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101.
102.
Gussoni M Greco F Bonazzi F Vezzoli A Botta D Dotelli G Natali Sora I Pelosato R Zetta L 《Magnetic resonance imaging》2004,22(6):877-889
Proton nuclear magnetic resonance (NMR) spin-spin relaxation and imaging have been applied to investigate white Portland cement pastes during hydration in the absence and in the presence of organic solvents. The main organic solvent investigated was methanol, alone or together with the organic waste 2-chloroaniline (2-CA), an aromatic amine representative of an important class of highly toxic compounds. For all the analysed samples, prepared with a solvent-to-cement ratio of 0.4, the decay of the echo magnetization has been fitted by adopting a model that combines an exponential component with a gaussian one. The calculated independent relaxation parameters have been discussed in terms of morphological and dynamical changes that occur during the cement hardening process and pore formation. Three kinds of water molecules: "solid-like" (chemically and physically bound), "liquid-like" (porous trapped) and "free" water, endowed with anisotropic, near isotropic and isotropic motion, respectively, were identified. Spin-echo images collected on the same samples during the hydration kinetics, allowed the changes of water and solvents spatial distribution in the porous network to be monitored, showing percolation phenomena and confirming the multimodal open channels structure of the hardened cement system. Both T(2) relaxation and imaging data indicated that a pronounced delay occurs in the cement hardening when organics are present. 相似文献
103.
We have prepared a flexible metal-organic framework and demonstrated that when activated by supercritical CO(2) it has greater gas sorption capacities than that activated by the heat-evacuation method, and it selectively adsorbs CO(2) over N(2) at room temperature. 相似文献
104.
Caronna T Castiglione F Famulari A Fontana F Malpezzi L Mele A Mendola D Sora IN 《Molecules (Basel, Switzerland)》2012,17(1):463-479
Quantum mechanics density functional calculations provided gas-phase electron distributions and proton affinities for several mono- and diaza[5]helicenes; computational results, together with experimental data concerning crystal structures and propensity to methylation of the nitrogen atom(s), provide a basis for designing azahelicene complexes with transition metal ions. 相似文献
105.
A selective and sensitive analytical method was developed for enantiomeric separation and determination of N‐methyl‐DL‐aspartic acid (NMA). The method involved the conversion of each enantiomer into N‐ethoxycarbonylated (S)‐(+)‐2‐octyl ester derivative for the direct separation by gas chromatography–mass spectrometry (GC‐MS). The diastereomeric derivatives showed characteristic mass spectral properties for analysis by selected ion monitoring mode (SIM) and enabling enantioseparation on an achiral capillary column. Two enantiomers were baseline separated, and the detection limits for N‐methyl‐L‐aspartic acid (NMLA) and N‐methyl‐D‐aspartic acid (NMDA) were 0.07 and 0.03 ng/g, respectively. When applied to rat brain tissues for absolute configuration of NMA, only NMDA was determined, while NMLA was monitored as lower than the limit of detection. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
106.
Gordon TR Cargnello M Paik T Mangolini F Weber RT Fornasiero P Murray CB 《Journal of the American Chemical Society》2012,134(15):6751-6761
Control over faceting in nanocrystals (NCs) is pivotal for many applications, but most notably when investigating catalytic reactions which occur on the surfaces of nanostructures. Anatase titanium dioxide (TiO(2)) is one of the most studied photocatalysts, but the shape dependence of its activity has not yet been satisfactorily investigated and many questions still remain unanswered. We report the nonaqueous surfactant-assisted synthesis of highly uniform anatase TiO(2) NCs with tailorable morphology in the 10-100 nm size regime, prepared through a seeded growth technique. Introduction of titanium(IV) fluoride (TiF(4)) preferentially exposes the {001} facet of anatase through in situ release of hydrofluoric acid (HF), allowing for the formation of uniform anatase NCs based on the truncated tetragonal bipyramidal geometry. A method is described to engineer the percentage of {001} and {101} facets through the choice of cosurfactant and titanium precursor. X-ray diffraction studies are performed in conjunction with simulation to determine an average NC dimension which correlates with results obtained using electron microscopy. In addition to altering the particle shape, the introduction of TiF(4) into the synthesis results in TiO(2) NCs that are blue in color and display a broad visible/NIR absorbance which peaks in the infrared (λ(max) ≈ 3400 nm). The blue color results from oxygen vacancies formed in the presence of fluorine, as indicated by electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) studies. The surfactants on the surface of the NCs are removed through a simple ligand exchange procedure, allowing the shape dependence of photocatalytic hydrogen evolution to be studied using monodisperse TiO(2) NCs. Preliminary experiments on the photoreforming of methanol, employed as a model sacrificial agent, on platinized samples resulted in high volumes of evolved hydrogen (up to 2.1 mmol h(-1) g(-1)) under simulated solar illumination. Remarkably, the data suggest that, under our experimental conditions, the {101} facets of anatase are more active than the {001}. 相似文献
107.
