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81.
[Reaction: see text] Ruthenium-catalyzed coupling of allyl ethyl ether to optically active 1-trimethylsilyl-1-alkyn-3-ols, followed by in situ ketalization and Lewis-acid-induced cyclization, affords enantiomerically pure 1,5-oxygen-bridged eight- and nine-membered carbocycles. Opening of the oxygen bridge under basic or electron transfer conditions provides optically pure medium-sized carbocycles, products that are difficult to construct using other currently available methodologies. 相似文献
82.
Fernando Ferreira 《Tetrahedron letters》2004,45(33):6287-6290
Oligonucleotides protected with N-(trimethylsilylethoxycarbonyl) (Teoc) and P-(trimethylsilylethanol) (Tse) groups were synthesized and deprotected by a single ZnBr2 treatment. Teoc group stabilized dA against depurination. This strategy was applied to the synthesis of base-sensitive oligonucleotide prodrugs bearing S-acetyl-2-thioethyl (Sate) phosphotriesters. 相似文献
83.
Laura Gagliardi Giorgio Orlandi Fernando Bernardi Alessandro Cembran Marco Garavelli 《Theoretical chemistry accounts》2004,111(2-6):363-372
In the present paper we report the results of a multiconfigurational computational study on potential-energy curves of azobenzene along the NN twisting to clarify the role of this coordinate in the decay of the S2(*) and S1(n*) states. We have found that there is a singlet state, S3 at the trans geometry, on the basis of the doubly excited configuration n2*2, that has a deep minimum at about 90° of twisting, where it is the lowest excited singlet state. The existence of this state provides an explanation for the short lifetime of S2(*) and for the wavelength-dependence of azobenzene photochemistry. We have characterized the S1(n*) state by calculating its vibrational frequencies, which are found to correspond to the recently observed transient Raman spectrum. We have also computed the potential-energy curve for the triplet T1(n*) at the density functional theory B3LYP level, which indicates that in this state the isomerization occurs along the twisting coordinate.Acknowledgement The financial support from MIUR (project Modellistica delle proprietà spettroscopiche di sistemi molecolari complessi funds ex 60% and project Dinamiche molecolari in sistemi di interesse chimico funds ex 40%), from the University of Bologna (Funds for Selected Research Topics) is gratefully acknowledged.Contribution to the Jacopo Tomasi Honorary Issue 相似文献
84.
David S. dos Santos Jr. Antonio Riul Jr. Roger R. Malmegrim Fernando J. Fonseca Osvaldo N. Oliveira Jr. Luiz H. C. Mattoso 《Macromolecular bioscience》2003,3(10):591-595
Chitosan is alternated with sulfonated polystyrene (PSS) to build layer‐by‐layer (LBL) films that are used as sensing units in an electronic tongue. Using impedance spectroscopy as the principle method of detection, an array using chitosan/PSS LBL film and a bare gold electrode as the sensing units was capable of distinguishing the basic tastes – salty, sweet, bitter, and sour – to a concentration below the human threshold. The suitability of chitosan as a sensing material was confirmed by using this sensor to distinguish red wines according to their vintage, vineyard, and brands.
85.
A tungsten-rhodium treatment on the integrated platform of a transversely heated graphite atomiser was used as a permanent chemical modifier for the determination of copper in biological materials by using digested samples as well as slurry sampling in electrothermal atomic absorption spectrometry. The W-Rh permanent modifier was as efficient as Pd+Mg(NO(3))(2) conventional modifier for obtaining good Cu thermal stabilisation in the digested and slurry samples. The permanent W-Rh modifier remained stable by approximately 300 and 250 firings when 20 mul of digested sample and 20 mul of slurry were delivered into the atomiser, respectively. In addition, the permanent modifier increased the tube lifetime up to 1370 and 744 analytical measurements in the digested and slurry samples, respectively. Also, when the W-Rh permanent modifier was employed, there was less variation of the slope of the analytical curves during the total atomiser lifetime, resulting in a decreased need of re-calibration during routine analysis, increasing the sample throughput, and consequently diminishing the variable analytical costs. Detection limits obtained with W-Rh permanent modifier were 0.64 and 0.33 mug g(-1) Cu for digested (dilution factor 100 ml g(-1)) and 1.0% m/v slurries of biological materials, respectively. Results for the determination of copper in the samples were in agreement with those obtained with decomposed sample solutions by using Pd+Mg(NO(3)), since no statistical differences were found after applying the paired t-test at the 95% level. 相似文献
86.
Cristóbal Valenzuela Calahorro Fernando José García Barros Angeles Díaz Díez Alvaro Bernalte García Eduardo Sabio Rey 《Monatshefte für Chemie / Chemical Monthly》1992,123(1-2):9-16
Summary Five Cu(II), Pd(II), Cd(II), Pt(IV), and Au(III) complexes of 6-chloropurine have been obtained. The complexes were characterized by elemental analysis, IR,1H-NMR and13C-NMR spectroscopy. On the basis of these data the structure of the complexes and the coordination of the ligand have been proposed. Thus, the physical and chemical methods supported evidence that in acidic medium, with exception of the Cu(II) complex, 6-chloropurine acts in the monoprotonated form neutralizing the charge of [PdCl4]2–, [CdCl4]2–, [AuCl4]– and [PtCl6]2– anions. The thermal behaviour of the complexes has also been studied.
