Search results for "molecule"

A theory ofnonverticaltriplet energy transfer in terms of accurate potential energy surfaces: The transfer reaction from π,π* triplet donors to 1,3,5…

2004

Triplet energy transfer (TET) from aromatic donors to 1,3,5,7-cyclooctatetraene (COT) is an extreme case of "nonvertical" behavior, where the transfer rate for low-energy donors is considerably faster than that predicted for a thermally activated (Arrhenius) process. To explain the anomalous TET of COT and other molecules, a new theoretical model based on transition state theory for nonadiabatic processes is proposed here, which makes use of the adiabatic potential energy surfaces (PES) of reactants and products, as computed from high-level quantum mechanical methods, and a nonadiabatic transfer rate constant. It is shown that the rate of transfer depends on a geometrical distortion paramet…

Data mining, dashboards and statistics: a powerful framework for the chemical design of molecular nanomagnets

2021

Abstract Three decades of intensive research in molecular nanomagnets have brought the magnetic memory in molecules from liquid helium to liquid nitrogen temperature. The enhancement of this operational temperature relies on a wise choice of the magnetic ion and the coordination environment. However, serendipity, oversimplified theories and chemical intuition have played the main role. In order to establish a powerful framework for statistically driven chemical design, we collected chemical and physical data for lanthanide-based nanomagnets to create a catalogue of over 1400 published experiments, developed an interactive dashboard (SIMDAVIS) to visualise the dataset, and applied inferentia…

Prediction and Discrimination of Pharmacological Activity by Using Artificial Neural Networks

2003

The design of new medical drugs is a very complex process in which combinatorial chemistry techniques are used. For this reason, it is very useful to have tools to predict and to discriminate the pharmacological activity of a given molecular compound so that the laboratory experiments can be directed to those molecule groups in which there is a high probability of finding new compounds with the desired properties. This work presents an application of Artificial Neural Networks to the problem of discriminating and predicting pharmacological characteristics of a molecular compound from its topological properties. A large amount of different configurations are tested, yielding very good perfor…

Ionic liquids/[bmim][N3] mixtures: promising media for the synthesis of aryl azides by SNAr

2008

The nucleophilic aromatic substitution of some activated aryl or heteroaryl halides has been performed in ionic liquid solution, using the 1-butyl-3-methylimidazolium azide as a nucleophile. The reaction course was studied varying the structures of both substrates and ionic liquids. In particular, in the latter case, the reaction of 2-bromo-5-nitrothiophene was carried out in five different ionic liquids ([bmim][BF 4], [bmim][PF 6], [bmim][NTf 2], [bm 2im][NTf 2], and [bmpyrr][NTf 2]). Finally, for all the substrates considered, a comparison with data obtained in MeOH solution in the presence of NaN 3 was also performed. Data collected indicate that in some cases it is possible to obtain ar…

Oxygen depletion in dense molecular clouds: a clue to a low O2 abundance?

2011

Context: Dark cloud chemical models usually predict large amounts of O2, often above observational limits. Aims: We investigate the reason for this discrepancy from a theoretical point of view, inspired by the studies of Jenkins and Whittet on oxygen depletion. Methods: We use the gas-grain code Nautilus with an up-to-date gas-phase network to study the sensitivity of the molecular oxygen abundance to the oxygen elemental abundance. We use the rate coefficient for the reaction O + OH at 10 K recommended by the KIDA (KInetic Database for Astrochemistry) experts. Results: The updates of rate coefficients and branching ratios of the reactions of our gas-phase chemical network, especially N + C…

The hyperfine structure in the rotational spectrum of CF+

2012

Context. CF+ has recently been detected in the Horsehead and Orion Bar photo-dissociation regions. The J=1-0 line in the Horsehead is double-peaked in contrast to other millimeter lines. The origin of this double-peak profile may be kinematic or spectroscopic. Aims. We investigate the effect of hyperfine interactions due to the fluorine nucleus in CF+ on the rotational transitions. Methods. We compute the fluorine spin rotation constant of CF+ using high-level quantum chemical methods and determine the relative positions and intensities of each hyperfine component. This information is used to fit the theoretical hyperfine components to the observed CF+ line profiles, thereby employing the h…

Caractérisation des figures myéliniques associées à l'accumulation de lipides polaires induites par différents oxystérols cytotoxiques identifiés dan…

2006

Atherosclerosis is a complex and chronic arterial process which is characterized by a remodeling of the vascular wall, associated with inflammatory reactions, proliferation and cell death process, and with accumulation of oxidized lipids among which oxysterols (cholesterol oxidation products) which might play key roles in the initiation and development of atheromatous lesions. Our work performed on U937 and THP1 promonocytic cells, rat aorta embryonic A7R5 cells, and breast carcinoma MCF7 cells (caspase-3 deficient). Different oxysterols, present in large quantity in atheromatous lesions, were used: 7-cétocholestérol (7KC), 7Β-hydroxycholestérol, 25-hydroxycholestérol, cholestérol-5Α, 6Α-ep…

Simulation of organics in the atmosphere: evaluation of EMACv2.54 with the Mainz Organic Mechanism (MOM) coupled to the ORACLE (v1.0) submodel

2021

Abstract. An updated and expanded representation of organics in the chemistry general circulation model EMAC (ECHAM5/MESSy for Atmospheric Chemistry) has been evaluated. First, the comprehensive Mainz Organic Mechanism (MOM) in the submodel MECCA (Module Efficiently Calculating the Chemistry of the Atmosphere) was activated with explicit degradation of organic species up to five carbon atoms and a simplified mechanism for larger molecules. Second, the ORACLE submodel (version 1.0) considers now condensation on aerosols for all organics in the mechanism. Parameterizations for aerosol yields are used only for the lumped species that are not included in the explicit mechanism. The simultaneous…

2016

Abstract. Gaseous formaldehyde (HCHO) is an important precursor of OH radicals and a key intermediate molecule in the oxidation of atmospheric volatile organic compounds (VOCs). Budget analyses reveal large discrepancies between modeled and observed HCHO concentrations in the atmosphere. Here, we investigate the interactions of gaseous HCHO with soil surfaces through coated-wall flow tube experiments applying atmospherically relevant HCHO concentrations of  ∼  10 to 40 ppbv. For the determination of uptake coefficients (γ), we provide a Matlab code to account for the diffusion correction under laminar flow conditions. Under dry conditions (relative humidity  =  0 %), an initial γ of (1.1 ± …

Synthesis and characterisation of peroxypinic acids as proxies for highly oxygenated molecules (HOMs) in secondary organic aerosol

2018

Abstract. Peroxy acids were recently found to be involved in new particle formation in the atmosphere and could also substantially contribute towards particle toxicity. However, a lack of suitable analytical methods for the detection and characterisation of peroxy acids in the particle phase is currently hindering the quantitative investigation of their contribution to these important atmospheric processes. Further development of appropriate techniques and relevant standards is therefore urgently needed. In this study, we synthesised three peroxypinic acids, developed a liquid chromatography separation method and characterised them with tandem mass spectrometry. The observed fragmentation p…