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71.
Silvestrini E Michelozzi M Skroppa T Brancaleoni E Ciccioli P 《Journal of chromatography. A》2004,1034(1-2):183-189
Head-space sampling (HS) has been combined with enantioselective gas chromatography (GC) for the analysis of chiral and non-chiral monoterpenes present in the cortical tissues of five different Norway spruce clones. (1S)-(-)-alpha-Pinene, (1S,5S)-(-)sabinene, (1S)-(-)-beta-pinene, and (4S)-(-)limonene dominated over (1R)-(+)-alpha-pinene, (1R,5R)-(+)-sabinene, (1R)-(+)-beta-pinene, and (4R)-(+)-limonene. Results showed a large variation in the enantiomeric composition of cortical tissues between different clones. The development of HS-GC greatly increased the speed of precise analyses of chiral monoterpenes in small samples and therefore offer excellent opportunities in studies on the ecophysiological and chemotaxomic roles of these chiral components. 相似文献
72.
Irene Conti Marco Garavelli 《Journal of photochemistry and photobiology. A, Chemistry》2007,190(2-3):258-273
The effect of substitution on the intrinsic (i.e. in vacuo) photoisomerization ability of retinal chromophore models has been explored using CASPT2//CASSCF minimum energy path computations to map the S1 photoisomerization paths of two substituted minimal models of the retinal chromophore: the 2-cis-penta-2,4-dieniminium and the all-trans-epta-2,4,6-trieniminium cations, which have been modified using fluorine or methoxyl substituents as representative examples of electron-withdrawing and electron-releasing groups, respectively. A systematic analysis has been performed involving substitutions in all the possible positions along the chain. It is shown that the photochemical reactivity and photoisomerization efficiency of these systems may be tuned or indeed changed, although this effect strongly depends on the position of the substituent. In particular, we have shown that (i) most of the systems preserves qualitatively the reactivity of the parent (i.e. unsubstituted) compound; (ii) substitution at positions C4 or C6 leads to a different relaxed excited state structure of the chromophore and in general to a very flat photoisomerization path (or to a tiny S1 energy barrier in some cases); (iii) the nature of the TICT state (i.e. the S1 → S0 decay funnel) may be turned from a conical intersection into an excited state minimum; (iv) for the C4 methoxy-substituted system the isomerization path as well as the S1/S0 decay funnel involve an unusual torsional angle. Thus, substitution turns out to be a good tool not only to tune the optical properties (i.e. the absorption and emission features) of the chromophore (as we have already shown in a previous work: I. Conti, F. Bernardi, G. Orlandi, M. Garavelli, Mol. Phys. 104 (2006) 915–924), but it may also play a crucial role in tuning and controlling photoisomerization selectivity and efficiency, affecting excited state lifetime and reaction rate. A rationale for these effects is presented, which provides a basis for understanding reactivity properties and the intrinsic photochemical behavior of substituted retinal chromophores. 相似文献
73.
Zusammenfassung Es werden einige Versuche an Kaninchen und Menschen über die Millon'sche Reaktion des Harns mitgeteilt. Ihre Intensität steigt an, wenn Tyrosin zugeführt wird, und zwar erheblich mehr nach dl-Tyrosin als nach l-Tyrosin. Ein Teil der Millon-Substanzen ist in Äther löslich, der ebenfalls nach der razemisierten stärker zunimmt als der nach der natürlichen Aminosäure. 相似文献
74.
Correa NM Zorzan DH D'Anteo L Lasta E Chiarini M Cerichelli G 《The Journal of organic chemistry》2004,69(24):8231-8238
Kinetics of the reduction of 3-chloroacetophenone (CAF) with sodium borohydride (NaBH(4)) were followed by UV-vis spectroscopy at 27.0 degrees C in different reverse micellar media, toluene/BHDC/water and toluene/AOT/water, and compared with results in an isooctane/AOT/water reverse micellar system. AOT is sodium 1,4-bis-2-ethylhexylsulfosuccinate, and BHDC is benzyl-n-hexadecyl dimethylammonium chloride. The kinetic profiles were investigated as a function of variables such as surfactant and NaBH(4) concentration and the amount of water dispersed in the reverse micelles, W(0) = [H(2)O]/[surfactant]. In all cases, the first-order rate constant, k(obs), increases with the concentration of surfactant as a consequence of incorporating the substrate into the interface of the reverse micelles where the reaction takes place. The reaction is faster at the cationic interface than at the anionic one probably because the negative ion BH(4)(-) is part of the cationic interface. The effect of the external solvent on the reaction shows that reduction is favored in the isooctane/AOT/water reverse micellar system than that with an aromatic solvent. This is probably due to BH(4)(-) being more in the water pool of the toluene/AOT/water reverse micellar system. The kinetic profile upon water addition depends largely on the type of interface. In the BHDC system, k(obs) increases with W(0) in the whole range studied while in AOT the kinetic profile has a maximum at W(0) approximately 5, probably reflecting the fact that BH(4)(-) is part of the cationic interface while, in the anionic one, there is a strong interaction between water and the polar headgroup of AOT below W(0) = 5 and, above that, BH(4)(-) is repelled from the interface once the water pool has formed. Application of a kinetic model based on the pseudophase formalism, which considers the distribution of the ketone between the continuous medium and the interface and assumes that reaction takes place only at the interface, has enabled us to estimate rate constants at the interface of the reverse micellar systems. At W(0) < 10, it was considered that NaBH(4) is wholly at the interface and, at W(0) >/= 10, where there are free water molecules, also the partitioning between the interface and the water pool was taken into account. The results were used to evaluate CAF and NaBH(4) distribution constants between the different pseudophases as well as the second-order reaction rate constant of the reduction reaction in the micellar interface. 相似文献
75.
