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81.
We present a low-temperature scanning tunneling microscopy study of the alpha-Sn/Si(111) surface that demonstrates the fluctuating behavior of the Sn adatoms. The dynamical fluctuation model, successfully applied in describing the alpha-Sn/Ge(111) surface, is proposed for the related alpha-Sn/Si(111) surface too, although with a much lower transition temperature. In addition, a new phenomenon appears responsible for the unexpected evidence that the average oscillation frequency remains constant at temperatures lower than 15 K, in contradiction to the Arrhenius law. We explain this phenomenon as quantum tunneling of Sn adatoms. 相似文献
82.
Wise RG Lujan BJ Schweinhardt P Peskett GD Rogers R Tracey I 《Magnetic resonance imaging》2007,25(6):801-810
BACKGROUND AND PURPOSE: Functional neuroimaging can distinguish components of the pain experience associated with anticipation to pain from those associated with the experience of pain itself. Anticipation to pain is thought to increase the suffering of chronic pain patients. Inappropriate anxiety, of which anticipation is a component, is also a cause of disability. We present a pharmacological functional magnetic resonance imaging (fMRI) study in which we investigate the selective modulation by midazolam of brain activity associated with anticipation to pain compared to pain itself. METHODS: Eight right-handed male volunteers underwent fMRI combined with a thermal pain conditioning paradigm and midazolam (30 mug/kg) or saline administration on different occasions, with order randomized across volunteers. Volunteers learned to associate a colored light with either painful, hot stimulation or nonpainful, warm stimulation to the back of the left hand. RESULTS: Comparison of the period during thermal stimulation (pain-warm) revealed a network of brain activity commonly associated with noxious stimulation, including activities in the anterior cingulate cortex (ACC), the bilateral insular cortices (anterior and posterior), the thalamus, S1, the motor cortex, the brainstem, the prefrontal cortex and the cerebellum. Comparison of the periods preceding thermal stimulation (anticipation to pain-anticipation to warm) revealed activity principally in the ACC, the contralateral anterior insular cortex and the ipsilateral S2/posterior insula. Detected by a region-of-interest analysis, midazolam reduced the activity associated specifically with anticipation to pain while controlling for anticipation to warm. This was most significant in the contralateral anterior insula (P<.05). There were no significant drug effects on the activity associated with pain itself. CONCLUSION: In identifying a pharmacological effect on activity preceding but not during pain, we have successfully demonstrated an fMRI assay that can be used to study the action of anxiolytic agents in a relatively small cohort of humans. 相似文献
83.
1,10‐Phenanthroline and Non‐Symmetrical 1,3,5‐Triazine Dipicolinamide‐Based Ligands For Group Actinide Extraction 下载免费PDF全文
Dr. Julia Bisson Dr. Jérémy Dehaudt Dr. Marie‐Christine Charbonnel Dr. Denis Guillaneux Dr. Manuel Miguirditchian Dr. Cécile Marie Nathalie Boubals Guy Dutech Dr. Muriel Pipelier Dr. Virginie Blot Prof. Didier Dubreuil 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7819-7829
The synthesis and evaluation of new extractants for spent nuclear fuel reprocessing are described. New bitopic ligands constituted of phenanthroline and 1,3,5‐triazine cores functionalized by picolinamide groups were designed. Synthetic routes were investigated and optimized to obtain twelve new polyaza‐heterocyclic ligands. In particular, an efficient and versatile methodology was developed to access non‐symmetric 2‐substituted‐4,6‐di(6‐picolin‐2‐yl)‐1,3,5‐triazines from the 1,3,5‐triazapentadiene precursor in the presence of anhydride reagents. Extraction studies showed the ability of both ligand series to extract and separate actinides selectively at different oxidation states (UVI, NpV,VI, AmIII, CmIII, and PuIV) from an acidic solution (3 M HNO3). Phenanthroline‐based ligands show the most promising efficiency for use in the group actinide extraction (GANEX) process due to a higher number of donor nitrogen atoms and a suitable pre‐organization of the dipicolinamide‐1,10‐phenanthroline architecture. 相似文献
84.
Skeleton Decoration of NHCs by Amino Groups and its Sequential Booster Effect on the Palladium‐Catalyzed Buchwald–Hartwig Amination 下载免费PDF全文
Yin Zhang Dr. Vincent César Golo Storch Dr. Noël Lugan Dr. Guy Lavigne 《Angewandte Chemie (International ed. in English)》2014,53(25):6482-6486
A challenging synthetic modification of PEPPSI‐type palladium pre‐catalysts consisting of a stepwise incorporation of one and two amino groups onto the NHC skeleton was seen to exert a sequential enhancement of the electronic donor properties. This appears to be positively correlated with the catalytic performances of the corresponding complexes in the Buchwald–Hartwig amination. This is illustrated, for example, by the quantitative amination of 4‐chloroanisole by morpholine within 2 h at 25 °C with a 2 mol % catalyst/substrate ratio or by a significant reduction of catalytic loading (down to 0.005 mol %) for the coupling of aryl chlorides with anilines (max TON: 19 600). 相似文献
85.
