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121.
Osuna RM Ortiz RP Ruiz Delgado MC Sakamoto Y Suzuki T Hernandez V López Navarrete JT 《The journal of physical chemistry. B》2005,109(44):20737-20745
In this Article, we report on the synthesis and full characterization of three perfluorinated oligothiophenes, ranging in length from the trimer to the pentamer (PF-nT, with n = 3, 4, or 5). The differential pulse voltammetry (DPV) analysis of the compounds showed that they can be both oxidized and reduced (i.e., they display a dual or amphoteric electrochemical behavior), with the reduction peaks positively shifted relative to those of the corresponding unsubstituted oligothiophenes. The electrochemically determined energy gaps are in agreement with those measured from the UV-vis-NIR absorption spectra in solution. The conjugational properties have been investigated by means of FT-Raman spectroscopy, both as pure solids and as dilute solutes in CH(2)Cl(2), revealing that: (i) pi-conjugation does not still reach saturation with chain length for the longest oligomer, and (ii) conformational distortions from a nearly coplanar arrangement of the successive thiophene units upon solution are not too large. DFT and TDDFT quantum chemical calculations have been performed, at the B3LYP/6-31G level, to assess information about the optimized molecular structure, equilibrium atomic charges distribution, energies and topologies of the frontier molecular orbitals (MO) around the gap, vibrational normal modes associated with the most outstanding Raman scatterings, and vertical one-electron excitations that give rise to the main optical absorptions. 相似文献
122.
Marcelo O. Santiago Alzir A. Batista Marcio P. de Araújo Claudio L. Donnici Icaro de S. Moreira Eduardo E. Castellano Javier Ellena Sauli dos Santos Jr Salete L. Queiroz 《Transition Metal Chemistry》2005,30(2):170-175
A series of cis-{RuCl2(PPh3)2[4,4-(X)2-2,2-bipy]} [cis-chlorines; X=-H, -Me, -SMe, and (-Cl,-Me)] complexes have had their structures determined by single crystal X-ray diffraction. The geometry of these complexes, also determined in CH2Cl2 solution by 31P{1H}-n.m.r. spectroscopy, showed that the chemical shifts for the phosphorus atoms are slightly dependent on the pKa of the 4,4-(-X)2-2,2-bipy ligands. 相似文献
123.
Ftima R. Moreira Cristina B. Maia Akie K. vila 《Spectrochimica Acta Part B: Atomic Spectroscopy》2002,57(12):2141-2149
The determination of cobalt in marine sediments by electrothermal atomic absorption spectrometry was studied using no modifier and magnesium and titanium as modifiers. Titanium is one of the major sediment constituents, which widely affects the cobalt determination and it was studied as a chemical modifier since it was the only concomitant that increased the cobalt signal in the concentration range usually found in sediments. The performance of Mg and Ti as chemical modifiers was compared relative to maximum pyrolysis and atomization temperatures, linear calibration range, sensitivity and matrix effects. The pyrolysis curves showed that the analyte could be stabilized up to 1400 °C when either Ti or Mg(NO3)2 was present, while only 1000 °C could be used in the absence of a modifier. The optimum atomization temperature was 2500 °C in all cases. Analytical curves were compared using no modifier, 5 μg Ti and 100 μg Mg(NO3)2 as modifiers, and the linear range found was up to approximately 4 ng Co whether a modifier was used or not. With Ti as a chemical modifier, analytical curves for cobalt in aqueous solution and in a synthetic matrix resulted in the same sensitivity (m0=55 pg), whereas the use of Mg led to characteristic mass values of 59 and 72 pg in aqueous solution and in a synthetic matrix, respectively, showing some matrix effect. The detection limits (3σ, n=10) were 0.4 μg g−1 using no modifier and 0.3 μg g−1 with Ti as a modifier in the original matrix. A reference estuarine sediment NIST 1646 with a non-certified content of 10.5 μg g−1 Co was analyzed and the found value of 10.9±2.4 μg g−1, (n=3), using Ti as chemical modifier and calibration against aqueous standards, was in good agreement with the recommended value. 相似文献
124.
