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31.
Klika KD Kivelä H Ovcharenko VV Nieminen V Sillanpää R Arpalahti J 《Dalton transactions (Cambridge, England : 2003)》2007,(35):3966-3970
The reaction of tetrapyrazine Pt(II) with adenine under basic conditions yielded two products both disubstituted by adenine and bound in all cases to the N-9 nitrogen of adenine. Crystals amenable to X-crystallographic analysis were obtained for one product which was consequently identified as trans-[Pt(II)(N9-adeH)2(pz)2](NO3)(4).H2O. The other product, though, was identified as the cis isomer based on extensive and comparative NMR structural studies whereby the two compounds were examined as both neutral and tetraprotonated species in solution. The major product of the reaction was unexpectedly the cis isomer, thus obtained in contrast to the trans effect, and the reason for this result is speculated on. Computational calculations using DFT at the B3LYP/TZVP-MARI-J level of theory provided the head-to-tail conformer as the overwhelmingly more stable species over the head-to-head conformer for both compounds whilst the trans product was found to be more stable than the cis. Thus the reaction does not follow a thermodynamic course and rather is kinetically controlled in concert with the speculated mode of reaction. 相似文献
32.
Ville Hyvrinen Mika Sorjonen Kai-Erik Peiponen Raimo Silvennoinen Tapani Niskanen Juha Kalliokoski 《Optics and Lasers in Engineering》2000,33(4):311
A technique for all-optical laser cleaning and surface quality monitoring of concave metal surfaces is suggested. Contaminated pharmaceutical punches from a tablet compression machine were cleaned using high-energy laser pulses. Image information obtained from a diffractive-optical-element-based sensor was used in inspection of the surface quality change of the concave punches due to laser cleaning. Alternative method for mechanical cleaning of punches is introduced, which is based on simultaneous laser cleaning and surface quality inspection of the punches. 相似文献
33.
34.
Functional magnetic resonance imaging (fMRI) is widely used to pinpoint active brain areas. Changes in neuronal activity modulate the local blood oxygenation level, and the associated modulation of the magnetic field homogeneity can be detected with magnetic resonance imaging. Thus, the blood oxygenation level-dependent (BOLD) fMRI indirectly measures neuronal activity. Similar modulation of magnetic field homogeneity was here elicited by other means to generate a BOLD-like change in a new phantom constructed to provide reference activations during fMRI. Magnetic inhomogeneities were produced by applying current to coils located near the phantom containing 1.5 ml of Gd-doped water. The signal-to-noise ratio of the images, produced by gradient-recalled echo-planar imaging, varied between 104 and 107 at a selected voxel when the field was and was not inhomogenized, respectively. The contrast of signals between homogeneous and inhomogeneous conditions was generally stable, except in 3% of time points. During the periods of greatest deviations an observable change would have been detected in a simultaneously measured BOLD signal. Such changes could result from the imaging method or occur through glitches in hardware or alterations in the measurement environment. With identical measurement setups, the phantom could allow comparing intersession or intersubject brain activations. 相似文献
35.
Scale factor local search in differential evolution 总被引:8,自引:0,他引:8
This paper proposes the scale factor local search differential evolution (SFLSDE). The SFLSDE is a differential evolution (DE) based memetic algorithm which employs, within a self-adaptive scheme, two local search algorithms. These local search algorithms aim at detecting a value of the scale factor corresponding to an offspring with a high performance, while the generation is executed. The local search algorithms thus assist in the global search and generate offspring with high performance which are subsequently supposed to promote the generation of enhanced solutions within the evolutionary framework. Despite its simplicity, the proposed algorithm seems to have very good performance on various test problems. Numerical results are shown in order to justify the use of a double local search instead of a single search. In addition, the SFLSDE has been compared with a standard DE and three other modern DE based metaheuristic for a large and varied set of test problems. Numerical results are given for relatively low and high dimensional cases. A statistical analysis of the optimization results has been included in order to compare the results in terms of final solution detected and convergence speed. The efficiency of the proposed algorithm seems to be very high especially for large scale problems and complex fitness landscapes. 相似文献
36.
Saario SM Palomäki V Lehtonen M Nevalainen T Järvinen T Laitinen JT 《Chemistry & biology》2006,13(8):811-814
Previous studies indicate that in brain tissue the endocannabinoid 2-AG is inactivated by monoglyceride lipase (MGL)-catalyzed hydrolysis, and a recent report has indicated that MGL activity could be specifically inhibited by URB754 . In the present study, URB754 failed to inhibit 2-AG hydrolysis in rat brain preparations. In addition, brain cryosections were employed to assess whether URB754 could facilitate the detection of 2-AG-stimulated G protein activity. Nevertheless, whereas pretreatment with PMSF readily allowed detection of 2-AG-stimulated G protein activity, URB754 was ineffective. In contrast to previous claims, brain FAAH activity was also resistant to URB754. Thus, in our hands URB754 was not able to block the endocannabinoid-hydrolyzing enzymes and cannot serve as a lead structure for future development of MGL-specific inhibitors. 相似文献
37.
