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121.
Makoto Hatakeyama Takako Mashiko Hisanao Hazama Kunio Awazu Masanori Tachikawa 《International journal of quantum chemistry》2013,113(2):125-129
To investigate the correlation between the wavelength dependence of ionization threshold fluence of target molecule in matrix‐assisted laser desorption/ionization by infrared (IR) laser and the IR absorption spectrum of matrix molecule, we have analyzed the IR absorption spectra of four matrix molecules using density functional theory and correlated ab initio molecular orbital method. The calculated IR absorption spectra of the isolated molecules showed more qualitative correlation with the wavelength dependence of ionization threshold fluence than those of the solid state structures. We can consider that a portion of matrix molecules lost the ordered crystal structure and that the transition to the diluted or isolated state occurred at the early process of IR laser irradiation. © 2012 Wiley Periodicals, Inc. 相似文献
122.
Ana Fragoso Dr. Pedro Lamosa Prof. Rita Delgado Dr. Olga Iranzo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(6):2076-2088
Designing small peptides that are capable of binding Cu2+ ions mainly through the side‐chain functionalities is a hard task because the amide nitrogen atoms strongly compete for Cu2+ ion coordination. However, the design of such peptides is important for obtaining biomimetic small systems of metalloenyzmes as well as for the development of artificial systems. With this in mind, a cyclic decapeptide, C‐Asp, which contained three His residues and one Asp residue, and its linear derivative, O‐Asp, were synthesized. The C‐Asp peptide has two Pro? Gly β‐turn‐inducer units and, as a result of cyclization, and as shown by CD spectroscopy, its backbone is constrained into a more defined conformation than O‐Asp, which is linear and contains a single Pro? Gly unit. A detailed potentiometric, mass spectrometric, and spectroscopic study (UV/Vis, CD, and EPR spectroscopy) showed that at a 1:1 Cu2+/peptide ratio, both peptides formed a major [CuHL]2+ species in the pH range 5.0–7.5 (C‐Asp) and 5.5–7.0 (O‐Asp). The corrected stability constants of the protonated species (log K*CuH(O?Asp)=9.28 and log K*CuH(C?Asp)=10.79) indicate that the cyclic peptide binds Cu2+ ions with higher affinity. In addition, the calculated value of Keff shows that this higher affinity for Cu2+ ions prevails at all pH values, not only for a 1:1 ratio but even for a 2:1 ratio. The spectroscopic data of both [CuHL]2+ species are consistent with the exclusive coordination of Cu2+ ions by the side‐chain functionalities of the three His residues and the Asp residue in a square‐planar or square‐pyramidal geometry. Nonetheless, although these data show that, upon metal coordination, both peptides adopt a similar fold, the larger conformational constraints that are present in the cyclic scaffold results in different behaviour for both [CuHL]2+ species. CD and NMR analysis revealed the formation of a more rigid structure and a slower Cu2+‐exchange rate for [CuH(C‐Asp)]2+ compared to [CuH(O‐Asp]2+. This detailed comparative study shows that cyclization has a remarkable effect on the Cu2+‐coordination properties of the C‐Asp peptide, which binds Cu2+ ions with higher affinity at all pH values, stabilizes the [CuHL]2+ species in a wider pH range, and has a slower Cu2+‐exchange rate compared to O‐Asp. 相似文献
123.
Dr. Sam C. K. Hau Prof. Dr. Thomas C. W. Mak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(17):5387-5400
Single‐crystal X‐ray diffraction of a series of ten crystalline silver(I)–trifluoroacetate complexes that contained designed ligands, each of which was composed of an aromatic system that was functionalized with terminal and internal ethynyl groups and a vinyl substituent, provided detailed information on the influence of ligand disposition and orientation, coordination preferences, and the co‐existence of different types of silver(I)–carbon bonding interactions (silver–ethynide, silver–ethynyl, silver–ethenyl, and silver–aromatic) on the construction of coordination networks that were consolidated by argentophilic and weak inter/intramolecular interactions. The complex Ag L10? 6 AgCF3CO2 ? H2O ? MeOH ( HL10 =1‐{[4‐(prop‐2‐ynyloxy)‐3‐vinylphenyl]ethynyl}naphthalene) is the first reported example that exhibits all four kinds of silver(I)–carbon bonding interactions in the solid state. 相似文献
124.
