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Prof. Piotr Bałczewski Dr. Emilia Kowalska Dr. Ewa Różycka-Sokołowska Dr. Joanna Skalik Dr. Krzysztof Owsianik Dr. Marek Koprowski Dr. Bernard Marciniak Dr. Dariusz Guziejewski Prof. Witold Ciesielski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(62):14148-14161
The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (Tdecomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S1 state by molecular oxygen. 相似文献
3.
Rodrigo París José Luis de la Fuente 《Journal of polymer science. Part A, Polymer chemistry》2007,45(16):3538-3549
Different diblock copolymers constituted by one segment of a monomer supporting a reactive functional group, like allyl methacrylate (AMA), were synthesized by atom transfer radical polymerization (ATRP). Bromo‐terminated polymers, like polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(butyl acrylate) (PBA) were employed as macroinitiators to form the other blocks. Copolymerizations were carried out using copper chloride with N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as the catalyst system in benzonitrile solution at 70 °C. At the early stage, the ATRP copolymerizations yielded well‐defined linear block copolymers. However, with the polymerization progress a change in the macromolecular architecture takes place due to the secondary reactions caused by the allylic groups, passing to a branched and/or star‐shaped structure until finally yielding gel at monomer conversion around 40% or higher. The block copolymers were characterized by means of size exclusion chromatography (SEC), 1H NMR spectroscopy, and differential scanning calorimetry (DSC). In addition, one of these copolymers, specifically P(BA‐b‐AMA), was satisfactorily modified through osmylation reaction to obtain the subsequent amphiphilic diblock copolymer of P(BA‐b‐DHPMA), where DHPMA is 2,3‐dihydroxypropyl methacrylate; demonstrating the feasibility of side‐chain modification of the functional obtained copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3538–3549, 2007 相似文献
4.
The influence of hydrogen bonds on the physical and chemical properties of hydrogen bonding fluid system of A a D d type is investigated from two viewpoints by the principle of statistical mechanics. In detail, we proposed two new ways that can be used to obtain the equilibrium size distribution of the hydrogen bonding clusters, and derived the analytical expression of a relationship between the hydrogen bonding free energy and hydrogen bonding degree. For the nonlinear hydrogen bonding systems, it is shown that the sol-gel phase transition can take place under proper conditions, which is further proven to be a kind of geometrical phase transition rather than a thermodynamic one. Moreover, several problems associated with the geometrical phase transition and liquid-solid phase transition in nonlinear hydrogen bonding systems are discussed. 相似文献
5.
Humberto César Chaves Fernandes Arthur Rodrigo Barros da Rocha 《International Journal of Infrared and Millimeter Waves》2003,24(7):1171-1176
The use of photonic materials has been used in the theory of optical waves. The PBG (Photonic Band Gap) theory and material, was developed recently for optical frequencies and can be easily applied to millimeter waves, microwaves and planar antenna frequencies. The presence of photonic materials as substrate in antennas has some good characteristics such as, supression of light spontaneous emission and suppression of surface waves, allowing the application in planar antenna array. In this work an elaborate analysis using the full wave Transverse Transmission Line - TTL method, that provides efficient and concise results is applied to the planar antennas array with PBG substrate. 相似文献
6.
This work presents a formulation based on UPML for truncating conductive media by using a local and non-orthogonal coordinate
system to solve Maxwell’s equations by the FDTD method. The detailed procedure for obtaining the UPML equations for this case
is shown and the complete equation set is provided. 相似文献
7.
Gianluigi Luppi Rodrigo J. Corrêa Angelo C. Pinto Quirinus B. Broxterman Claudia Tomasini 《Tetrahedron》2006,62(51):12017-12024
The first total synthesis of (R)-convolutamydine A has been achieved by the organocatalytic addition of acetone to 4,6-dibromoisatin. The absolute configuration was determined by single crystal X-ray diffraction. DFT studies were used to model the transition states for the aldol reaction and equilibrium geometries of the post-aldol reaction intermediates. The DFT study revealed that the aldol bond forming reaction was considerably endothermic. 相似文献
8.
Jos Luis Rodrigo 《纯数学与应用数学通讯》2005,58(6):821-866
We consider the problem of the evolution of sharp fronts for the surface quasi‐geostrophic (QG) equation. This problem is the analogue to the vortex patch problem for the two‐dimensional Euler equation. The special interest of the quasi‐geostrophic equation lies in its strong similarities with the three‐dimensional Euler equation, while being a two‐dimen‐sional model. In particular, an analogue of the problem considered here, the evolution of sharp fronts for QG, is the evolution of a vortex line for the three‐dimensional Euler equation. The rigorous derivation of an equation for the evolution of a vortex line is still an open problem. The influence of the singularity appearing in the velocity when using the Biot‐Savart law still needs to be understood. We present two derivations for the evolution of a periodic sharp front. The first one, heuristic, shows the presence of a logarithmic singularity in the velocity, while the second, making use of weak solutions, obtains a rigorous equation for the evolution explaining the influence of that term in the evolution of the curve. Finally, using a Nash‐Moser argument as the main tool, we obtain local existence and uniqueness of a solution for the derived equation in the C∞ case. © 2004 Wiley Periodicals, Inc. 相似文献
9.
Classification of conformally flat n-dimensional pseudo-Riemannian spaces via Plebanski's method is discussed. It is based on embedding these spaces into a flat (n + 2)-dimensional space and on finding their minimal isometry groups which are subgroups of the conformal group. In particular, the case n = 4 is given in full detail and compared with incomplete results known in the literature. The found conformally flat spacetimes are identified with the associated solutions of the Einstein equations and with the spacetimes used in various cosmological considerations. 相似文献
10.
We focus on continuous Markov chains as a model to describe the evolution of credit ratings. In this work it is checked whether a simple, tridiagonal type of generator provides a good approximation to a general one. Three different tridiagonal approximations are proposed and their performance is checked against two generators, corresponding to a volatile and a stable period, respectively. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献