Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Controlling Selectivity by Controlling Energy Partitioning in a Thermal Reaction in Solution.

ABSTRACT: The comparison of experimental and predicted kinetic isotope effects in the ?-cleavage of alkoxy radicals is used here to judge the applicability of statistical rate theories. It is found that the governing rate theory and the statistical versus nonstatistical nature of the cleavage depend on the cleavage barrier and how much energy is imparted to the radical. The latter can then be controlled by changing the size of substituents in the system. With a large alkyl group substituent, the vibrational energy of the alkoxy radical is increased, but this energy is not statistically distributed, leading to a lower isotope effect than predicted by statistical theories. The observed isotope effect can be approximately rationalized using a semistatistical localized RRKM model.

SUBMITTER: Kurouchi H

PROVIDER: S-EPMC5358507 | biostudies-literature | 2016 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Controlling Selectivity by Controlling Energy Partitioning in a Thermal Reaction in Solution.

Kurouchi Hiroaki H Andujar-De Sanctis Ivonne L IL Singleton Daniel A DA

Journal of the American Chemical Society 20161027 44

The comparison of experimental and predicted kinetic isotope effects in the α-cleavage of alkoxy radicals is used here to judge the applicability of statistical rate theories. It is found that the governing rate theory and the statistical versus nonstatistical nature of the cleavage depend on the cleavage barrier and how much energy is imparted to the radical. The latter can then be controlled by changing the size of substituents in the system. With a large alkyl group substituent, the vibration ...[more]

PMID: 27764943

Similar Datasets

Labelling and determination of the energy in reactive intermediates in solution enabled by energy-dependent reaction selectivity.

Project description:Any long-lived chemical structure in solution is subject to statistical energy equilibration, so the history of any specific structure does not affect its subsequent reactions. This is not true for very short-lived intermediates because energy equilibration takes time. Here, this idea is applied to achieve the 'energy labelling' of a reactive intermediate. The selectivity of the ring-opening ?-cleavage reaction of the 1-methylcyclobutoxy radical is found here to vary broadly depending on how the radical was formed. Reactions that provide little excess energy to the intermediate lead to a high selectivity in the subsequent cleavage (measured as a kinetic isotope effect), whereas reactions that provide more excess energy to the intermediate exhibit a lower selectivity. Accounting for the expected excess energy allows the prediction of the observed product ratios and, in turn, the product ratios can be used to determine the energy present in an intermediate.

| S-EPMC5785089 | biostudies-literature

Controlling Reaction Selectivity over Hybrid Plasmonic Nanocatalysts.

Project description:The localized surface plasmon resonance (LSPR) excitation in plasmonic nanoparticles has been used to accelerate several catalytic transformations under visible-light irradiation. In order to fully harness the potential of plasmonic catalysis, multimetallic nanoparticles containing a plasmonic and a catalytic component, where LSPR-excited energetic charge carriers and the intrinsic catalytic active sites work synergistically, have raised increased attention. Despite several exciting studies observing rate enhancements, controlling reaction selectivity remains very challenging. Here, by employing multimetallic nanoparticles combining Au, Ag, and Pt in an Au@Ag@Pt core-shell and an Au@AgPt nanorattle architectures, we demonstrate that reaction selectivity of a sequential reaction can be controlled under visible light illumination. The control of the reaction selectivity in plasmonic catalysis was demonstrated for the hydrogenation of phenylacetylene as a model transformation. We have found that the localized interaction between the triple bond in phenylacetylene and the Pt nanoparticle surface enables selective hydrogenation of the triple bond (relative to the double bond in styrene) under visible light illumination. Atomistic calculations show that the enhanced selectivity toward the partial hydrogenation product is driven by distinct adsorption configurations and charge delocalization of the reactant and the reaction intermediate at the catalyst surface. We believe these results will contribute to the use of plasmonic catalysis to drive and control a wealth of selective molecular transformations under ecofriendly conditions and visible light illumination.

| S-EPMC6348440 | biostudies-literature

Bipyrrole boomerangs via Pd-mediated tandem cyclization-oxygenation. Controlling reaction selectivity and electronic properties.

