Predicting Climate Change Using Response Theory: Global Averages and Spatial Patterns

Journal of Statistical Physics - The provision of accurate methods for predicting the climate response to anthropogenic and natural forcings is a key contemporary scientific challenge. Using a...     

Comparing the enantioselective power of steric and electrostatic effects in transition-metal-catalyzed asymmetric synthesis

The current approach to improve and tune the enantioselective performances of transition-metal catalysts for asymmetric synthesis is mostly focused to modifications of the steric properties of the ancillary ligands of the active metal. Nevertheless, it is also known that electrostatic effects can have a remarkable role to promote selectivity in asymmetric synthesis. Using the Rh-catalyzed asymmetric 1,4-addition of phenylboronic acid to 2-cyclohexenone leading to chiral 3-phenylcyclohexanone as an example, we could show that high enantioselectivity can be indeed achieved using catalysts essentially based either on steric or electrostatic effects as the main source of enantioselective induction. In this contribution we suggest that the analysis of the surface of interaction between the catalyst and the substrate could be a useful tool to quantify the power of steric and electrostatic effects of catalysts.     

The pivotal role of symmetry in the ruthenium-catalyzed ring-closing metathesis of olefins

The synthesis of Ru-based precatalysts with N-heterocyclic carbene (NHC) ligands bearing syn- and anti-methyl groups on the NHC backbone and aryl N-substituents with differing steric bulk was carried out. The catalytic behavior of the monophospine Ru precatalysts (7a, 7b, 8a, and 8b) was compared to the corresponding family of phosphine-free catalysts (9a, 9b, 10a and 10b) in the ring-closing metathesis (RCM) of olefins. These catalysts showed high efficiency in RCM reactions and the syn-isomers 7a and 9a, in particular, proved to be among the most active catalysts in the formation of tetrasubstituted olefins through RCM. DFT studies on the entire RCM catalytic cycle of hindered olefins were performed to rationalize the different behaviors of catalysts with syn- and anti-methyl groups on the NHC backbone. Theoretical results not only disclosed how NHC symmetry influences the overall activity of the catalyst, but also gave relevant and more general indications on the crucial steps of the RCM of olefins.     

Structural resolution of the stereochemistry of a spirooxirane derived from an α-arylidene heterocyclic carbonyl. The crystal and molecular structure of 2-(p-chlorophenyl)-5-phenyl-7-methyl-1-oxa-5,6-diazaspiro[2.4]hept-6-en-4-one

The stereochemical assignment of molecular geometry for α-arylidene carbonyl compounds and spirooxirane derived from them have continued to be a challenging problem for which the most satisfactory solution continues to be an x-ray diffraction structure determination. In that regard, the title compound (a spirooxirane) has been found to crystallize in the monoclinic space group P2_1/c with cell dimensions of a = 5.989(1)Å, b = 27.625(4)Å, c = 9.374(2)Å, β = 99.06(1)°. The structure of the compound has been determined, with the refinement to R = 0.059. The previous, tentative assignment of structure has been confirmed substantiating our prediction that the oxidation of the enone system proceeds with rotation of the phenyl group on the β-carbon away from the carbonyl group, minimizing adverse steric interactions and allowing orbitals of the carbonyl group to overlap with those of the carbanionic center during the closure of the oxirane ring. The agreement between predictions based on nmr data and the x-ray diffraction determination will support a stronger reliance on the nmr data predictions in subsequent studies.     

Conformational diseases and structure-toxicity relationships: lessons from prion-derived peptides

The physiological form of the prion protein is normally expressed in mammalian cell and is highly conserved among species, although its role in cellular function remains elusive. Available evidence suggests that this protein is essential for neuronal integrity in the brain, possibly with a role in copper metabolism and cellular response to oxidative stress. In prion diseases, the benign cellular form of the protein is converted into an insoluble, protease-resistant abnormal scrapie form. This conversion parallels a conformational change of the polypeptide from a predominantly alpha-helical to a highly beta-sheet secondary structure. The scrapie form accumulates in the central nervous system of affected individuals, and its protease-resistant core aggregates into amyloid fibrils outside the cell. The pathogenesis and molecular basis of the nerve cell loss that accompanies this process are not understood. Limited structural information is available on aggregate formation by this protein as the possible cause of these diseases and on its toxicity. A large amount of structure-activity studies is based on the prion fragment approach, but the resulting information is often difficult to untangle. This overview focuses on the most relevant structural and functional aspects of the prion-induced conformational disease linked to peptides derived from the unstructured N-terminal and globular C-terminal domains.     