Nakamura Y Arima T Tomita S Yamago S 《Journal of the American Chemical Society》2012,134(12):5536-5539
An efficient and simple method for the synthesis of symmetric macromolecules by photoinduced switching from radical polymerization to a radical coupling reaction is reported. Structurally well-defined telechelic polyisoprenes and ABA-triblock copolymers were prepared by successive organotellurium-mediated living radical polymerization (TERP) under thermal conditions, followed by a polymer-end radical coupling reaction under photoirradiation. 相似文献
108.
Point process diagnostics based on weighted second-order statistics and their asymptotic properties 总被引:2,自引:0,他引:2
Giada Adelfio Frederic Paik Schoenberg 《Annals of the Institute of Statistical Mathematics》2009,61(4):929-948
A new approach for point process diagnostics is presented. The method is based on extending second-order statistics for point
processes by weighting each point by the inverse of the conditional intensity function at the point’s location. The result
is generalized versions of the spectral density, R/S statistic, correlation integral and K-function, which can be used to test the fit of a complex point process model with an arbitrary conditional intensity function,
rather than a stationary Poisson model. Asymptotic properties of these generalized second-order statistics are derived, using
an approach based on martingale theory. 相似文献
109.
A two-frame PIV (particle image velocimetry) technique was used to investigate the flow characteristics of a complicated propeller
wake influenced by a hull wake. As the propeller is significantly affected by the hull wake of a marine vessel, measurements
of the propeller wake under the hull wake are certainly needed for more reliable validation of numerical predictions. Velocity
field measurements were conducted in a cavitation tunnel with a simulated hull wake. Generally, the hull wake generated by
the hull of a marine ship may cause different loading distributions on the propeller blade in both the upper and the lower
propeller planes. The unstable propeller wake caused by the ship’s hull was interpreted in terms of turbulent kinetic energy
(T
KE) to obtain useful information for flow modeling. The unstable or unsteady phenomenon in the upper propeller wake was identified
by using the proper orthogonal decomposition (POD) method to characterize the coherent flow structure with turbulent kinetic
energy. Strong unsteadiness appeared in the second and higher modes, largely affecting the downstream flow characteristics.
The first eigenmode can be used to appropriately identify the tip vortex positions even in the unstable downstream region,
which are helpful for establishing reliable wake modeling. 相似文献
110.
Beom Soo Shin Tae Hwan Kim Soo Heui Paik Yong Ha Chi Joo Han Lee Hyun Kwang Tan Yohan Choi Minki Kim Sun Dong Yoo 《Biomedical chromatography : BMC》2011,25(11):1208-1214
Fimasartan, 2‐butyl‐5‐dimethylaminothiocarbonylmethyl‐6‐methyl‐3‐[[2'‐(1H tetrazol ‐5‐yl)biphenyl‐4‐yl]methyl]pyrimidin‐4(3H)‐one (BR‐A‐657), is a novel angiotensin II receptor blocker exhibiting potent and selective AT1 receptor blocking activity. This study reports the liquid chromatography–tandem mass spectrometry assay for the simultaneous determination of fimasartan and its active metabolite, BR‐A‐557, in rat plasma. The assay was validated to demonstrate the specificity, linearity, recovery, lower limit of quantification, accuracy, precision and stability. The multiple reaction monitoring was based on the transition of m/z 502.1 → 207.1 for fimasartan, 486.2 → 207.1 for BR‐A‐557 and 526.1 → 207.1 for BR‐A‐563 (internal standard). The assay utilized a simple precipitation procedure with acetonitrile and isocratic elution. The LLOQ was 0.2 ng/mL for fimasartan and BR‐A‐557 using 50 μL plasma samples. The assay was linear over a concentration range from 0.2 to 500 ng/mL for fimasartan and BR‐A‐557, with correlation coefficients >0.9995. The intra‐ and inter‐day assay accuracies were 93.6–108.0 and 90.8–101.4% for fimasartan and 102.2–107.1 and 99.6–103.3% for BR‐A‐557, respectively. The intra‐ and inter‐day precision were 2.4–4.4 and 3.0–13.4% for fimasartan and 3.1–5.2 and 2.8–9.8% for BR‐A‐557, respectively. The developed assay may be used to study the metabolism and mechanistic pharmacokinetics of fimasartan in future studies. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献