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131.
In the present work we examine a series of hypervalent molecules, namely, FClO(x) (x = 1-3), Cl(3)PO, Cl(3)PCH(2), Cl(3)CClO, and C(ClO)(4), through single-reference [CCSD(T)] and multireference (MRCI) ab initio methods, the principal aim being the deciphering of their binding pattern. Our electronic structure calculations consistently show that the bonding occurs through an electron pair transfer from the Cl or P atoms of the molecules considered to the (1)D state of the O atom(s). We strongly believe that the term "hypervalency" when viewed from an unbiased side and with a critical eye reveals a simple chemical bonding situation that is in conformity with a scientific parsimony that dissolves the mythology of an enormous class of molecular systems that are categorized under the term hypervalent. 相似文献
132.
Stamatakis G Knuutinen U Laitinen K Spyros A 《Analytical and bioanalytical chemistry》2010,398(7-8):3203-3214
Two original art installations constructed from unsaturated polyester resins (UPR) and four different reference UPR products (before and after UVB aging) were analyzed by high-resolution 1D and 2D nuclear magnetic resonance (NMR) spectroscopy. Breaking strain studies were also conducted for the four UPR model products before and after different aging procedures (moisture, UVB exposure, melt/freeze). NMR analysis of the chemical composition of the UPR resin extracts showed they contain several low MW organic compounds and oligomers rich in polar -OH groups that play a significant role in the degradation behavior of the composite UPR materials. Statistical analysis of the NMR compositional data showed that styrene and benzaldehyde contents can be used to differentiate between fresh and aged UPR samples. The phthalate and propylene glycol unit speciation (esterified, primary or secondary -OH) of the extracts provided evidence that UPR resin C was used in the construction of the two art installations, and direct comparison of (1)H and (13)C NMR spectra verified this compositional similarity. UPR resin C was shown by both NMR and breaking strain studies to be the reference UPR most susceptible to degradation by different aging procedures, a characteristic attributed to the lower styrene content of resin C. 相似文献
133.
Sofia Rangou Dimitrios Moschovas Ioannis Moutsios Gkreti-Maria Manesi Konstantina Tsitoni Polina V. Bovsunovskaya Dimitri A. Ivanov Edwin L. Thomas Apostolos Avgeropoulos 《Molecules (Basel, Switzerland)》2020,25(24)
To the best of our knowledge, this is the very first time that a thorough study of the synthetic procedures, molecular and thermal characterization, followed by structure/properties relationship for symmetric and non-symmetric second generation (2-G) dendritic terpolymers is reported. Actually, the synthesis of the non-symmetric materials is reported for the first time in the literature. Anionic polymerization enables the synthesis of well-defined polymers that, despite the architecture complexity, absolute control over the average molecular weight, as well as block composition, is achieved. The dendritic type macromolecular architecture affects the microphase separation, because different morphologies are obtained, which do not exhibit long range order, and various defects or dislocations are evident attributed to the increased number of junction points of the final material despite the satisfactory thermal annealing at temperatures above the highest glass transition temperature of all blocks. For comparison reasons, the initial dendrons (miktoarm star terpolymer precursors) which are connected to each other in order to synthesize the final dendritic terpolymers are characterized in solution and in bulk and their self-assembly is also studied. A major conclusion is that specific structures are adopted which depend on the type of the core connection between the ligand and the active sites of the dendrons. 相似文献
134.
Comparing linear and cyclic synthetic homopolypeptides: Synthesis and molecular characterization
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Nikolaos Politakos George Liontos Galder Kortaberria Jamie M. Messman Javier Calvo Sergio E. Moya Jimmy W. Mays Apostolos Avgeropoulos 《Journal of polymer science. Part A, Polymer chemistry》2015,53(3):393-404
The synthesis and molecular characterization of a linear and a cyclic homopolypeptide of protected l ‐tyrosine are reported. In this work, the successful synthesis of polypeptides exhibiting the desired linear and cyclic structures through various characterization methods such as high temperature gel permeation chromatography, Fourier transform infrared spectroscopy, proton and carbon nuclear magnetic resonance spectroscopy, mass spectrometry, dynamic light scattering, differential scanning calorimetry, and thermogravimetric analysis was verified. The results are very promising especially if such cyclic materials will be potentially used as carriers for drug delivery, either through conjugation with specific ligands or directly through the functional hydroxyl groups of the monomeric units of poly(l ‐Tyr) after deprotection. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 393–404 相似文献
135.
