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81.
Frontispiece: Reversal of a Single Base‐Pair Step Controls Guanine Photo‐Oxidation by an Intercalating Ruthenium(II) Dipyridophenazine Complex 下载免费PDF全文
82.
Assembling and chelating properties of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) towards divalent metal ions have been investigated in the gas phase by electrospray ionization mass spectrometry. A variety of positively charged monometallated and mixed metal aggregates are formed. Interestingly, several ions contain solvent (MeOH, H(2)O) molecules and constitute the most abundant AOT cationic aggregates not containing sodium. These species are the first example of solvated AOT-metal ion aggregates in the gas phase. By increasing the surfactant aggregation number, the abundance of solvated species becomes lower than that of unsolvated ones. Decompositions of ionic species have been studied by tandem mass spectrometry, and their stability has been determined through energy resolved mass spectrometry. In contrast with positively charged AOT-alkaline metal ion aggregates, whose decompositions are dominated by the loss of individual surfactant molecules, AOTNa-divalent ion aggregates mainly dissociate through the cleavage of the AOT H(2)C-O bond followed by further intramolecular fragmentations. This finding, that is consistent with an enhanced chelation of divalent ions with AOT(-) head groups, has been taken as an indication that such aggregates are characterized by a reverse micelle-like organization with a ionic core formed by the metal cations interacting with the negatively charged surfactant polar heads, whereas the surfactant alkyl chains point outside. 相似文献
83.
Bongiorno D Ceraulo L Giorgi G Indelicato S Ferrugia M Ruggirello A Liveri VT 《Journal of mass spectrometry : JMS》2011,46(2):195-201
Self-assembling of amphiphilic molecules under electrospray ionization (ESI) conditions is characterized by quite unexpected phenomenology. The noticeable differences with respect to the condensed phase are attributable to the absence of the surfactant-solvent interactions, the presence of net charge in the aggregates, and the strong deviation from equilibrium conditions. Aiming to investigate the effects of the net charge on abundance and stability of supramolecular surfactant aggregates, positively and negatively charged aggregates of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and sodium methane sulfonate (MetS), butane sulfonate (ButS) and octane sulfonate (OctS) have been studied by ESI mass spectrometry, energy resolved mass spectrometry and density functional theory calculations. The negatively charged aggregates are found to be less stable than their positive counterparts. The results are consistent with a self-assembling pattern dominated by electrostatic interactions involving the counterions and head groups of the investigated amphiphilic compounds while the alkyl chains point outwards, protecting the aggregates from unlimited growth processes. 相似文献
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86.
2‐Acetylcyclopentanone (2‐ACP), which is a β‐dicarbonyl compound, undergoes keto–enol isomerization, and its enol tautomers are stabilized by a cyclic intramolecular hydrogen bond. 2‐ACP (keto form) has symmetric and asymmetric vibrational modes of the two carbonyl groups at 1748 and 1715 cm?1, respectively, which are well separated from the carbonyl modes of its enol tautomers in the FTIR spectrum. We have investigated 2‐ACP dissolved in carbon tetrachloride by 2D IR spectroscopy and IR pump–probe spectroscopy. Vibrational population transfer dynamics between the two carbonyl modes were observed by 2D IR spectroscopy. To extract the population exchange dynamics (i.e., the down‐ and uphill population transfer rate constants), we used the normalized volumes of the cross‐peaks with respect to the diagonal peaks at the same emission frequency and the survival and conditional probability functions. As expected, the downhill population transfer time constant (3.2 ps) was measured to be smaller than the uphill population transfer time constant (3.8 ps). In addition, the vibrational population relaxation dynamics of the two carbonyl modes were observed to be the same within the experimental error and were found to be much slower than vibrational population transfer between two carbonyl modes. 相似文献
87.