Determination of phenols in environmental samples by liquid chromatography – electrochemistry

A reverse-phase high-performance liquid chromatography procedure with gradient elution and electrochemical detection is described for the determination of phenolic compounds, including several priority pollutant chlorophenols, in sea-water and sediments. In addition, a method for concentrating phenols from sea-water was examined. A solid-phase extraction using a derivatized poly(styrene-divinylbenzene) copolymer is discussed. The recovery, repeatability and detection limits are shown. Electrochemical detection provided selectivity as well as sensitivity. Phenols at the ng/l level were detected. The method was applied to the analysis of the most important phenolic compounds in sea-water and marine sediments. Received: 12 April 1996 / Revised: 30 October 1996 / Accepted: 28 November 1996     

Local stress measurement using the thermoelastic effect

A technique for measuring local stresses in metallic specimens is proposed and tested. The technique depends on the experimental measurement of temperature changes in stressed members due to adiabatic elastic deformation. At a free boundary in a body under plane stress, these temperature changes are directly related to the value of the tangential principal stress. The technique is suited for measurement of stress-concentration effects, since the temperature changes can be measured with thermocouples featuring extremely small junctions. A simple stress-concentration geometry, the finitewidth strip with a central circular hole, is chosen as a model system for this study. Heat transfer in this geometry due to the temperature gradients produced by elastic deformation is analyzed. It is shown that the ratio of the temperature change at a reference section to the change at the locale of the stress concentration can be used to determine the stress-concentration factor, allowing for heat-transfer effects. An experimental measurement system capable of obtaining reproducible results with the thermal-measurement technique is described, and experimental results are given for the model geometry which agree favorably with theoretical predictions. Application of the technique to other problems is discussed.     

Mechanistic insights into the cis-trans isomerization of ruthenium complexes relevant to catalysis of olefin metathesis

The mechanism of the trans to cis isomerization in Ru complexes with a chelating alkylidene group has been investigated by using a combined theoretical and experimental approach. Static DFT calculations suggest that a concerted single‐step mechanism is slightly favored over a multistep mechanism, which would require dissociation of one of the ligands from the Ru center. This hypothesis is supported by analysis of the experimental kinetics of isomerization, as followed by ¹H NMR spectroscopy. DFT molecular dynamics simulations revealed that the variation of geometrical parameters around the Ru center in the concerted mechanism is highly uncorrelated; the mechanism actually begins with the transformation of the square‐pyramidal trans isomer, with the Ru?CHR bond in the apical position, into a transition state that resembles a metastable square pyramidal complex with a Cl atom in the apical position. This high‐energy structure collapses into the cis isomer. Then, the influence of the N‐heterocyclic carbene ligand, the halogen, and the chelating alkylidene group on the relative stability of the cis and trans isomers, as well as on the energy barrier separating them, was investigated with static calculations. Finally, we investigated the interconversion between cis and trans isomers of the species involved in the catalytic cycle of olefin metathesis; we characterized an unprecedented square‐pyramidal metallacycle with the N‐heterocyclic carbene ligand in the apical position. Our analysis, which is relevant to the exchange of equatorial ligands in other square pyramidal complexes, presents evidence for a remarkable flexibility well beyond the simple cis–trans isomerization of these Ru complexes.     

RESOLUTION OF OVERLAPPING BANDS IN THE NEAR-UV ABSORPTION SPECTRUM OF INDOLE DERIVATIVES

Abstract— The second derivative spectra of tryptophan in water and in ethylene glycol at 22°C have been integrated in order to obtain the corresponding primitive functions. The integration was carried out by making use of Tchebychev polynomials. The results show that the integrated primitive functions do not correspond to the original absorption spectra of tryptophan in various solvents, but they reflect only the contributions of the ¹L_b bands of the indolic chromophore. The identification of the electronic component, which generates the second derivative spectrum, was based on the solvent insensitivity of the derivative peaks. The comparison between the absorption spectra reported in this paper and those calculated for the ¹L_b←¹A electronic transition of indole confirmed the assumption that the derivation process eliminates the broad, although more intense, contributions coming from the ¹L_a←¹A electronic transition.     

Effect of a Weak Electrolyte on the Critical Micellar Concentration of Sodium Dodecyl Sulfate

The critical micellar concentration of sodium dodecyl sulfate is strongly altered bytris(hydroxy-methyl)methylammonium ions. The effect of buffer solutions containing this weak electrolyte as the counterion source has been studied using various concentrations of the acid–base system as well as modifying the pH. Results show that counterion concentrations ranging from 0 to 340 × 10⁻³M induce an appreciable diminution of the critical micellar concentration from 8 to 0.7 × 10⁻³M. The analysis of data suggests that the critical micellar concentration of sodium dodecyl sulfate depends on the concentration of weak electrolytes in a way very similar to that of strong electrolytes.