Nicolas?Ferré Alessandro?Cembran Marco?Garavelli Massimo?OlivucciEmail author 《Theoretical chemistry accounts》2004,112(4):335-341
A special hybrid quantum mechanics/molecular mechanics forcefield is defined, parameterized and validated for studying the photoisomerization path of the retinal chromophore in the rhodopsin protein. It couples a multireference ab initio Hamiltonian (CASSCF and second-order multireference many-body perturbation theory using a CASSCF reference) to describe the chromophore while the rest of the protein is approximated with the Amber forcefield. The frontier has been carefully parameterized in order to reproduce full quantum mechanics torsional energy profiles, for both the ground state and the first excited state. It is also shown that replacing the chromophore counterion with point charges is a valid approximation. This result is interpreted in terms of a cancellation effect for which a possible explanation is given. 相似文献
76.
Yossef A. Elabd Marco Giacinti Baschetti Timothy A. Barbari 《Journal of Polymer Science.Polymer Physics》2003,41(22):2794-2807
Over the past 2 decades, the use of time‐resolved Fourier transform infrared/attenuated total reflection (ATR) spectroscopy for the measurement of diffusion in polymers has grown. ATR is a powerful technique for the measurement of diffusion in polymers because it is an in situ technique that is relatively inexpensive, provides reliable short‐time data, and provides a wealth of information at the molecular level. This article highlights the technique and its application to numerous studies, ranging from the diffusion of drugs in human skin to chemical warfare agents in barrier materials. In addition to these topics, recent studies with ATR to quantify and model molecular interactions during the diffusion process are reviewed. In the future, the ATR technique may have an impact on a variety of emerging fields in which diffusion in polymers plays an important role, such as fuel cells, membrane separation, sensors, and drug delivery. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2794–2807, 2003 相似文献
77.
Marco Häser 《Theoretical chemistry accounts》1993,87(1-2):147-173
Summary A novel formulation of MP2 theory is presented which starts from the Laplace transform MP2 ansatz, and subsequently moves from a molecular orbital (MO) representation to an atomic orbital (AO) representation. Consequently, the new formulation is denoted AO-MP2. As in traditional MP2 approaches electron repulsion integrals still need to be transformed. Strict bounds on the individual MP2 energy contribution of each intermediate four-index quantity allow to screen off numerically insignificant integrals with a single threshold parameter. Implicit in our formulation is a bound to two-particle density matrix elements. For small molecules the computational cost for AO-MP2 calculations is about a factor of 100 higher than for traditional MO-based approaches, but due to screening the computational effort in larger systems will only grow with the fourth power of the size of the system (or less) as is demonstrated both in theory and in application. MP2 calculations on (non-metallic) crystalline systems seem to be a feasible extension of the Laplace transform approach. In large molecules the AO-MP2 ansatz allows massively parallel MP2 calculations without input/output of four-index quantities provided that each processor has in-core memory for a limited number of two-index quantities. Energy gradient formulas for the AO-MP2 approach are derived.Dedicated to Prof. W. Kutzelnigg whose books on theoretical chemistry aroused my interest in this field 相似文献
78.
Acetylcholine and choline sensors are prepared by immbilizing enzymes on nylon net attached to a hydrogen peroxide snsor. Choline oxidase is used for the choline sensor; acetylcholinesterase choline oxidase are used for acetylcholine. The platinum/silver electrode pair is polarized at +0.6 V. The assembly is protected with an acetate cellulose membrane to enhance selectivity. The ranges measured are 1–10 μmol l?1 in 0.1–1 ml of sample. The response times are 1–2 min. 相似文献
79.
Arosio D Fontanella M Baldini L Mauri L Bernardi A Casnati A Sansone F Ungaro R 《Journal of the American Chemical Society》2005,127(11):3660-3661
A high-affinity ligand of cholera toxin, the divalent glycocalix[4]arene 1, was obtained by exploiting a combination of structure-based design of glycomimetic monovalent ligands and affinity enhancements by multivalent presentation through a calix[4]arene scaffold. It exhibits a slightly higher affinity for the toxin than its natural ligand, the GM1 oligosaccharide. 相似文献
80.
Highly reliable and accurate analytical methods are needed for the determination of magnetic resonance imaging (MRI) contrast agents in complex matrices of clinical interest. We demonstrate the reliability of capillary zone electrophoresis (CZE) coupled with electrospray ionization-mass spectrometry (ESI-MS) for the analysis of MultiHance (gadobenate dimeglumine), a gadolinium-based MRI agent. A sheath liquid interface connected the CE system with an electrospray mass spectrometer equipped with an ion-trap analyzer. CZE with ultraviolet (CZE-UV) and with mass detection (CZE-MS) were compared by analyzing gadobenate dimeglumine and the free ligand diluted in water and in biological fluids (i.e., human serum and urine). The optimization of some relevant CZE-MS parameters was accomplished, like CE buffer composition, sheath liquid composition and flow, and type and length of the separation capillary. CZE-UV was highly influenced by the biological sample components, which hindered a reliable quantification of both gadobenate and free ligand in serum and urine. In CZE-MS, on the other hand, the electrophoretic runs turned out to be independent of the clinical matrices, due to the informative potential and to the selectivity of MS detection. 相似文献