García-Río L Leis JR Moreira JA Araujo E Norberto F Ribeiro L 《The Journal of organic chemistry》2003,68(11):4330-4337
A kinetic study was carried out on the hydrolysis of two N-nitrosoguanidines, 1-nitroso-1-methyl-3-tolylsulfonylguanidine (TSGNO) and 1-nitroso-1-methyl-3-benzoylguanidine (BCGNO). We observed an absence of buffer catalysis using H(2)PO(4)(-)/HPO(4)(2)(-), H(3)BO(3)/H(2)BO(3)(-), and HCO(3)(-)/CO(3)(2)(-) regulators and a complex dependency of the rate constant on the pH. We discovered the existence of three simultaneous reaction paths: spontaneous decomposition of the neutral form of the N-nitrosoguanidine, decomposition of the monoanion, and decomposition through the form of the dianion. The analysis of the kinetic data has allowed us to obtain the acidity constant for the formation of the monoanion of the N-nitrosoguanidine, with values of p = 11.5. The reaction rate for the process through the monoanion, k(2), decreases as the acidity increases. The application of the principle of nonperfect synchronization shows that the basicity and reactivity do not correlate when there exists a possibility of stabilization of the negative charge by resonance. This behavior is consistent with the mechanism E1cB whereby the stabler the negative charge, the slower the elimination reaction. When dealing with the case of the elimination through the neutral form we observe that the reaction rate increases together with the capacity of stabilization of the positive charge on the nitrogen atom adjacent to the imino group. For the reaction through the dianion we used a maximum value of k(3) = 10(10) s(-)(1) to estimate the value of p for the formation of the dianion of the N-nitrosoguanidine, obtaining values of p < 24. 相似文献
125.
M. S. Rahman M. Parre?o R. Bossi A. B. Payá-Pérez B. Larsen 《Fresenius' Journal of Analytical Chemistry》1998,360(5):556-563
Six extraction methods for the analysis of PCBs (CB-28, CB-52, CB-101, CB-118, CB-138, CB-153 and CB-180) in sewage sludge
were tested. A certified reference material (CRM 392) was used for the evaluation of the performance of the methods. Soxhlet-Dean-Starch
with toluene as solvent, Soxhlet with hexane:acetone (2:3), cold digestion/saponification with 2 mol/L KOH in methanol followed
by partition with hexane, and sonicated liquid-solid extraction with hexane:acetone (1:1) produced accurate results (97%,
93%, 104%, and 88%, respectively) with acceptable precisions (6.2%, 6.8%, 15% and 12%, respectively). Results in close agreement
with the certified value for all congeners were obtained by treatment with BF3-methanol prior to partition with dichloromethane. However, this is a tedious procedure and involves the use of hazardous
compounds. Cyclic steam distillation produced results with an accuracy of around 80% and a good precision (5.2%). The very
low consumption of solvents and other expensive chemicals by this technique and the possibility of analyzing the extract directly
without clean-up make it an interesting alternative to the more sophisticated methods. Column elution with dichloromethane
was found to be less efficient (61%), but it is a rapid, direct method with a low consumption of solvents and it may therefore
serve as screening method.
Received: 29 April 1997 / Revised: 30 July 1997 / Accepted: 6 August 1997 相似文献
126.
Versatile and stereocontrolled synthetic entries to novel types of cyclopropyl carbocyclic nucleosides are described. The target products have been synthesized from suitable cyclopropane precursors obtained, in turn, from olefinic compounds derived from D-glyceraldehyde as a chiral precursor. Selective manipulation of the functional groups has allowed the preparation of enantiopure nucleosides, some of them displaying opposite chirality. All these molecules contain a quaternary stereogenic carbon at C-1 or C-3 of the cyclopropane ring and bear an amino, a hydroxymethyl, or a methyl group as an additional substituent. In one instance, thymine is directly linked to the cyclopropane. A methylene unit serves as the spacer in the other synthesized nucleosides. 相似文献
127.
