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1.
Dr. Aleksandra Markovic Luca Gerhards Dr. Pia Sander Dr. Carsten Dosche Prof. Dr. Thorsten Klüner Prof. Dr. Rüdiger Beckhaus Prof. Gunther Wittstock 《Chemphyschem》2020,21(22):2506-2514
Multinuclear transition metal complexes bridged by ligands with extended π-electronic systems show a variety of complex electronic transitions and electron transfer reactions. While a systematic understanding of the photochemistry and electrochemistry has been attained for binuclear complexes, much less is known about trinuclear complexes such as hexaphenyl-5,6,11,12,17,18-hexaazatrinaphthylene-tristitanocene [(Cp2Ti)3HATN(Ph)6]. The voltammogram of [(Cp2Ti)3HATN(Ph)6] shows six oxidation and three reduction waves. Solution spectra of [(Cp2Ti)3HATN(Ph)6] and of the electrochemically formed oxidation products show electronic transitions in the UV, visible and the NIR ranges. Density functional theory (DFT) and linear response time-dependent DFT show that the three formally titanium(II) centers transfer an electron to the HATN ligand in the ground state. The optically excited transitions occur exclusively between ligand-centered orbitals. The charged titanium centers only provide an electrostatic frame to the extended π-electronic system. Complete active self-consistent field (CASSCF) calculation on a structurally simplified model compound, which considers the multi-reference character imposed by the three titanium centers, can provide an interpretation of the experimentally observed temperature-dependent magnetic behavior of the different redox states of the title compound in full consistency with the interpretation of the electronic spectra. 相似文献
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Mathematical Programming - A classic result by Cook, Gerards, Schrijver, and Tardos provides an upper bound of $$n \Delta $$ on the proximity of optimal solutions of an Integer Linear Programming... 相似文献
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José Elguero Ibon Alkorta Janet E. Del Bene 《Magnetic resonance in chemistry : MRC》2020,58(8):727-732
Equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) calculations have been performed to determine coupling constants 1J(X–Y) for 65 molecules HmX–YHn, with X,Y ═ 1H, 7Li, 9Be, 11B, 13C, 15N, 17O, 19F, 31P, 33S, and 35Cl. The computed 1J(X–Y) values are in good agreement with available experimental data. The reduced coupling constants 1K(X–Y) have been derived from 1J(X–Y) by removing the dependence on the magnetogyric ratios of X and Y. Patterns are found for the reduced coupling constants on a 1K(X–Y) surface that are related to the positions of X and Y in the periodic table. 相似文献
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Michele Iannone Anna Pia Dima Francesca Sciarra Francesco Botrè Andrea M. Isidori 《Biomedical chromatography : BMC》2022,36(5):e5344
We present a liquid chromatography tandem mass spectrometry method for the simultaneous analysis of 16 endogenous steroids (androgens, estrogens, glucocorticoids and progestogens) in human serum. Samples (250 μl of matrix) were extracted with t-butylmethyl ether prior to LC–MS/MS analysis. The chromatographic separation was achieved on a reversed-phase column using a methanol–water gradient. The HPLC was coupled to a triple quadrupole mass spectrometer equipped with an electrospray ionization source with acquisition in multiple reaction monitoring mode. The method was validated using surrogate matrices and human serum samples. The specificity of the method was confirmed for all of the considered steroids; linearity was also assessed (R2 > 0.99, lack-of-fit test) in the ranges of concentrations investigated. The lower limits of quantification were in the range 10–400 pg/ml depending on the target steroid. Accuracy was in the range 85–115% for all target steroids except for the lower limit of quantitation levels where it was 80–120%. The extraction recovery was always >65%. No significant matrix effects were observed. To test the reliability of the method, the analysis of serum samples collected from 10 healthy subjects (5 M/5F) was performed. The present method can be used to identify the trajectories of deviation from the concentration normality ranges applied to disorders of the gonadal and adrenal axes. 相似文献
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Simone Brannetti Serena Gentile Dr. Alejandro Chamorro-Garcia Luca Barbero Dr. Erica Del Grosso Prof. Francesco Ricci 《Angewandte Chemie (International ed. in English)》2023,62(47):e202313243
Here we develop Lateral Flow Assays (LFAs) that employ as functional elements DNA-based structures decorated with reporter tags and recognition elements. We have rationally re-engineered tile-based DNA tubular structures that can act as scaffolds and can be decorated with recognition elements of different nature (i.e. antigens, aptamers or proteins) and with orthogonal fluorescent dyes. As a proof-of-principle we have developed sandwich and competitive multiplex lateral flow platforms for the detection of several targets, ranging from small molecules (digoxigenin, Dig and dinitrophenol, DNP), to antibodies (Anti-Dig, Anti-DNP and Anti-MUC1/EGFR bispecific antibodies) and proteins (thrombin). Coupling the advantages of functional DNA-based scaffolds together with the simplicity of LFAs, our approach offers the opportunity to detect a wide range of targets with nanomolar sensitivity and high specificity. 相似文献
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Adriana C. Casabuono Cecilia Czibener Mariela G. Del Giudice Ezequiel Valguarnera Juan E. Ugalde Alicia S. Couto 《Journal of the American Society for Mass Spectrometry》2017,28(12):2716-2723
Brucellaceae are Gram-negative bacteria that cause brucellosis, one of the most distributed worldwide zoonosis, transmitted to humans by contact with either infected animals or their products. The lipopolysaccharide exposed on the cell surface has been intensively studied and is considered a major virulence factor of Brucella. In the last years, structural studies allowed the determination of new structures in the core oligosaccharide and the O-antigen of this lipopolysaccharide. In this work, we have reinvestigated the lipid A structure isolated from B. suis and B. abortus lipopolysaccharides. A detailed study by MALDI-TOF mass spectrometry in the positive and negative ion modes of the lipid A moieties purified from both species was performed. Interestingly, a new feature was detected: the presence of a pyrophosphorylethanolamine residue substituting the backbone. LID-MS/MS analysis of some of the detected ions allowed assurance that the Lipid A structure composed by the diGlcN3N disaccharide, mainly hexa-acylated and penta-acylated, bearing one phosphate and one pyrophosphorylethanolamine residue. 相似文献
10.
Pierre?Del?Moral Ajay?JasraEmail author Yan?Zhou 《Methodology and Computing in Applied Probability》2017,19(3):727-749
We consider Bayesian online static parameter estimation for state-space models. This is a very important problem, but is very computationally challenging as the state-of-the art methods that are exact, often have a computational cost that grows with the time parameter; perhaps the most successful algorithm is that of SM C2 (Chopin et al., J R Stat Soc B 75: 397–426 2013). We present a version of the SM C2 algorithm which has computational cost that does not grow with the time parameter. In addition, under assumptions, the algorithm is shown to provide consistent estimates of expectations w.r.t. the posterior. However, the cost to achieve this consistency can be exponential in the dimension of the parameter space; if this exponential cost is avoided, typically the algorithm is biased. The bias is investigated from a theoretical perspective and, under assumptions, we find that the bias does not accumulate as the time parameter grows. The algorithm is implemented on several Bayesian statistical models. 相似文献