Search results for "coupled"
showing 10 items of 742 documents
Isotope-dilution ICP-MS for trace element determination and speciation: from a reference method to a routine method?
2003
This critical review discusses the conditions under which inductively coupled plasma-isotope dilution mass spectrometry (ICP-IDMS) is suitable as a routine method for trace element and element-speciation analysis. It can, in general, be concluded that ICP-IDMS has high potential for routine analysis of trace elements if the accuracy of results is of predominant analytical importance. Hyphenated techniques with ICP-IDMS suffer both from lack of commercially available isotope-labeled spike compounds for species-specific isotope dilution and from the more complicated system set-up required for species-unspecific ICP-IDMS analysis. Coupling of gas or liquid chromatography with species-specific …
Approximate treatment of higher excitations in coupled-cluster theory.
2005
The possibilities for the approximate treatment of higher excitations in coupled-cluster (CC) theory are discussed. Potential routes for the generalization of corresponding approximations to lower-level CC methods are analyzed for higher excitations. A general string-based algorithm is presented for the evaluation of the special contractions appearing in the equations specific to those approximate CC models. It is demonstrated that several iterative and noniterative approximations to higher excitations can be efficiently implemented with the aid of our algorithm and that the coding effort is mostly reduced to the generation of the corresponding formulas. The performance of the proposed and …
Theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis-, and trans-1,2-difluoroethylenes.
2014
A theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis- and trans-1,2-difluoroethylenes is reported. The results obtained using density functional theory (DFT) combined with large basis sets and gauge-independent atomic orbital calculations were critically compared with experiment and conventional, higher level correlated electronic structure methods. Accurate structural, vibrational, and NMR parameters of difluoroethylenes were obtained using several density functionals combined with dedicated basis sets. B3LYP/6-311++G(3df,2pd) optimized structures of difluoroethylenes closely reproduced experimental geometries and earlier reported b…
Coupled-Cluster study of ‘no-pair’ bonding in the tetrahedral Cu4 cluster
2011
Abstract Ab initio Coupled-Cluster calculations with single and double excitations and perturbative correction to the triple, CCSD(T), have been carried out for the high-spin electronic state, ( 5 A 2 ) , of the copper cluster Cu 4 in its tetrahedral arrangement. Like alkali metals clusters, tetrahedral Cu 4 presents a bound quintet state, i.e., a situation where all the valence electrons are unpaired. This rather exotic wavefunction, also known as no-pair bonding state, is examined in detail. The influence of the basis set is also analyzed, as well as the importance of the core correlation and the effect of the basis-set superposition errors.
Probes for studying cholesterol binding and cell biology.
2011
Cholesterol is a multifunctional lipid in eukaryotic cells. It regulates the physical state of the phospholipid bilayer, is crucially involved in the formation of membrane microdomains, affects the activity of many membrane proteins, and is the precursor for steroid hormones and bile acids. Thus, cholesterol plays a profound role in the physiology and pathophysiology of eukaryotic cells. The cholesterol molecule has achieved evolutionary perfection to fulfill its different functions in membrane organization. Here, we review basic approaches to explore the interaction of cholesterol with proteins, with a particular focus on the high diversity of fluorescent and photoreactive cholesterol prob…
Ligation Tunes Protein Reactivity in an Ancient Haemoglobin: Kinetic Evidence for an Allosteric Mechanism in Methanosarcina acetivorans Protoglobin
2012
Abstract: Protoglobin from Methanosarcina acetivorans (MaPgb) is a dimeric globin with peculiar structural properties such as a completely buried haem and two orthogonal tunnels connecting the distal cavity to the solvent. CO binding to and dissociation from MaPgb occur through a biphasic kinetics. We show that the heterogenous kinetics arises from binding to (and dissociation from) two tertiary conformations in ligation-dependent equilibrium. Ligation favours the species with high binding rate (and low dissociation rate). The equilibrium is shifted towards the species with low binding (and high dissociation) rates for the unliganded molecules. A quantitative model is proposed to describe t…
A comparative study on sample preparation procedures for supplementary foods by ICP-OES: Green chemistry considerations
2015
An inductively coupled plasma optical emission (ICP-OES) method was developed for the simultaneous determination of major, minor and trace elements in food. Preliminary studies focused on selecting suitable operational conditions in order to provide the highest sensitivity and to maximize the number of analytes to be determined without spectral or matrix interference. Ruthenium and rhenium were evaluated as internal standards and samples were analyzed at different dilution levels. Furthermore, a comparative study was carried out by using three sample digestion methods, microwave-assisted digestion with HNO3/H2O2, dry ashing and dry ashing with Mg(NO3)2/MgO as an ashing aid. Adequate precisi…
Infrared evolved gas analysis during thermal investigation of lanthanum, europium and samarium carbonates
2003
Abstract The characterisation of rare earth elements carbonates (REECs) was performed by thermal analysis (TG–DTG) combined with simultaneous infrared evolved gas analysis–Fourier transform infrared (EGA–FTIR) spectroscopy. The TG–DTG curves were obtained using the Perkin-Elmer PC series TGA-7 thermogravimetric analyser in the temperature range 25–800 °C both in dynamic air and nitrogen atmosphere. La 2 (CO 3 ) 3 · n H 2 O, Eu 2 (CO 3 ) 3 · n H 2 O and Sm 2 (CO 3 ) 3 · n H 2 O were analysed, the dehydration and decarbonation steps were investigated and the water content was calculated. The trace rare earth elements in lanthanum, europium and samarium carbonates were determined by Philips PU…
Electronic Structures and Molecular Properties of Chalcogen Nitrides Se2N2 and SeSN2
2006
The electronic structures and molecular properties of S2N2 as well as the currently unknown chalcogen nitrides Se2N2 and SeSN2 have been studied using various ab initio and density functional methods. All molecules share a qualitatively similar electronic structure and can be primarily described as 2π-electron aromatics having minor singlet diradical character of 6−8% that can be attributed solely to the nitrogen atoms. This diradical character is manifested in the prediction of their molecular properties, in which coupled cluster and multiconfigurational approaches, as well as density functional methods, show the best performance. The conventional ab initio methods RHF and MP2 completely f…
Photochemical Synthesis of Water-Soluble Gold Nanorods: The Role of Silver Ions in Assisting Anisotropic Growth
2009
The role of Ag+ ions in the ultraviolet-driven photochemical synthesis of Au nanorods (NRs) in aqueous surfactant mixtures has been investigated in order to elucidate the mechanism that drives anisotropic nanoparticle growth. The samples, grown in the presence of varying amounts of Ag+ ions for scheduled irradiation times, have been characterized by ultraviolet−visible−near infrared (UV−vis−NIR) absorption spectroscopy, analytical transmission electron microscopy (ATEM), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and extended X-ray absorption fine structure (EXAFS) measurements. Moreover, the time evolution of size and shape distribution has been investigated by stat…