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991.
Insulin administration can increase muscle glycogen by utilising hyperinsulinaemic clamps prior to sports events or during the recovery phases, and increase muscle size by its chalonic action to inhibit protein breakdown. In order to control insulin abuse in equine sports, a method to detect effectively the use of insulins in horses would be required. Besides the readily available human insulin and its synthetic analogues, structurally similar insulins from other species can also be used as doping agents. This study describes a method for the simultaneous detection of bovine, porcine and human insulins, as well as the synthetic analogues Humalog (Lilly) and Novolog (Novo Nordisk) in equine plasma. Insulins were isolated from equine plasma by immunoaffinity purification, followed by centrifugal filtration, and analysed by nano-liquid chromatography-tandem mass spectrometry (LC/MS/MS). Insulin and analogues were detected and confirmed by comparing their retention times and major product ions. All five insulins (human insulin, Humalog, Novolog, bovine insulin and porcine insulin), which are exogenous in the horse, could be detected and confirmed at 0.05ng/mL. This method was successful in confirming the presence of human insulin in plasma collected from horses up to 4h after having been administered a single low dose of recombinant human insulin (Humulin R, Eli Lilly). To our knowledge, this is the first identification of exogenous insulin from post-administration horse plasma samples. 相似文献
992.
Glauser G Guillarme D Grata E Boccard J Thiocone A Carrupt PA Veuthey JL Rudaz S Wolfender JL 《Journal of chromatography. A》2008,1180(1-2):90-98
A LC-MS approach is presented for the isolation of minor key plant biomarkers, in view of their characterization by NMR at the microgram scale. Due to the complexity of plant extracts, the purification of metabolites present in low concentrations is critical. The strategy used relies on the optimization of the chromatographic analysis using ultra-performance liquid chromatography-time-of-flight mass spectrometry (UPLC-TOF-MS), thanks to modelling software. The optimized method is then transferred to semi-preparative LC conditions with MS detection. The approach is illustrated by the isolation of wound-induced jasmonate derivatives revealed by a metabolomic study in Arabidopsis thaliana leaves and their subsequent characterization by capillary NMR (CapNMR). 相似文献
993.
The catalytic activity of the ruthenium(II) complex [RuCp∗(CH3CN)3][PF6] 1 in the transposition of allylic alcohols into carbonyl compounds, in acetonitrile, is reported. This catalyst has proven to be able to catalyze the transformation of poorly reactive and/or functionalized substrates under smooth conditions. 相似文献
994.
Jayla Morgan Young Ju Yun Abdelqader M. Jamhawi Shahidul M. Islam A. Jean-Luc Ayitou 《Photochemistry and photobiology》2023,99(2):761-768
We report the synthesis and photophysical characterization of novel halogenated dipyrrolonaphthyridine-diones (X2–DPNDs, X = Cl, Br, and I), as candidates for photodynamic therapy (PDT) application. Apart from the heavy atom-induced spin-orbit coupling (SOC) dynamics in the investigated X2–DPNDs, it was found that the position of the halogen atom (relative to the nitrogen of the pyrrole ring) also influenced the triplet excited state behavior. Interestingly, the faster/efficiency sensitization of 3O2 to 1O2 using X2–DPND correlates with the rate of triplet population, kISC >1.6 × 108 s−1 for I2–DPND vs kISC >2.9 × 109 s−1 for Cl2–DPND and Br2–DPND (where τISC = 343 ± 3 ps for I2–DPND and τISC = 5–6 ns for Cl2–DPND and Br2–DPND are the lowest time constants/values for ISC). Furthermore, the heavy atom-induced SOC in Cl2–DPND and Br2–DPND did not lead to a reduction of the corresponding fluorescence (ca 75% vs 67% for the parent DPND). The attractive photophysical characteristics of Cl2/Br2–DPND put them on the landscape as not only promising PDT agents but also as fluorescence probes. The present study is a stepping stone in the development of novel organic photosystems for synergistic photomedicinal applications. 相似文献
995.
Bouziane A Hélou M Carboni B Carreaux F Demerseman B Bruneau C Renaud JL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(18):5630-5637
Secondary allylic alcohols were synthesized from linear allylic halides or carbonates using a catalytic amount of a ruthenium complex in the presence of boronic acid. The effects of solvent, base, ruthenium precursor, and boronic acid were fully explored, and the scope of the reaction was extended to various substrates. We also describe a preliminary investigation towards an enantioselective process. 相似文献
996.
C Kisielowski B Freitag M Bischoff H van Lin S Lazar G Knippels P Tiemeijer M van der Stam S von Harrach M Stekelenburg M Haider S Uhlemann H Müller P Hartel B Kabius D Miller I Petrov E A Olson T Donchev E A Kenik A R Lupini J Bentley S J Pennycook I M Anderson A M Minor A K Schmid T Duden V Radmilovic Q M Ramasse M Watanabe R Erni E A Stach P Denes U Dahmen 《Microscopy and microanalysis》2008,14(5):469-477
The ability of electron microscopes to analyze all the atoms in individual nanostructures is limited by lens aberrations. However, recent advances in aberration-correcting electron optics have led to greatly enhanced instrument performance and new techniques of electron microscopy. The development of an ultrastable electron microscope with aberration-correcting optics and a monochromated high-brightness source has significantly improved instrument resolution and contrast. In the present work, we report information transfer beyond 50 pm and show images of single gold atoms with a signal-to-noise ratio as large as 10. The instrument's new capabilities were exploited to detect a buried Sigma3 {112} grain boundary and observe the dynamic arrangements of single atoms and atom pairs with sub-angstrom resolution. These results mark an important step toward meeting the challenge of determining the three-dimensional atomic-scale structure of nanomaterials. 相似文献
997.
