Search results for "COMPUTATION"

SN1 Reactions in Supercritical Carbon Dioxide in the Presence of Alcohols: the Role of Preferential Solvation

2016

Ethanol (3b) inhibits SN1 reactions of alkyl halides 1 in supercritical carbon dioxide (scCO2) and gives no ethers as products. The unexpected behaviour of alcohols 3 in the reaction of alkyl halides 1 with 1,3-dimethoxybenzene (2) in scCO2 under different conditions is rationalised in terms of Bronsted and Lewis acid–base equilibria of reagents, intermediates, additives and products in a singular solvent characterised by: (i) the strong quadrupole and Lewis acid character of carbon dioxide, which hinders SN2 paths by strongly solvating basic solutes; (ii) the weak Lewis base character of carbon dioxide, which prevents it from behaving as a proton sink; (iii) the compressible nature of scCO…

Monte Carlo methods for polymer chains in two - dimensional geometries (polymers at surfaces and interfaces)

1993

Coarse-grained models of polymers at interfaces can be defined such that their treatment by Monte Carlo simulation is most convenient and efficient for the problem at hand. This simulation strategy is briefly illustrated with three examples: (1) The orientational ordering of rigid rod-like polymers grafted to a surface, where “table methods” can be used, applying a fine discretization of the angles describing rod orientation. (2) Surface enrichment of one species in a polymer blend is treated by a semi-grand-canonical technique. (3) The number of configurations and structure of a star polymer attached with its center to a wall is studied by a “growth technique” generalizing simple sampling …

A fast algorithm for the exhaustive analysis of 12-nucleotide-long DNA sequences. Applications to human genomics

2004

We have developed a new algorithm that allows the exhaustive determination of words of up to 12 nucleotides in DNA sequences. It is fast enough as to be used at a genomic scale running on a standard personal computer. As an example, we apply the algorithm to compare the number of all 12-nucleotide long words in human chromosomes 21 and 22, each of them more than 33 million nucleotides long. Sequences that are chromosome specific are detected in less than 2 minutes, being analyzed any pair of chromosomes at a rate of 45 millions of nucleotides (45 Mb) per minute. The size of the words is long enough as to allow further analyses of all significant sequences using conventional database searche…

ChemInform Abstract: Benzoxetes and Benzothietes - Heterocyclic Analogues of Benzocyclobutene

2012

Benzo-condensed four-ring heterocycles, such as benzoxetes 1 and benzothietes 3 represent multi-purpose starting compounds for the preparation of various higher heterocyclic ring systems. The thermal or photochemical valence isomerizations between the benzenoid forms 1,3 and the higher reactive o-quinoid structures 2,4 provide the basis for the synthetic applications. On the other hand, this valence isomerization impedes in particular the generation and storage of 1 because the thermal equilibrium 1 2 is completely on the side of 2. Thus, the number of erroneous or questionable benzoxete structures published to date is surprisingly high. On the contrary, the thermal equilibrium 3 4 is on th…

Inside Cover: Efficient Self-Assembly of Di-, Tri-, Tetra-, and Hexavalent Hosts with Predefined Geometries for the Investigation of Multivalency (Ch…

2015

Analysis of the proteins involved in the structure and synthesis of the cell wall of Ustilago maydis

2008

Abstract A study of the proteins involved in the synthesis and structure of the cell wall of Ustilago maydis was made by in silico analysis of the fungal genome, with reference to supporting experimental evidence. The composition of the cell wall of U. maydis shows similarities with the structural composition of the walls of Ascomycetes, but also shows important differential features. Accordingly, the enzymes involved in the synthesis of the U. maydis wall polysaccharides chitin and β-1,6 glucans displayed some differential characteristics. The most salient difference in protein composition was the predicted absence of Pir proteins, an important class of proteins present in the Ascomycetes.…

Equilibrium solution coordination chemistry

2018

Welcome to this themed issue of New Journal of Chemistry entitled “Equilibrium Solution Coordination Chemistry”.

Modification of Chiral Properties Due to Interaction of Polymers and Small Molecules or Ions

1979

The first part of this report deals with changes in the optical rotatory dispersion and circular dichroism resulting from the chemical modification of optically active polymers. Amylose derivatives have very different chiroptical properties compared with cellulose derivatives. Variations in glucosidic bonds and differing secondary structures are described and suggested as causes for this. The N-chlorination of synthetic optically active polyamides is also described, which in all probability proceeds without changing the configuration at the asymmetric C atoms. Reactions of inactive polymers with low molecular weight chiral reagents usually give optical rotation values proportional to the de…

Theoretical Study of the Elimination Kinetics of Carboxylic Acid Derivatives in the Gas Phase. Decomposition of 2-Chloropropionic Acid

1997

The reaction mechanism for the decomposition of 2-chloropropionic acid in the gas phase to form hydrogen chloride, carbon monoxide, and acetaldehyde has been theoretically characterized. Analytical gradients have been used by means of AM1 and PM3 semiempirical procedures and ab initio methods at HF and DFT (BLYP) levels with the 6-31G** basis set. The correlation effects were also included by using the perturbational approach at the MP2 level with the 6-31G** and 6-31++G** basis sets and the variational approach at the CISD/6-31G** level and by means of MCSCF wave functions with a (6,6) complete active space and the 6-31G** basis set. The global potential energy surface has been studied, an…

Nucleic Acids and Nuclear Proteins

1994

DNA deserves the most attention in any book dealing with molecular variety in animals. The complete genetic information of the organism is encoded in the order of the bases, and with it also is the whole spectrum of genetically determined variation within and between individuals. One can view DNA as a text in which each of the four letters at each position has a unique meaning. Some information and variety is lost en route from the DNA via RNA to the proteins and the complex morphological and physiological characters because only part of the DNA is transcribed into RNA, and not all RNA codes for proteins; furthermore, the genetic code is degenerate and the 64 possible triplet codons define …