Project description:Boomerang-shaped bipyrroles containing donor-acceptor units were obtained through a tandem palladium-mediated reaction consisting of a cyclization step, involving double C-H bond activation, and a double ?-oxygenation. The latter reaction can be partly suppressed for the least reactive systems, providing access to ?-unsubstituted boomerangs for the first time. These "?-free" systems are highly efficient fluorophores, with emission quantum yields exceeding 80% in toluene. Preliminary measurements show that helicene-like boomerangs may be usable as circularly polarized luminescent materials.

| S-EPMC7214875 | biostudies-literature

Acclimation temperature affects thermal reaction norms for energy reserves in Drosophila.

Project description:Organisms have evolved various physiological mechanisms to cope with unfavourable environmental conditions. The ability to tolerate non-optimal thermal conditions can be substantially improved by acclimation. In this study, we examined how an early-life acclimation to different temperatures (19 °C, 25 °C and 29 °C) influences thermal reaction norms for energy stores in Drosophila adults. Our results show that acclimation temperature has a significant effect on the amount of stored fat and glycogen (and their relative changes) and the optimal temperature for their accumulation. Individuals acclimated to 19 °C had, on average, more energy reserves than flies that were initially maintained at 25 °C or 29 °C. In addition, acclimation caused a shift in optimal temperature for energy stores towards acclimation temperature. We also detected significant population differences in this response. The effect of acclimation on the optimal temperature for energy stores was more pronounced in flies from the temperate climate zone (Slovakia) than in individuals from the tropical zone (India). Overall, we found that the acclimation effect was stronger after acclimation to low (19 °C) than to high (29 °C) temperature. The observed sensitivity of thermal reaction norms for energy reserves to acclimation temperature can have important consequences for surviving periods of food scarcity, especially at suboptimal temperatures.

| S-EPMC7729904 | biostudies-literature

Controlling Selectivity by Controlling the Path of Trajectories.

Project description:Consideration of the role of dynamic trajectories in [1,2]- and [2,3]-sigmatropic rearrangements suggests a counterintuitive approach to controlling the selectivity. In our hypothesis, [2,3] selectivity can be promoted by reaction conditions that thermodynamically disfavor the [2,3] rearrangement step and thereby make the transition state later. The application of this idea has led to a successful prescription for dictating the selectivity in Stevens/Sommelet-Hauser rearrangements of ammonium ylides. A combination of kinetic isotope effects, crossover experiments, and computational dynamic trajectories support the idea that the selectivity is controlled through control of the path of trajectories.

| S-EPMC4672743 | biostudies-literature

An efficient networking solution for extending and controlling wireless sensor networks using low-energy technologies.

Project description:Wireless sensor networks connect a set of highly flexible wireless devices with small weight and size. They are used to monitor and control the environment by organizing the acquired data at a central device. Constructing fully connected networks using low power consumption sensors, devices, and protocols is one of the main challenges facing wireless sensor networks, especially in places where it is difficult to establish wireless networks in a normal way, such as military areas, archaeological sites, agricultural districts, construction sites, and so on. This paper proposes an approach for constructing and extending Bi-Directional mesh networks using low power consumption technologies inside various indoors and outdoors architectures called "an adaptable Spider-Mesh topology". The use of ESP-NOW protocol as a communication technology added an advantage of longer communication distance versus a slight increase of consumed power. It provides 15 times longer distance compared to BLE protocol while consuming only twice as much power. Therefore, according to our theoretical and experimental comparisons, the proposed approach could provide higher network coverage while maintaining an acceptable level of power consumption.

| S-EPMC8627223 | biostudies-literature

Subcellular Partitioning and Intramacrophage Selectivity of Antimicrobial Compounds against Mycobacterium tuberculosis.