136.
Michail Bourmpos Apostolos Argyris Dimitris Syvridis 《Fiber and Integrated Optics》2014,33(3):205-223
AbstractA continuously growing number of municipalities has optical fiber networks supporting communications at their disposal. These fiber installations can also be utilized to convey low data optical signals from a large number of deployed sensing elements, usually positioned in critical infrastructure locations, providing a variety of useful information. Such information can be used in the context of a “smart city” to provide citizens with higher-level services or even to proactively ensure public security and safety. This work demonstrates a fiber sensing network based on low-cost fiber Bragg grating sensors that are able to appropriately oversee diverse monitoring parameters. 相似文献
137.
Theodorou D Meligotsidou L Karavoltsos S Burnetas A Dassenakis M Scoullos M 《Talanta》2011,83(5):692-1574
The propagation stage of uncertainty evaluation, known as the propagation of distributions, is in most cases approached by the GUM (Guide to the Expression of Uncertainty in Measurement) uncertainty framework which is based on the law of propagation of uncertainty assigned to various input quantities and the characterization of the measurand (output quantity) by a Gaussian or a t-distribution. Recently, a Supplement to the ISO-GUM was prepared by the JCGM (Joint Committee for Guides in Metrology). This Guide gives guidance on propagating probability distributions assigned to various input quantities through a numerical simulation (Monte Carlo Method) and determining a probability distribution for the measurand.In the present work the two approaches were used to estimate the uncertainty of the direct determination of cadmium in water by graphite furnace atomic absorption spectrometry (GFAAS). The expanded uncertainty results (at 95% confidence levels) obtained with the GUM Uncertainty Framework and the Monte Carlo Method at the concentration level of 3.01 μg/L were ±0.20 μg/L and ±0.18 μg/L, respectively. Thus, the GUM Uncertainty Framework slightly overestimates the overall uncertainty by 10%. Even after taking into account additional sources of uncertainty that the GUM Uncertainty Framework considers as negligible, the Monte Carlo gives again the same uncertainty result (±0.18 μg/L). The main source of this difference is the approximation used by the GUM Uncertainty Framework in estimating the standard uncertainty of the calibration curve produced by least squares regression. Although the GUM Uncertainty Framework proves to be adequate in this particular case, generally the Monte Carlo Method has features that avoid the assumptions and the limitations of the GUM Uncertainty Framework. 相似文献
138.
The present study examines the isotopic and hydrochemical composition of 18 inland spring waters and 3 coastal karstic spring waters, covering the period between October 2005 and March 2008. The stable isotopes ((18)O, (2)H) processing has revealed the absence of significant evaporation phenomena and that the origin of fresh water samples is meteoric. Using (18)O values in rainfall waters, an average line of isotopic depletion with altitude has been constructed, extracting a rate of-0.45‰/100?m as typical for the study area. Furthermore, the mean altitude of recharge of the springs has been estimated by plotting the groundwater sampling points on a δ(18)O versus altitude diagram. Hydrochemistry results have shown that the dissolution of carbonate, flysch and ophiolitic formations defines the hydrochemical characteristics of groundwater. Moreover, seawater intrusion in the coastal area is significantly high, causing the water in the three karstic springs to be brackish. 相似文献
139.
140.
Admission control with batch arrivals 总被引:1,自引:0,他引:1
We consider the problem of dynamic admission control in a multi-class Markovian loss system receiving random batches, where each admitted class-i job demands an exponential service with rate μ, and brings a reward ri. We show that the optimal admission policy is a sequential threshold policy with monotone thresholds. 相似文献