Höfener S Bischoff FA Glöss A Klopper W 《Physical chemistry chemical physics : PCCP》2008,10(23):3390-3399
In the recent years, Slater-type geminals (STGs) have been used with great success to expand the first-order wave function in an explicitly-correlated perturbation theory. The present work reports on this theory's implementation in the framework of the Turbomole suite of programs. A formalism is presented for evaluating all of the necessary molecular two-electron integrals by means of the Obara-Saika recurrence relations, which can be applied when the STG is expressed as a linear combination of a small number (n) of Gaussians (STG-nG geminal basis). In the Turbomole implementation of the theory, density fitting is employed and a complementary auxiliary basis set (CABS) is used for the resolution-of-the-identity (RI) approximation of explicitly-correlated theory. By virtue of this RI approximation, the calculation of molecular three- and four-electron integrals is avoided. An approximation is invoked to avoid the two-electron integrals over the commutator between the operators of kinetic energy and the STG. This approximation consists of computing commutators between matrices in place of operators. Integrals over commutators between operators would have occurred if the theory had been formulated and implemented as proposed originally. The new implementation in Turbomole was tested by performing a series of calculations on rotational conformers of the alkanols n-propanol through n-pentanol. Basis-set requirements concerning the orbital basis, the auxiliary basis set for density fitting and the CABS were investigated. Furthermore, various (constrained) optimizations of the amplitudes of the explicitly-correlated double excitations were studied. These amplitudes can be optimized in orbital-variant and orbital-invariant manners, or they can be kept fixed at the values governed by the rational generator approach, that is, by the electron cusp conditions. Electron-correlation effects beyond the level of second-order perturbation theory were accounted for by conventional coupled-cluster calculations with single, double and perturbative triple excitations [CCSD(T)]. The explicitly-correlated perturbation theory results were combined with CCSD(T) results and compared with literature data obtained by basis-set extrapolation. 相似文献
998.
A simple method using ultra performance LC (UPLC) coupled with UV detection was developed and validated for the determination of antituberculosis drugs in combined dosage form, i. e. isoniazid (ISN), pyrazinamide (PYR) and rifampicin (RIF). Drugs were separated on a short column (2.1 mm x 50 mm) packed with 1.7 mum particles, using an elution gradient procedure. At 30 degrees C, less than 2 min was necessary for the complete separation of the three antituberculosis drugs, while the original USP method was performed in 15 min. Further improvements were obtained with the combination of UPLC and high temperature (up to 90 degrees C), namely HT-UPLC, which allows the application of higher mobile phase flow rates. Therefore, the separation of ISN, PYR and RIF was performed in less than 1 min. After validation (selectivity, trueness, precision and accuracy), both methods (UPLC and HT-UPLC) have proven suitable for the routine quality control analysis of antituberculosis drugs in combined dosage form. Additionally, a large number of samples per day can be analysed due to the short analysis times. 相似文献
999.
Jean-Luc Marichal 《Discrete Applied Mathematics》2008,156(1):11-24
The Lovász extension of a pseudo-Boolean function f:{0,1}n→R is defined on each simplex of the standard triangulation of [0,1]n as the unique affine function that interpolates f at the n+1 vertices of the simplex. Its degree is that of the unique multilinear polynomial that expresses f. In this paper we investigate the least squares approximation problem of an arbitrary Lovász extension by Lovász extensions of (at most) a specified degree. We derive explicit expressions of these approximations. The corresponding approximation problem for pseudo-Boolean functions was investigated by Hammer and Holzman [Approximations of pseudo-Boolean functions; applications to game theory, Z. Oper. Res. 36(1) (1992) 3-21] and then solved explicitly by Grabisch et al. [Equivalent representations of set functions, Math. Oper. Res. 25(2) (2000) 157-178], giving rise to an alternative definition of Banzhaf interaction index. Similarly we introduce a new interaction index from approximations of and we present some of its properties. It turns out that its corresponding power index identifies with the power index introduced by Grabisch and Labreuche [How to improve acts: an alternative representation of the importance of criteria in MCDM, Internat. J. Uncertain. Fuzziness Knowledge-Based Syst. 9(2) (2001) 145-157]. 相似文献
1000.
Shilin Yu Arkady Kupryakov James E. M. Lewis Vicente Martí-Centelles Stephen M. Goldup Jean-Luc Pozzo Gediminas Jonusauskas Nathan D. McClenaghan 《Chemical science》2021,12(26):9196
We demonstrate the first example of bidirectional reversible electronic energy transfer (REET) between the mechanically bonded components of a rotaxane. Our prototypical system was designed such that photoexcitation of a chromophore in the axle results in temporary storage of electronic energy in a quasi-isoenergetic “reservoir” chromophore in the macrocycle. Over time, the emissive state of the axle is repopulated from this reservoir, resulting in long-lived, delayed luminescence. Importantly, we show that cation binding in the cavity formed by the mechanical bond perturbs the axle chromophore energy levels, modulating the REET process, and ultimately providing a luminescence read-out of cation binding. Modulation of REET processes represents an unexplored mechanism in luminescent molecular sensor development.Delayed emission due to reversible electronic energy transfer (REET) between chromophores in the axle and macrocycle components of a rotaxane is demonstrated. The REET process can be modulated by metal ion binding in the cavity of the rotaxane. 相似文献