RNA molecules probably with a “self-organized process.” 相似文献
990.
Alice Senizza Gabriele Rocchetti Juana I. Mosele Vania Patrone Maria Luisa Callegari Lorenzo Morelli Luigi Lucini 《Molecules (Basel, Switzerland)》2020,25(23)
Plant polyphenols are a broad group of bioactive compounds characterized by different chemical and structural properties, low bioavailability, and several in vitro biological activities. Among these compounds, lignans (a non-flavonoid polyphenolic class found in plant foods for human nutrition) have been recently studied as potential modulators of the gut–brain axis. In particular, gut bacterial metabolism is able to convert dietary lignans into therapeutically relevant polyphenols (i.e., enterolignans), such as enterolactone and enterodiol. Enterolignans are characterized by various biologic activities, including tissue-specific estrogen receptor activation, together with anti-inflammatory and apoptotic effects. However, variation in enterolignans production by the gut microbiota is strictly related to both bioaccessibility and bioavailability of lignans through the entire gastrointestinal tract. Therefore, in this review, we summarized the most important dietary source of lignans, exploring the interesting interplay between gut metabolites, gut microbiota, and the so-called gut–brain axis. 相似文献