Sachin Rawalekar Sreejith Kaniyankandy Sandeep Verma Dr. Hirendra N. Ghosh 《Chemphyschem》2011,12(9):1729-1735
Herein, we report the synthesis of aqueous CdTe/CdSe type‐II core–shell quantum dots (QDs) in which 3‐mercaptopropionic acid is used as the capping agent. The CdTe QDs and CdTe/CdSe core–shell QDs are characterized by X‐ray diffraction (XRD), high‐resolution transmission electron microscopy (HR‐TEM), steady‐state absorption, and emission spectroscopy. A red shift in the steady‐state absorption and emission bands is observed with increasing CdSe shell thickness over CdTe QDs. The XRD pattern indicates that the peaks are shifted to higher angles after growth of the CdSe shell on the CdTe QDs. HR‐TEM images of both CdTe and CdTe/CdSe QDs indicate that the particles are spherical, with a good shape homogeneity, and that the particle size increases by about 2 nm after shell formation. In the time‐resolved emission studies, we observe that the average emission lifetime (τav) increases to 23.5 ns for CdTe/CdSe (for the thickest shell) as compared to CdTe QDs (τav=12 ns). The twofold increment in the average emission lifetime indicates an efficient charge separation in type‐II CdTe/CdSe core–shell QDs. Transient absorption studies suggest that both the carrier cooling and the charge‐transfer dynamics are affected by the presence of traps in the CdTe QDs and CdTe/CdSe core–shell QDs. Carrier quenching experiments indicate that hole traps strongly affect the carrier cooling dynamics in CdTe/CdSe core–shell QDs. 相似文献
88.
Arnab Bagchi Yu‐Hsuan Huang Z. F. Xu P. Raghunath Yuan T. Lee Chi‐Kung Ni M. C. Lin Yuan‐Pern Lee 《化学:亚洲杂志》2011,6(11):2961-2976
The photodissociation of gaseous benzaldehyde (C6H5CHO) at 193, 248, and 266 nm using multimass ion imaging and step‐scan time‐resolved Fourier‐transform infrared emission techniques is investigated. We also characterize the potential energies with the CCSD(T)/6‐311+G(3df,2p) method and predict the branching ratios for various channels of dissociation. Upon photolysis at 248 and 266 nm, two major channels for formation of HCO and CO, with relative branching of 0.37:0.63 and 0.20:0.80, respectively, are observed. The C6H5+HCO channel has two components with large and small recoil velocities; the rapid component with average translational energy of approximately 25 kJ mol?1 dominates. The C6H6+CO channel has a similar distribution of translational energy for these two components. IR emission from internally excited C6H5CHO, ν3 (v=1) of HCO, and levels v≤2, J≤43 of CO are observed; the latter has an average rotational energy of approximately 13 kJ mol?1 and vibrational energy of approximately 6 kJ mol?1. Upon photolysis at 193 nm, similar distributions of energy are observed, except that the C6H5+HCO channel becomes the only major channel with a branching ratio of 0.82±0.10 and an increased proportion of the slow component; IR emission from levels ν1 (v=1) and ν3 (v=1 and 2) of HCO and v≤2, J≤43 of CO are observed; the latter has an average energy similar to that observed in photolysis at 248 nm. The observed product yields at different dissociation energies are compared to statistical‐theory predicted results based on the computed singlet and triplet potential‐energy surfaces. 相似文献
89.
Maria Brzhezinskaya Alexander Firsov Karsten Holldack Torsten Kachel Rolf Mitzner Niko Pontius Jan‐Simon Schmidt Mike Sperling Christian Stamm Alexander Föhlisch Alexei Erko 《Journal of synchrotron radiation》2013,20(4):522-530
Aiming at advancing storage‐ring‐based ultrafast X‐ray science, over the past few years many upgrades have been undertaken to continue improving beamline performance and photon flux at the Femtoslicing facility at BESSY II. In this article the particular design upgrade of one of the key optical components, the zone‐plate monochromator (ZPM) beamline, is reported. The beamline is devoted to optical pump/soft X‐ray probe applications with 100 fs (FWHM) X‐ray pulses in the soft X‐ray range at variable polarization. A novel approach consisting of an array of nine off‐axis reflection zone plates is used for a gapless coverage of the spectral range between 410 and 1333 eV at a designed resolution of E/ΔE = 500 and a pulse elongation of only 30 fs. With the upgrade of the ZPM the following was achieved: a smaller focus, an improved spectral resolution and bandwidth as well as excellent long‐term stability. The beamline will enable a new class of ultrafast applications with variable optical excitation wavelength and variable polarization. 相似文献
90.
杜传梅 《原子与分子物理学报》2013,30(6)
在350- 600nm 波长范围内测定了激光烧蚀Ni等离子体中Ni原子的空间分辨发射光谱.测定了385.83 nm发射光谱线的相对强度和STARK展宽及其随径向的变化特性。结果表明, 在沿激光束方向上, 当距离靶表面0-2.5mm范围内变化时,谱线的STARK展宽和谱线的强度都随距靶面距离的增大先增大,但增大到最大值后随距离的进一步增大而减小。谱线强度和STARK加宽的最大值都出现在离靶面约1.5mm处。 相似文献