Project description:The efficacy of antimicrobial drugs against Mycobacterium tuberculosis, an intracellular bacterial pathogen, is generally first established by testing compounds against bacteria in axenic culture. However, inside infected macrophages, bacteria encounter an environment which differs substantially from broth culture and are subject to important host-dependent pharmacokinetic phenomena which modulate drug activity. Here, we describe how pH-dependent partitioning drives asymmetric antimicrobial drug distribution in M. tuberculosis-infected macrophages. Specifically, weak bases with moderate activity against M. tuberculosis (fluoxetine, sertraline, and dibucaine) were shown to accumulate intracellularly due to differential permeability and relative abundance of their ionized and nonionized forms. Nonprotonatable analogs of the test compounds did not show this effect. Neutralization of acidic organelles directly with ammonium chloride or indirectly with bafilomycin A1 partially abrogated the growth restriction of these drugs. Using high-performance liquid chromatography, we quantified the degree of accumulation and reversibility upon acidic compartment neutralization in macrophages and observed that accumulation was greater in infected than in uninfected macrophages. We further demonstrate that the efficacy of a clinically used compound, clofazimine, is augmented by pH-based partitioning in a macrophage infection model. Because the parameters which govern this effect are well understood and are amenable to chemical modification, this knowledge may enable the rational development of more effective antibiotics against tuberculosis.

| S-EPMC5328571 | biostudies-literature

Connecting thermal physiology and latitudinal niche partitioning in marine Synechococcus.

Project description:Marine Synechococcus cyanobacteria constitute a monophyletic group that displays a wide latitudinal distribution, ranging from the equator to the polar fronts. Whether these organisms are all physiologically adapted to stand a large temperature gradient or stenotherms with narrow growth temperature ranges has so far remained unexplored. We submitted a panel of six strains, isolated along a gradient of latitude in the North Atlantic Ocean, to long- and short-term variations of temperature. Upon a downward shift of temperature, the strains showed strikingly distinct resistance, seemingly related to their latitude of isolation, with tropical strains collapsing while northern strains were capable of growing. This behaviour was associated to differential photosynthetic performances. In the tropical strains, the rapid photosystem II inactivation and the decrease of the antioxydant β-carotene relative to chl a suggested a strong induction of oxidative stress. These different responses were related to the thermal preferenda of the strains. The northern strains could grow at 10 °C while the other strains preferred higher temperatures. In addition, we pointed out a correspondence between strain isolation temperature and phylogeny. In particular, clades I and IV laboratory strains were all collected in the coldest waters of the distribution area of marine Synechococus. We, however, show that clade I Synechococcus exhibit different levels of adaptation, which apparently reflect their location on the latitudinal temperature gradient. This study reveals the existence of lineages of marine Synechococcus physiologically specialised in different thermal niches, therefore suggesting the existence of temperature ecotypes within the marine Synechococcus radiation.

| S-EPMC4030225 | biostudies-literature

Partitioning a reaction-diffusion ecological network for dynamic stability.

Project description:The loss of dispersal connections between habitat patches may destabilize populations in a patched ecological network. This work studies the stability of populations when one or more communication links is removed. An example is finding the alignment of a highway through a patched forest containing a network of metapopulations in the patches. This problem is modelled as that of finding a stable cut of the graph induced by the metapopulations network, where nodes represent the habitat patches and the weighted edges model the dispersal between habitat patches. A reaction-diffusion system on the graph models the dynamics of the predator-prey system over the patched ecological network. The graph Laplacian's Fiedler value, which indicates the well-connectedness of the graph, is shown to affect the stability of the metapopulations. We show that, when the Fiedler value is sufficiently large, the removal of edges without destabilizing the dynamics of the network is possible. We give an exhaustive graph partitioning procedure, which is suitable for smaller networks and uses the criterion for both the local and global stability of populations in partitioned networks. A heuristic graph bisection algorithm that preserves the preassigned lower bound for the Fiedler value is proposed for larger networks and is illustrated with examples.

| S-EPMC6451970 | biostudies-literature

Crystallization Selectivity of Ribavirin Solution and Amorphous Phase.

Project description:Crystallization selectivity is an important principle in polymorph control. Ribavirin Form I, Form II, DMSO solvate, and amorphous ribavirin are prepared, and the short-range order similarities between these solid forms and ribavirin aqueous solution and DMSO solution are compared via mid-frequency Raman difference spectra (MFRDS). The crystallization process from amorphous ribavirin to Form I and from solution to amorphous phase is explained. Reasons for the difficulty in preparing the DMSO solvate are proposed. The rationale provided for the crystallization selectivity provides a foundation for the synthesis of metastable phases with a robust and convenient method.

| S-EPMC10488721 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data