A new mechanism of photosensitized formation of thymine (Thy) dimers is proposed, which involves generation of a delocalized triplet excited state as the key step. This is supported by chemical evidence obtained by combining one benzophenone and two Thy units with different degrees of freedom, whereby the photoreactivity is switched from a clean Paternò–Büchi reaction to a fully chemo‐, regio‐, and stereoselective [2+2] cycloaddition. 相似文献
Laser desorption ionization using time-of-flight mass spectrometer afforded with quadrupole ion trap was used to study As2Ch3 (Ch = S, Se, and Te) bulk chalcogenide materials. The main goal of the study is the identification of species present in the plasma originating from the interaction of laser pulses with solid state material. The generated clusters in both positive and negative ion mode are identified as 10 unary (Sp+/– and Asm+/–) and 34 binary (AsmSp+/–) species for As2S3 glass, 2 unary (Seq+/–) and 26 binary (AsmSeq+/–) species for As2Se3 glass, 7 unary (Ter+/–) and 23 binary (AsmTer+/–) species for As2Te3 material. The fragmentation of chalcogenide materials was diminished using some polymers and in this way 45 new, higher mass clusters have been detected. This novel approach opens a new possibility for laser desorption ionization mass spectrometry analysis of chalcogenides as well as other materials.
We report on the structures exhibited by two different diblock poly(styrene)-b-poly(acrylic acid) (PS-b-PAA) copolymers in water, a selective solvent. Using a combination of X-ray scattering and freeze fracture-transmission electron microscopy (FF-TEM), we show that these structures can be widely swollen while retaining their initial morphology and a high degree of long-range order. The analysis of the FF-TEM pictures also evidences the presence of water crystallites of regular size and shape within the confined water domains. We relate the growth of these crystallites to the high local ionic strength of the water swelling the PAA brushes. Moreover, the confinement of the crystallites growth shows that the swollen phases have a very robust structure, potentially useful for confining colloidal particles. 相似文献
The efficiency of an Ir(I)/HI system has been studied. The association of hydroiodic acid with iridium has been tested in the catalytic hydroiodination of alkynes. The use of [Ir(cod)Cl]2 dimer led to clean hydroiodination reactions and afforded the corresponding vinyliodides as a mixture of derivatives, where the Markovnikov type adduct was found to be the major product (80/20 to 93/7 ratio), in good yields. The mechanism was investigated and two main pathways seemed to be involved, one based on an initial oxidative addition of HI to the Ir(I) complex and the other one based on a π-activation of the alkyne moiety. The corresponding vinyliodides were engaged in Pd-catalyzed cross-coupling (Sonogashira and Suzuki-Miyaura) reactions under organoaqueuous conditions. 相似文献
The aim of this article is to propose a mathematical model describing the electronic structure of crystals with local defects in the framework of the Thomas–Fermi–von Weizsäcker (TFW) theory. The approach follows the same lines as that used in Cancès et al. (Commun Math Phys 281:129–177, 2008) for the reduced Hartree–Fock model, and is based on thermodynamic limit arguments. We prove, in particular, that it is not possible to model charged defects within the TFW theory of crystals. 相似文献
This paper aims to demonstrate the quantitative simulation of photoacoustic signals using finite element modelling software. The software Comsol Multiphysics is used to calculate the response of a differential Helmholtz resonator cell previously modeled using an electrical analogy. Quality factors and resonance frequencies are compared with experimental ones. Moreover, for the first time, the absorption coefficient of the gas sample and the laser intensity are also used to quantitatively predict photoacoustic signal that can be obtained in such a configuration. 相似文献
Recent crystal structures of nicotine bound to the acetylcholine binding protein (AChBP) ended a long debate confirming that the pyridine nitrogen of nicotine is indeed hydrogen-bonded to receptor residues through a bridging water molecule. Here, we describe the first direct experimental evaluation of the hydrogen-bond affinity of the nicotinium pyridine nitrogen. The equilibrium constant of its association with a phenol is 1 order of magnitude greater than the association of the acetylcholine carbonyl oxygen. 相似文献
The Neumann realization for the Schr?dinger operator with magnetic field is considered in a bounded two-dimensional domain
with corners. This operator is associated with a small semi-classical parameter h or, equivalently, with a large magnetic field.We investigate the behavior of its eigenpairs as h tends to zero, like in a semi-classical limit. We prove, in the situation where the domain is a polygon and the magnetic
field is constant, that the lowest eigenvalues are exponentially close to those of model problems associated with the corners.
We approximate the corresponding eigenvectors by linear combinations of functions concentrated in corners at the scale
If the domain has curved sides and the magnetic field is smoothly varying, we exhibit a full asymptotics for eigenpairs in
powers of
Communicated by Christian Gérard
Submitted: October 13, 2005 Accepted: December 19, 2005 相似文献