Metallkomplexe von 6-Chlorpurin
Zusammenfassung Es wurden fünf Komplexe von 6-Chlorpurin mit Cu(II), Pd(II), Cd(II), Pt(IV) und Au(III) erhalten. Die Komplexe wurden mittels Elementaranalysen, IR,1H-NMR und13C-NMR charakterisiert. Auf der Basis dieser Daten wurde eine Komplexstruktur und eine bestimmte Koordination der Liganden vorgeschlagen. Physikalische und chemische Methoden beweisen, daß im sauren Bereich [mit der Ausnahme von Cu(II)] das 6-Chlorpurin in der monoprotonierten Form koordiniert, wobei die Ladung von [PdCl4]2–, [CdCl4]2–, [AuCl4]– und [PtCl6]2– jeweils neutralisiert wird. Das thermische Verhalten der Komplexe wurde ebenfalls untersucht.相似文献
87.
The electronic structure and the spectroscopic properties of [Au2(CS3)2]?2, [Au2(pym‐2‐S)2] (pym = pyrimidethiolate), [Au2(dpm)2]+2 (dpm = bis(diphosphino)methane) were studied using density functional theory (DFT) at the B3LYP level. The absorption spectrum of these binuclear gold(I) complexes was calculated by single excitation time‐dependent (TD) method. All complexes showed a 1(5dσ* → 6pσ) transition associated with a metal–metal charge transfer, which is strongly interrelated with the gold–gold distance. Furthermore, we have calculated the frequency of the gold–gold vibration (νAu2) on the above complexes. The values obtained are theoretically in agreement with experimental range. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
88.
Field LM Lahti PM Palacio F Paduan-Filho A 《Journal of the American Chemical Society》2003,125(33):10110-10118
Mn(hfac)(2) and Cu(hfac)(2) form coordination complexes with 5-(4-[N-tert-butyl-N-aminoxyl]phenyl)pyrimidine, PyrimPh-NIT. (Mn[PyrimPh-NIT](hfac)(2))(2) and (Cu[PyrimPh-NIT](hfac)(2))(2), 1 and 2, respectively, are cyclic M(2)L(2) dimers that exhibit strong exchange coupling between the coordinated paramagnetic dication (M) and nitroxide (NIT) unit. The M-NIT exchange is strongly antiferromagnetic (AFM) in 1 and strongly ferromagnetic (FM) in 2. Magnetic susceptibility measurements for 1 were fitted to an AFM spin pairing model with J/k = -0.25 K between Mn-NIT spin sites units. Complex 2 also exhibits AFM spin pairing between S = 1 Cu-NIT spin units that is somewhat field dependent at low temperature. The fit of corrected paramagnetic susceptibility chi(T) to an AFM spin pairing model at 200 Oe yields J/k = (-)3.8 K, quite similar to earlier measurements at 1000 Oe yielding J/k = (-)5.0 K. At 1.40 K, the magnetization of 2 does not approach saturation until somewhat above 170 kOe, giving an S-shaped curve; at 0.55 K, the magnetization curve shows steps characteristic of field-induced crossover between the S = 0 ground state and excited spin states. From the steps in the 0.55 K data, we estimate J/k = (-)3.8-4.0 K for 2, in good agreement with the analysis of chi(T). 相似文献
89.
M. del Carmen Núñez Fernando Rodríguez-Serrano Antonia Aránega Antonio Espinosa 《Tetrahedron》2005,61(43):10363-10369
On the basis of molecular variations on isosteric replacements from the prototype 1-(2,3-dihydro-5H-1,4-benzodioxepin-3-yl)-5-fluorouracil a series of 3-(2,3-dihydro-5H-4,1-benzoxathiepin-3-yl)-uracil or -thymine O,N-acetals was prepared. The nature of the cis- and trans-sulfoxide isomers was established by means of their conformational analyses carried out with Sybyl and after comparing the theoretical results with the 1H NMR responses of the target molecules. (RS)-3-(1,1-Dioxo-2,3-dihydro-5H-4,1-benzoxathiepin-3-yl)thymine and (1S*,3S*)-1-(1-oxo-3,5-dihydro-2H-4,1-benzoxathiepin-3-yl)thymine were found to be inhibitors of the MCF-7 cell growth. 相似文献
90.
Moncada MC Parola AJ Lodeiro C Pina F Maestri M Balzani V 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(6):1519-1526
We have investigated the network of reactions observed for the photochromic 4'-hydroxy-6-nitroflavylium compound in aqueous solutions upon pH changes (including pH jump and stopped flow experiments) and light excitation. The changes observed in the NMR and UV/Vis spectra allowed identification of ten different forms in which this compound can be transformed depending on the experimental conditions. Equilibrium and kinetic constants have been determined. Compared with other members of the flavylium family, 4'-hydroxy-6-nitroflavylium is characterized by a large cis-->trans isomerization barrier, and a very efficient hydration reaction. These peculiar features allow writing, reading, storing and erasing photonic information on 4'-hydroxy-6-nitroflavylium by a novel cyclic process that involves the following steps: write-lock/read/unlock/enable-erase/erase. 相似文献