Ramo Marceli Fernandes Gelson Manzoni de Oliveira Ernesto Schulz Lang Ezequiel M. Vzquez‐Lpez 《无机化学与普通化学杂志》2004,630(15):2687-2691
The reaction of tellurium(IV) tetrahalides with hydrochloric and hydrobromic acid leads to the formation of (H3O)2[TeX6], which reacts subsequently with (2‐Br‐C5NH5)+X‐ to afford (2‐Br‐C5NH5)2[TeCl6] ( 1 ) and (2‐Br‐C5NH5)2[TeBr6] ( 2 ). The structure of the complex salts were analysed by X‐ray diffractometry affording the centrosymmetric space groups P21/n (monoclinic, 1 ) and P1¯ (triclinic, 2 ). Interionic hydrogen bondings hold their lattices in bidimensional supramolecular arrays not yet described in the literature. The lone electron pair of the AX6E‐system of the hexahalotellurates [TeX6]2‐ (X = Cl, Br) seems to be fully delocalized since only small octahedral deviations were observed for the anionic species. The structures of the title compounds were refined with the Te atoms occupying sites with full point symmetry, approximately m3¯m. In both cases the Te atoms enclose centers of inversion and the octahedrally dynamic structures are enforced and stabilized along the supramolecular lattices by the crystal field of the 2‐Br‐pyridinium cations. 相似文献
128.
B. Skwarzec D. I. Strumińska A. Boryło J. Falandysz 《Journal of Radioanalytical and Nuclear Chemistry》2004,261(3):661-663
238U, 234U and 210Po activity concentrations were determined in beer in Poland by alpha-spectrometry with low-level activity silicon detectors.
The results revealed that the mean concentrations of 238U, 234U and 210Po in the analyzed beer samples were 4.63, 4.11 and 4.94 mBq·dm−3, respectively, the highest in Tyskie (5.71 for 210Po, 5.06 for 234U and 6.11 for 238U) and the lowest in Lech (2.49 for 210Po). The effective radiation dose due to uranium and polonium ingestions by beer was calculated and were compared to the effective
radiation dose from drinking water.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
129.
During the reactions of lithium oxide with aluminium nitride, and of lithium nitride with aluminium oxide, the formation has been observed of a previously unknown compound, of composition Li2AlNO. The course of its thermal decomposition has also been determined.
Zusammenfassung Es wurde das Auftreten einer bisher unbekannten Verbindung der Zusammensetzung LiAlNO bei den Reaktionen von Lithiumoxid mit Aluminiumnitrid und Lithiumnitrid mit Aluminiumoxid beobachtet. Der Verlauf der thermischen Zersetzung dieser Verbindung wurde bestimmt.
Li2AlNO. .相似文献
130.
Jesús M. Ruiz Gonzalez Marcos Loroo Tania Crdova Gabriel Chuchani 《Journal of Molecular Structure》2005,732(1-3):55-61
Møller-Plesset MP2/6-31G method was used to examine the gas-phase elimination of 2-substituted alkyl ethyl N,N-dimethylcarbamates. The results of these calculations support a concerted non-synchronous six-membered cyclic transition state mechanism for carbamates containing a Cβ–H bond at the alkyl side of the ester. These substrates produce the N,N-dimethylcarbamic acid and the corresponding olefin. The unstable intermediate, N,N-dimethylcarbamic acid, rapidly decomposes through a four-membered cyclic transition state to dimethylamine and CO2 gas. Correlation of the logarithm of theoretical rate coefficients against original Taft's σ* values gave an approximate straight line (ρ*=−1.39, r=0.9558 at 360 °C). In addition to this fact, when log krel is plotted against the theoretical log krel for 2-substituted ethyl N,N-dimethylcarbamates a reasonable straight line (r=0.9919 at 360 °C) is obtained, suggesting similar mechanism. 相似文献