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991.
Gawinkowski S Orzanowska G Izdebska K Senge MO Waluk J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(36):10039-10049
2,3,7,8,12,13,17,18‐Octaethyl‐5,15‐diphenylporphyrin ( 1 ) is characterized by an inner cavity with a rectangular shape and small NH???N distances. It resembles porphycene, which is a constitutional isomer of porphyrin known for its strong intramolecular hydrogen bonds and rapid tautomerization. Such distortion of the porphyrin cavity leads to tautomeric properties of 1 that are intermediate between those of porphyrin and porphycene. In particular, a tautomerization in the lowest excited singlet state of 1 has been discovered, occurring with a rate three orders of magnitude lower than that in porphycene, but three to four orders of magnitude higher than that in porphyrin. An isomer of 1 , 2,3,7,8,12,13,17,18‐octaethyl‐5,10‐diphenylporphyrin ( 2 ), exhibits a different kind of geometry distortion. This molecule is nonplanar, but the inner cavity shape and dimensions are similar to those of the parent porphyrin. The same hydrogen‐bonding strength as that in porphyrin is observed for 2 . In contrast, the nonplanarity of 2 significantly influences the photophysics, leading to a decrease in fluorescence quantum yield and lifetime. Absorption, magnetic circular dichroism, and fluorescence spectra are similar for 1 and 2 and resemble those of parent porphyrin. This is a consequence of comparable energy splittings of the frontier orbitals, ΔHOMO≈ΔLUMO. The results demonstrate that judicious selection of substituents and their position enables a controlled modification of geometry, hydrogen‐bonding strength, tautomerization rate, and photophysical and spectral parameters of porphyrinoids. 相似文献
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994.
Mathias Sawall Christoph Kubis Detlef Selent Armin Brner Klaus Neymeyr 《Journal of Chemometrics》2013,27(5):106-116
The multicomponent factorization of multivariate data often results in nonunique solutions. The so‐called rotational ambiguity paraphrases the existence of multiple solutions that can be represented by the area of feasible solutions (AFS). The AFS is a bounded set that may consist of isolated subsets. The numerical computation of the AFS is well understood for two‐component systems and is an expensive numerical process for three‐component systems. In this paper, a new fast and accurate algorithm is suggested that is based on the inflation of polygons. Starting with an initial triangle located in a topologically connected subset of the AFS, an automatic extrusion algorithm is used to form a sequence of growing polygons that approximate the AFS from the interior. The polygon inflation algorithm can be generalized to systems with more than three components. The efficiency of this algorithm is demonstrated for a model problem including noise and a multicomponent chemical reaction system. Further, the method is compared with the recent triangle‐boundary‐enclosing scheme of Golshan, Abdollahi, and Maeder (Anal. Chem. 2011, 83, 836–841). Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
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996.
Anja S. Goldmann Mathias Glassner Andrew J. Inglis Christopher Barner‐Kowollik 《Macromolecular rapid communications》2013,34(10):810-849
The establishment of advanced living/controlled polymerization protocols allows for engineering synthetic polymers in a precise fashion. Combining advanced living/controlled polymerization techniques with highly efficient coupling chemistries facilitates quantitative, modular, and orthogonal functionalization of synthetic polymer strands at their chain termini as well as side‐chain functionalization. The review highlights the current status of selected post‐functionalization techniques of polymers via orthogonal ligation chemistries, major characteristics of the specific transformation chemistry, as well as the characterization of the products.
997.
Hala J. El-Khozondar Mathias S. Müller Corbinian Wellenhofer Rifa J. El-Khozondar Alexander W. Koch 《Fiber and Integrated Optics》2013,32(5):420-430
Abstract The four-mode coupling in shear-strain-loaded fiber Bragg grating sensors has been demonstrated to have influence on the measured spectra and, thus, on the application of embedded fiber Bragg gratings for strain field measurements. In a recent work, these coupling coefficients were derived using a set of assumptions on the properties of the fiber's modes. However, the validity of these approximations was not explicitly tested. Here, the required coupling coefficients are computed, making use of the full-field components. It is demonstrated that additional terms will appear; however, they are negligible in practical fibers, and thus, the made approximations are valid. 相似文献
998.
Srinivas Basavoju Dan Boström Sitaram P. Velaga 《Molecular Crystals and Liquid Crystals》2013,570(1):254-264
Novel organic salts of norfloxacin and ciprofloxacin with artificial sweeteners such as saccharin and acesulfame were prepared. The two salts 1 and 2 were characterized by differential scanning calorimetry (DSC) and powder X-ray diffraction (PXRD). Finally, the crystal structures were solved by single crystal X-ray diffraction data and the structures were analyzed in terms of supramolecular synthons. In norfloxacin acesulfamate 1, two norfloxacin cations and two acesulfame anions form an eight membered cyclic tetramer supramolecular synthon. The salt, ciprofloxacin acesulfamate 2, has a similar structure as salt 1. This study contributes the importance of crystal engineering and supramolecular chemistry to the pharmaceutical applications in terms of interactions and structural correlations in the design of new solid phases. Supplemental materials are available for this article. Go to the publisher's online edition of Molecular Crystals and Liquid Crystals to view the free supplemental file. 相似文献
999.
Mathias Rafler 《Journal of Theoretical Probability》2013,26(4):1097-1116
Zessin (J. Contemp. Math. Anal. 44(1):36–44, 2009) constructed the so-called Pólya sum process via partial integration technique. This process shares some important properties with the Poisson process such as complete randomness and infinite divisibility. This work discusses H-sufficient statistics for the Pólya sum process as was done for the Poisson process by Nguyen and Zessin (Z. Wahrscheinlichkeitstheor. Verw. Geb. 37(3):191–200, 1976/77). 相似文献
1000.
Nunes ET Bechara GH Saito KC Denardi SE Oliveira PR Mathias MI 《Micron (Oxford, England : 1993)》2005,36(5):437-447
The present study describes the morphology and ultrastructure of the salivary glands of semi-engorged females of the southern cattle-tick Rhipicephalus (Boophilus) microplus. The acini that compose these glands, at that specific feeding stage, show cells featuring degenerative process of the salivary glands, such as: vacuolated cytoplasm, condensed chromatin, fragmented nuclei, and presence of apoptotic bodies. In addition, the presence of microorganisms was detected, with morphology typical of protozoa, inside these organs. 相似文献