The effect of hydrogen bonding on the excited-state proton transfer in 2-(2'-hydroxyphenyl)benzothiazole: a TDDFT molecular dynamics study

The dynamics of the excited-state proton transfer (ESPT) in a cluster of 2-(2'-hydroxyphenyl)benzothiazole (HBT) and hydrogen-bonded water molecules was investigated by means of quantum chemical simulations. Two different enol ground-state structures of HBT interacting with the water cluster were chosen as initial structures for the excited-state dynamics: (i) an intramolecular hydrogen-bonded structure of HBT and (ii) a cluster where the intramolecular hydrogen bond in HBT is broken by intermolecular interactions with water molecules. On-the-fly dynamics simulations using time-dependent density functional theory show that after photoexcitation to the S(1) state the ESPT pathway leading to the keto form strongly depends on the initial ground state structure of the HBT-water cluster. In the intramolecular hydrogen-bonded structures direct excited-state proton transfer is observed within 18 fs, which is a factor two faster than proton transfer in HBT computed for the gas phase. Intermolecular bonded HBT complexes show a complex pattern of excited-state proton transfer involving several distinct mechanisms. In the main process the tautomerization proceeds via a triple proton transfer through the water network with an average proton transfer time of approximately 120 fs. Due to the lack of the stabilizing hydrogen bond, intermolecular hydrogen-bonded structures have a significant degree of interring twisting already in the ground state. During the excited state dynamics, the twist tends to quickly increase indicating that internal conversion to the electronic ground state should take place at the sub-picosecond scale.     

Propylene polymerization by C1‐symmetric {ONNO′}‐type salan zirconium complexes

The activities of C₁‐symmetric dibenzyl zirconium complexes of Salan ligands that bear a halo‐substituted phenolate ring and an alkyl‐substituted phenolate ring in propylene polymerization with methylaluminoxane as cocatalyst were studied. These {ONNO′}ZrBn₂‐type catalysts exhibited moderate‐to‐high activities and yielded polypropylene of low molecular weight. The degree of tacticity was found to depend on the steric bulk of the substituents on both phenolate rings and ranged from practically atactic to substantially isotactic (74–78% [mmmm] for polymerizations at room temperature by Lig⁵ZrBn₂). Hemi‐isotactic polypropylene was not obtained, despite the diastereotopicity of the two positions. The pattern of stereo errors was consistent with the enantiomorphic site control of propylene insertion typically observed for C₂‐symmetric catalysts and implied a facile site‐averaging mechanism. A regular 1,2‐insertion and a β‐H transfer to an incoming monomer correspond to the main propagation and termination processes, respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Thionation of a cyanoxime derivative to form the sulphur-containing derivative,a novel ligand for complexation with transitional metal ions

Structural Chemistry - 2-Cyano-2-(hydroxyimino)dithioacetic acid was prepared starting from cyanoacetic acid methylester via 2-cyano-2-(hydroxyimino)acetic acid methylester. Before thionation, the...     

Organocatalyzed Domino [3+2] Cycloaddition/Payne‐Type Rearrangement using Carbon Dioxide and Epoxy Alcohols

An unprecedented organocatalytic approach towards highly substituted cyclic carbonates from tri‐ and tetrasubstituted oxiranes and carbon dioxide has been developed. The protocol involves the use of a simple and cheap superbase under mild, additive‐ and metal‐free conditions towards the initial formation of a less substituted carbonate product that equilibrates to a tri‐ or even tetrasubstituted cyclic carbonate under thermodynamic control. The latter are conveniently trapped in situ, providing overall a new domino process for synthetically elusive heterocyclic scaffolds. Control experiments provide a rationale for the observed cascade reactions, which demonstrate similarity to the well‐known Payne rearrangement of epoxy alcohols.     

The Orthogonal Subcategory Problem and the Small Object Argument

A classical result of P. Freyd and M. Kelly states that in “good” categories, the Orthogonal Subcategory Problem has a positive solution for all classes of morphisms whose members are, except possibly for a subset, epimorphisms. We prove that under the same assumptions on the base category and on , the generalization of the Small Object Argument of D. Quillen holds—that is, every object of the category has a cellular -injective weak reflection. In locally presentable categories, we prove a sharper result: a class of morphisms is called quasi-presentable if for some cardinal λ every member of the class is either λ-presentable or an epimorphism. Both the Orthogonal Subcategory Problem and the Small Object Argument are valid for quasi-presentable classes. Surprisingly, in locally ranked categories (used previously to generalize Quillen’s result), this is no longer true: we present a class of morphisms, all but one being epimorphisms, such that the orthogonality subcategory is not reflective and the injectivity subcategory Inj is not weakly reflective. We also prove that in locally presentable categories, the injectivity logic and the Orthogonality Logic are complete for all quasi-presentable classes. Financial support by Centre for Mathematics of University of Coimbra and by School of Technology of Viseu is acknowledged by the third author.     

Proper Efficiency in Vector Optimization on Real Linear Spaces

In this paper, we use an algebraic type of closure, which is called vector closure, and through it we introduce some adaptations to the proper efficiency in the sense of Hurwicz, Benson, and Borwein in real linear spaces without any particular topology. Scalarization, multiplier rules, and saddle-point theorems are obtained in order to characterize the proper efficiency in vector optimization with and without constraints. The usual convexlikeness concepts used in such theorems are weakened through the vector closure.     

Influence of the coulomb interaction on the liquid-gas phase transition and nuclear multifragmentation

The liquid-gas phase transition is analyzed from the topologic properties of the event distribution in the observables space. A multicanonical formalism allows one to directly relate the standard phase transition with neutral particles to the case where the nonsaturating Coulomb interaction is present, and to interpret the Coulomb effect as a deformation of the probability distributions and a rotation of the order parameter. This formalism is applied to a statistical multifragmentation model and consequences for the nuclear multifragmentation phase transitions are drawn.     

Kochen-Specker theorem for a single qubit using positive operator-valued measures

A proof of the Kochen-Specker theorem for a single two-level system is presented. It employs five eight-element positive operator-valued measures and a simple algebraic reasoning based on the geometry of the dodecahedron.