Dr. Chao Xu Dr. Guoxin Tian Dr. Simon J. Teat Dr. Guokui Liu Dr. Linfeng Rao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16690-16698
The complexation of NpO22+ and PuO22+ with dipicolinic acid (DPA) has been investigated in 0.1 M NaClO4 by spectrophotometry, microcalorimetry, and single crystal diffractometry. Formation of 1:1 and 1:2 (metal/ligand molar ratio) complexes of DPA with NpO22+ and PuO22+ were identified and the thermodynamic parameters were determined and compared with those of UO22+. All three hexavalent actinyl cations form strong 1:1 DPA complexes with slightly decreasing but comparable stability constants from UO22+ to PuO22+, whereas the stability constants of the 1:2 complexes (log β2) decrease substantially along the series (16.3 for UO2L22?, 15.17 for NpO2L22?, and 14.17 for PuO2L22? at 25 °C). The enthalpies of complexation for the 1:2 complexes become less exothermic from UO2L22? (?28.9 kJ mol?1), through NpO2L22? (?27.2 kJ mol?1), and to PuO2L22? (?22.7 kJ mol?1). The trends in the thermodynamic parameters are discussed in terms of the effective charge of the cations and the steric constraints in the structures of the complexes. In addition, the features of the absorption spectra, including the wavelength and intensity of the absorption bands, are related to the perturbation of the ligand field and the symmetry of the actinyl complexes. 相似文献
125.
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128.
The focus of this article is on the analysis of repairable systems that are subject to multiple sources of recurrence. The event of interest at the system level is assumed to be caused by the earliest occurrence of a source, thereby conforming to a series system competing risks framework. Parametric inference is carried out under the power law process model that has found significant attention in industrial applications. Dependence among the cause‐specific recurrent processes is induced via a shared frailty structure. The theoretical inference results are implemented to a warranty database for a fleet of automobiles, for which the warranty repair is triggered by the failure of one of many components. Extensive finite‐sample simulation is carried out to supplement the asymptotic findings. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
129.
Crystals of the bis(tert‐butyl)silylene (DTBS) derivatives of the tartaric acids were synthesized from D ‐, L ‐, rac‐, and meso‐tartaric acid and DTBS bis(trifluoromethanesulfonate): two polymorphs of Si2tBu4(L ‐Tart1,2;3,4H–4) (L ‐ 1a and L ‐ 1b ), the mirror image of the denser modification (D ‐ 1b ) as well as the racemate ( 2 ), and the meso analogue Si2tBu4(meso‐Tart1,3;2,4H–4) ( 3 ). The structures were determined by single‐crystal X‐ray diffraction. The threo‐configured D ‐ and L ‐ (and rac‐) tartrates were coordinated by two tBu2Si units forming five‐membered chelate rings, whereas the erythro‐configured meso‐tartrate formed six‐membered chelate rings. The new compounds were analyzed by NMR techniques, including 29Si NMR spectroscopy, and single‐crystal X‐ray crystallography. 相似文献
130.
The power supply for IEF based on features of the Cockcroft‐Walton voltage multiplier (CW VM) is described in this work. The article describes a design of the IEF power supply, its electric characteristics, and testing by IEF analysis. A circuit diagram of the power supply included two opposite charged branches (each consisting of four voltage doublers). The designed CW VM was powered by 230 V/50 Hz alternate current and it generated up to 5 kV and 90 mW at the output. Voltage and current characteristics of the power supply were measured by known load resistances in the range from 10 kΩ to 1 GΩ, which is a common resistance range for IEF strip geometry. Further, the power supply was tested by a separation of a model mixture of colored pI markers using a 175 × 3 × 0.5 mm focusing bed. Automatically limited power load enabled analysis of samples without previous optimization of the focusing voltage or electric current time courses according to sample composition. Moreover, the developed power supply did not produce any intrinsic heat and was easy to set up with cheap and commonly available parts. 相似文献