MR imaging of fatigue stress injuries to bones: intra- and interobserver agreement 总被引:11,自引:0,他引:11
Ahovuo JA Kiuru MJ Kinnunen JJ Haapamaki V Pihlajamaki HK 《Magnetic resonance imaging》2002,20(5):401-406
The aim of this study was to determine the validity of MR imaging (MRI) in the assessment of stress-related injuries to bone.MR images of 50 military recruits (8 females and 42 males; 18-27 (mean 20) years of age) were retrospectively evaluated twice for stress injuries to bone by 4 radiologists (2 musculoskeletal radiologists, 2 radiology residents). Coronal T1-weighed (T1W) and STIR images, as well as axial and coronal T2-weighted (T2W) fat-suppressed images were taken using a 1.0T scanner. Rates for sensitivity, specificity, and accuracy of MRI of the stress-related injuries were calculated. Intraobserver and interobserver agreement was determined with kappa statistics.Rates for MRI sensitivity were 27-96%, for specificity 65-100%, and for diagnostic accuracy 58-97%. Lowest rates were seen when reading T1W images and highest when reading STIR images. Readers showed moderate to excellent intraobserver agreement (kappa 0.75-0.95). Interobserver agreement was fair to excellent (kappa 0.41-0.91), and the lowest values were seen in the interpretation of T1W images. Normal findings could be differentiated from various grades of stress injury to bone.MRI is a valid means of revealing the presence of stress injuries to bone and their staging. Observer agreement is good to excellent when using T2W images and STIR images, while T1W images are of lesser value. 相似文献
38.
CL Heinecke TW Ni S Malola V Mäkinen OA Wong H Häkkinen CJ Ackerson 《Journal of the American Chemical Society》2012,134(32):13316-13322
Ligand exchange reactions are widely used for imparting new functionality on or integrating nanoparticles into devices. Thiolate-for-thiolate ligand exchange in monolayer protected gold nanoclusters has been used for over a decade; however, a firm structural basis of this reaction has been lacking. Herein, we present the first single-crystal X-ray structure of a partially exchanged Au(102)(p-MBA)(40)(p-BBT)(4) (p-MBA = para-mercaptobenzoic acid, p-BBT = para-bromobenzene thiol) with p-BBT as the incoming ligand. The crystal structure shows that 2 of the 22 symmetry-unique p-MBA ligand sites are partially exchanged to p-BBT under the initial fast kinetics in a 5 min timescale exchange reaction. Each of these ligand-binding sites is bonded to a different solvent-exposed Au atom, suggesting an associative mechanism for the initial ligand exchange. Density functional theory calculations modeling both thiol and thiolate incoming ligands postulate a mechanistic pathway for thiol-based ligand exchange. The discrete modification of a small set of ligand binding sites suggests Au(102)(p-MBA)(44) as a powerful platform for surface chemical engineering. 相似文献
39.
Katja Lappalainen Mikko Manninen Ville Alopaeus Juhani Aittamaa John Dodds 《Transport in Porous Media》2009,77(1):17-40
Capillary pressure is considered in packed-beds of spherical particles. In the case of gas–liquid flows in packed-bed reactors,
capillary pressure gradients can have a significant influence on liquid distribution and, consequently, on the overall reactor
performance. In particular, capillary pressure is important for non-uniform liquid distribution, causing liquid spreading
as it flows down the packing. An analytical model for capillary pressure–saturation relation is developed for the pendular
and funicular regions and the factors affecting capillary pressure in the capillary region are discussed. The present model
is compared to the capillary pressure models of Grosser et al. (AIChE J., 34:1850–1860, 1988) and Attou and Ferschneider (Chem.
Eng. Sci., 55:491–511, 2000) and to the experiments of Dodds and Srivastava (Part Part Syst. Charact., 23:29–39, 2006) and
Dullien et al. (J. Colloid Interface Sci., 127:362–372, 1989). The non-homogeneity of real packings is considered through
particle size and porosity distributions. The model is based on the assumption that the particles are covered with a liquid
film, which provides hydrodynamic continuity. This makes the model more suitable for porous or rough particles than for non-porous
smooth particles. The main improvements of the present model are found in the pendular region, where the liquid dispersion
due to capillary pressure gradients is most significant. The model can be used to improve the hydrodynamic models (e.g., CFD
and cellular automata models) for packed-bed reactors, such as trickle-bed reactors, where gas, liquid, and solid phases are
present. Models for such reactors have become quite common lately (Sáez and Carbonell, AIChE J., 31:52–62, 1985; Holub et al.,
Chem. Eng. Sci, 47, 2343–2348, 1992; Attou et al., Chem. Eng. Sci., 54:785–802, 1999; Iliuta and Larachi, Chem. Eng. Sci.,
54:5039–5045, 1999, IJCRE 3:R4, 2005; Narasimhan et al., AIChE J., 48:2459–2474, 2002), but they still lack proper terms causing
liquid dispersion. 相似文献
40.