Kinetic Modeling of α‐Hydrogen Abstractions from Unsaturated and Saturated Oxygenate Compounds by Carbon‐Centered Radicals 下载免费PDF全文
Paschalis D. Paraskevas Dr. Maarten K. Sabbe Prof. Marie‐Françoise Reyniers Prof. Dr. Nikos Papayannakos Prof. Dr. Guy B. Marin 《Chemphyschem》2014,15(9):1849-1866
Hydrogen abstractions are important elementary reactions in a variety of reacting media at high temperatures in which oxygenates and hydrocarbon radicals are present. Accurate kinetic data are obtained from CBS‐QB3 ab initio (AI) calculations by using conventional transition‐state theory within the high‐pressure limit, including corrections for hindered rotation and tunneling. From the obtained results, a group‐additive (GA) model is developed that allows the Arrhenius parameters and rate coefficients for abstraction of the α‐hydrogen from a wide range of oxygenate compounds to be predicted at temperatures ranging from 300 to 1500 K. From a training set of 60 hydrogen abstractions from oxygenates by carbon‐centered radicals, 15 GA values (ΔGAVos) are obtained for both the forward and reverse reactions. Among them, four ΔGAVos refer to primary contributions, and the remaining 11 ΔGAVos refer to secondary ones. The accuracy of the model is further improved by introducing seven corrections for cross‐resonance stabilization of the transition state from an additional set of 43 reactions. The determined ΔGAVos are validated upon a test set of AI data for 17 reactions. The mean absolute deviation of the pre‐exponential factors (log A) and activation energies (Ea) for the forward reaction at 300 K are 0.238 log(m3 mol?1 s?1) and 1.5 kJ mol?1, respectively, whereas the mean factor of deviation <ρ> between the GA‐predicted and the AI‐calculated rate coefficients is 1.6. In comparison with a compilation of 33 experimental rate coefficients, the <ρ> between the GA‐predicted values and these experimental values is only 2.2. Hence, the constructed GA model can be reliably used in the prediction of the kinetics of α‐hydrogen‐abstraction reactions between a broad range of oxygenates and oxygenate radicals. 相似文献
86.
Back Cover: Assessment of DNA Binding to Human Rad51 Protein by using Quartz Crystal Microbalance and Atomic Force Microscopy: Effects of ADP and BRC4‐28 Peptide Inhibitor (ChemPhysChem 17/2014) 下载免费PDF全文
87.
Niels De Meirleir Linda Pellens Walter Broeckx Guy van Assche Wim De Malsche 《Colloid and polymer science》2014,292(10):2539-2547
The present study focuses on the rheological performance of a surfactant-rich aqueous suspension containing hydrogenated castor oil (HCO) crystals. HCO can be typically crystallized in five distinct shapes: spherically shaped, irregularly shaped, star-shaped (also called rosettes), short needles, and thick or thin fibers. The effect of the differences in shape on the rheological performance is studied, and the rheological properties are compared to the behavior of other triacylglycerol’s (TAG) suspensions. A suspension of TAG crystals usually behaves as a colloidal gel wherein a colloidal gel is defined as a network of flocs, with each floc being an aggregate of smaller subunits. All of these surfactant-rich aqueous suspensions of HCO crystals behaved according to a colloidal gel in the transient regime, independent of the studied crystal shapes, except the long thin fibers at a concentration above 0.1 wt% HCO transitioning from a heterogeneous fractal rod network to a homogeneous rod network, shifting from a colloidal gel to a glass. 相似文献
88.
89.
Jing Zhao Yanan Zhu Xuehong Song Yuanyuan Xiao Guowei Su Xinyue Liu Zhangjie Wang Yongmei Xu Jian Liu David Eliezer Trudy F. Ramlall Guy Lippens James Gibson Fuming Zhang Robert J. Linhardt Lianchun Wang Chunyu Wang 《Angewandte Chemie (International ed. in English)》2020,59(5):1818-1827
Prion‐like transcellular spreading of tau in Alzheimer's Disease (AD) is mediated by tau binding to cell surface heparan sulfate (HS). However, the structural determinants for tau–HS interaction are not well understood. Microarray and SPR assays of structurally defined HS oligosaccharides show that a rare 3‐O‐sulfation (3‐O‐S) of HS significantly enhances tau binding. In Hs3st1?/? (HS 3‐O‐sulfotransferase‐1 knockout) cells, reduced 3‐O‐S levels of HS diminished both cell surface binding and internalization of tau. In a cell culture, the addition of a 3‐O‐S HS 12‐mer reduced both tau cell surface binding and cellular uptake. NMR titrations mapped 3‐O‐S binding sites to the microtubule binding repeat 2 (R2) and proline‐rich region 2 (PRR2) of tau. Tau is only the seventh protein currently known to recognize HS 3‐O‐sulfation. Our work demonstrates that this rare 3‐O‐sulfation enhances tau–HS binding and likely the transcellular spread of tau, providing a novel target for disease‐modifying treatment of AD and other tauopathies. 相似文献
90.
Nathalie Poulain Evelyne Nakache Annabelle Pina Guy Levesque 《Journal of polymer science. Part A, Polymer chemistry》1996,34(5):729-737
The polymerization of isodecyl acrylate (ISODAC) in vesicles made from an anionic surfactant—sodium di-2-ethylhexyl phosphate (SEHP)—and from water is studied by 1H-NMR, transmission electron microscopy, and quasielastic light scattering. High polymerization rates and high conversion rates are achieved with both water-soluble initiator, K2S2O8 (potassium persulfate), and oil-soluble initiator, AIBN (azoisobisbutyronitrile). ISODAC is probably located inside the vesicle bilayer(s) because of its high hydrophobicity. Particles stable at room temperature with a mean diameter of about 50 nm are obtained. Kinetic orders of ISODAC polymerization are determined and the characterization of the resulting particles during and after polymerization are studied. © 1996 John Wiley & Sons, Inc. 相似文献