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51.
We describe the synthesis and photophysical properties of a series of neutral and cationic 3,4-tetrapyridinoporphyrazines, potential lead photosensitizers for photodynamic inactivation of bacteria. Tetracationic TPyPzs exist essentially as monomers in aqueous systems, but the presence of trialkylated compounds due to incomplete quaternization of the outer nitrogen atoms induces severe aggregation. The absorption, fluorescence, triplet, and singlet oxygen quantum yields for both the neutral and cationic compounds are comparable to those of the related phthalocyanines. 相似文献
52.
Jorge Labella Gonzalo Durn-Sampedro M. Victoria Martínez-Díaz Toms Torres 《Chemical science》2020,11(39):10778
Here we report gold(i)-catalyzed cycloisomerization as a new powerful synthetic tool for the preparation of π-extended BODIPY derivatives. The catalytic system PPhF3AuCl/AgSbF6 enables the synthesis of [b]-[2,1]naphtho-fused-BODIPYs (2a–2c) under mild conditions, in excellent yields and short reaction times. The reaction is totally regioselective to the 6-endo-dig product and for the α-position of the BODIPY, which is both the kinetically and thermodynamically favored pathway, as supported by the free energy profile calculated by means of Density Functional Theory (DFT). Moreover, this methodology also allows the synthesis of two new families of [b]-aryl-fused-BODIPYs, namely, [3,4]phenanthro- (2e and 2f) and [1,2]naphtho-fused (2g) BODIPYs. Their molecular and electronic structures were established by NMR and UV-vis spectroscopies as well as single-crystal X-ray diffraction analysis. As can be noted from the X-ray structures, 2a, 2e and 2g present interesting structural differences at both the molecular and packing level. Interestingly, despite being isomers, the UV/vis spectra of 2a and 2g revealed significant differences in their electronic structures. The origin of this finding was studied by Time-Dependent DFT calculations. Calculated DFT Nuclear Independent Chemical Shift (NICS(0)) values also supported the different electronic structures of 2a and 2g.Here we report gold(i)-catalyzed cycloisomerization as a new powerful synthetic tool for the preparation of π-extended BODIPY derivatives. 相似文献
53.
Genivaldo Julio Perptuo Jan Janczak 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):o431-o432
In the crystal structure of 3‐amino‐1,2,4‐triazine, C3H4N4, the molecules form hydrogen‐bonded chains that are almost parallel to the b axis (3.2°), and which are inclined to the a and c axes by ~21 and ~69°, respectively. The distortion of the 1,2,4‐triazine ring in the crystal is compared with gas‐phase ab initio molecular‐orbital calculations. 相似文献
54.
Robin J. Marles James B. Hudson Elizabeth A. Graham Chantal Soucy-Breau Peter Morand R. Lilia Compadre Cesar M. Compadre G. H. Neil Towers J. Thor Arnason 《Photochemistry and photobiology》1992,56(4):479-487
The photoactivated antiviral and cytotoxic activities of the naturally occurring thiophene, alpha-terthienyl (1), and 15 synthetic analogues were evaluated against murine cytomegalovirus and Sindbis virus, and murine mastocytoma cells. After irradiation with near UV light, alpha-terthienyl and most of its analogues had significant toxicity, with minimum inhibitory concentrations in the range of 0.02-40 microM. In the absence of near UV irradiation, only one analogue had antiviral activity and five were cytotoxic. The most active analogues were those containing carboxylic acid, hydroxyl, or cyano substituents. Quantitative structure-activity relationship analysis of thiophene phototoxicity suggested that the rate of singlet oxygen production is the primary determinant of antiviral and cytotoxic activities. For phototoxicity against murine cytomegalovirus, a significant role for hydrophobicity was also demonstrated. Tricyclic thiophenes show significant potential for photochemotherapy of viral infections and cancer, and further evaluation in animal models is recommended. 相似文献
55.
Briceo-Arias Luis Deride Julio Vega Cristian 《Journal of Optimization Theory and Applications》2022,192(1):56-81
Journal of Optimization Theory and Applications - In this paper, we propose a numerical approach for solving composite primal-dual monotone inclusions with a priori information. The underlying a... 相似文献
56.
Silva Julio Cezar Soares de Lima Silva Diogo Ferreira Ferreira Luciano de Almeida-Filho Adiel Teixeira 《4OR: A Quarterly Journal of Operations Research》2022,20(1):139-164
4OR - Even though sovereign bonds represent low-risk alternatives that give investors a healthy income, the risk assessment process for these bonds is still considered subjective because of the... 相似文献
57.
58.
A. González Arias A. del Cueto J. M. Muñoz C. de Francisco L. Torres A. G. Flores M. Zazo J. Iñiguez 《Applied Physics A: Materials Science & Processing》1996,63(5):453-459
Silica may dissolve up to about 0.05 wt% in an iron excess NiZnCo spinel matrix, affecting noticeably the magnetic properties at low and high values of the applied field. The initial permeability is reduced by about 50% with the addition of only 0.1 % SiO2, while the coercivity almost triples, without noticeable changes in porosity or grain distribution. The vacancy and Fe2+ content of the sintered material also show a considerable change. The energy associated to the transformation Fe3+ Fe2+ for the samples without SiO2 was found to be 0.41–0.42 eV, while for the samples with SiO2 additions it decreased to 0.26 eV. The changes in magnetic properties are thought to be caused, more than because of the mentioned changes in ion distribution, by the stresses and defects created in the lattice due to the very small size of the Si4+ ion, which substitutes Fe3+ ions in tetrahedral sites. The transition Fe3+ Fe2+ seems to take place exclusively in the octahedral sites. 相似文献
59.
60.
We simulate the classical diffusion of a particle of massM in an infinite one-dimensional system of hard point particles of massm in equilibrium. Each computer run corresponds to about 108 collisions of the diffusive particle. We find that (t) 1/t
fort large enough, and a crossover from an M m regime where=2 to=3 forM=m. The diffusion constant has a sharp maximum atM=m. We study moments x(t)2 and x(t)4, and examine the behavior ofq
2
(t)=x(t)4/3x(t)22. We find thatq(t)1 (consistent with a normal distribution) in theM limit (for all timest) and in the t limit for allM.
On sabbatical leave from IVIC-Instituto Venezolano de Investigaciones Cientificas. 相似文献