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51.
Hedin N Graf R Christiansen SC Gervais C Hayward RC Eckert J Chmelka BF 《Journal of the American Chemical Society》2004,126(30):9425-9432
The structure of a novel molecularly ordered two-dimensional (2D) silicate framework in a surfactant-templated mesophase has been established by using a combination of solid-state nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction, and quantum chemical and empirical force-field modeling. These materials are unusual in their combination of headgroup-directed 2D crystalline framework ordering, zeolite-like ring structures within the layers, and long-range mesoscopic organization without three-dimensional (3D) atomic periodicity. The absence of registry between the silicate sheets, resulting from the liquidlike disorder of the alkyl surfactant chains, has presented significant challenges to the determination of framework structures in these and similar materials lacking 3D crystalline order. Double-quantum (29)Si NMR correlation experiments establish the interactions and connectivities between distinct intra-sheet silicon sites from which the structure of the molecularly ordered inorganic framework is determined. 相似文献
52.
A generalization of a theorem on off-diagonal hypervirial relations is obtained and is used to demonstrate when to expect exact solutions of eigenvalue problems using the hypervirial method. Links are established between the hypervirial method and other approximation methods. The harmonic oscillator and hydrogen atom problems are given as examples. 相似文献
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Bradley M Bruno N Vincent B 《Langmuir : the ACS journal of surfaces and colloids》2005,21(7):2750-2753
CdSe quantum dots (QDs) are semiconducting nanoparticles that fluoresce when stimulated by visible light. This property has been exploited in their use as tracer particles in biomedical applications. In this study, confocal microscopy has been used to determine the distribution of QDs within polystyrene microgel particles, dispersed in an organic solvent. It was found that the extent of microgel swelling affected the penetration of the QDs into the particles. Only when the microgel particles were swollen to their maximum extent were the QDs able to penetrate into the central core region of the particles. 相似文献
56.
Sonia M AlessoZhanru Yu David PearsPaul A Worthington Richard W.A LukeMark Bradley 《Tetrahedron》2003,59(36):7163-7169
The preparation, characterisation and application of a series of non-grafted polystyrene (PS) resins containing a styrenic methoxypoly(ethylene glycol) (MPEG) derivative is presented. These novel PS-MPEG resins were designed to balance swelling and solvation with improved handling. The monomer, 1-[2-(2-methoxyethoxy)ethoxy]-4-vinyl-benzene, contained an inert phenyl ether linkage designed to provide broad chemical compatibility and stability, yet imparting all the favourable properties of the PEG group into the new resin, whilst maintaining a high loading capacity. The synthetic performance of the new resins compared very favourably to those of TentaGel™, ArgoGel™ and aminomethyl PS. 相似文献
57.
Hui Yang Xing Chen Guoxiang Hu Wan-Ting Chen Siobhan J. Bradley Weijie Zhang Gaurav Verma Thomas Nann De-en Jiang Paul E. Kruger Xiangke Wang He Tian Geoffrey I. N. Waterhouse Shane G. Telfer Shengqian Ma 《Chemical science》2020,11(13):3523
Optimizing interfacial contacts and thus electron transfer phenomena in heterogeneous electrocatalysts is an effective approach for enhancing electrocatalytic performance. Herein, we successfully synthesized ultrafine β-Mo2C nanoparticles confined within hollow capsules of nitrogen-doped porous carbon (β-Mo2C@NPCC) and found that the surface layer of molybdenum atoms was further oxidized to a single Mo–O surface layer, thus producing intimate O–Mo–C interfaces. An arsenal of complementary technologies, including XPS, atomic-resolution HAADF-STEM, and XAS analysis clearly reveals the existence of O–Mo–C interfaces for these surface-engineered ultrafine nanostructures. The β-Mo2C@NPCC electrocatalyst exhibited excellent electrocatalytic activity for the hydrogen evolution reaction (HER) in water. Theoretical studies indicate that the highly accessible ultrathin O–Mo–C interfaces serving as the active sites are crucial to the HER performance and underpinned the outstanding electrocatalytic performance of β-Mo2C@NPCC. This proof-of-concept study opens a new avenue for the fabrication of highly efficient catalysts for HER and other applications, whilst further demonstrating the importance of exposed interfaces and interfacial contacts in efficient electrocatalysis.Ultrafine β-Mo2C nanostructures encapsulated in N-doped carbon capsules featuring O–Mo–C interfaces as the active sites for HER have been unveiled. 相似文献
58.
Dan F. Bradley 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(3):741-755
From the universe of polymeric materials which appear in biology and medicine we select for discussion that set whose principal function is to recognize and respond appropriately to specific substances in their environment. They may be 1.2, 2.2, or 3 dimensional shapes such as messenger RNA, cellulose acetate membranes, or artificial esophagi. They may function by recognizing the difference between right and wrong chemical species and responding by binding the correct ones and rejecting the wrong ones, e.g., enzymes and their substrates, codons and their anticodons. What happens after recognition and response is not of interest at the moment, e.g., the catalytic effect of the enzyme on the bound substrate or the codonanticodon binding effect on protein synthesis. Another example is in the chemical senses where there is sketchy evidence that proteins are involved in recognizing tastants. This could be done by having a protein on the tongue bind all tastants (rather close contact is required to make fine distinctions) and then recognize them by very intimate contacts and sending signals to the brain for conscious recognition. Alternatively, each taste modality may have a protein that excludes all but one type and generates only one signal for the CNS. Another important class are antibodies that recognize their own antigens out of about 104 different ones and complex with them and exclude the others. A model for antigen-antibody interaction must account for the non-binding of nonantigens as well as the much simpler case of the binding of the antigen. Another class are the permselective membranes that recognize some species and let them pass while recognizing others and not let them pass. A final class to be discussed will be implant polymers which have an un-desired ability to recognize and bind platelets. The question we are asking is whether it is possible to establish general principles in chemical physics that govern these different types of molecular recognition so that the principles could be incorporated into polymer design. Recent advances in “intermolecular” force theory suggests that this goal is achievable in the foreseeable future. Intermolecular has been put in quotes because when two molecules are in sufficiently close contact to recognize one another they probably have an appreciable exchange term and are therefore not two molecules but one. The recent advances referred to involve computer simulation of complex formation using the new 1-4-6-12 potential forms corresponding to a long range (R?1) coulombic electrostatic interaction, a medium range (R?4) electrostatic-induced dipole attraction, a short range (R?6) dispersive attraction, and a very short range (R?12) orbital overlap repulsion. In the cases of interest, e.g., in an aqueous environment, all four terms are important and statements such as “the binding is purely electrostatic,” i.e., all R?1, are misleading as well as wrong (since even ions need the R?12 repulsion to keep them at their equilibrium distance). Discussions of permeability in terms of “pore sizes” is equally limiting for it implies that only the R?12repulsion is appreciable. The fallacy of using competitive equilibria to determine the relative contributions of terms will be discussed. The im: portant use in biology of “other contacts” within the system to give a variable base line so that the typical binding-no binding discrimination can be made with attraction-less attraction rather than the more awkward attraction-repulsion potentials will also be discussed. 相似文献
59.
Abstract Organic-inorganic composites (OICs) were prepared via the in-situ polymerization of an organically (phenyl) substituted trialkoxysilane, phenyltriethoxysilane (PhTEOS), in the presence of poly(vinyl acetate) (PVAc). The mechanical reinforcement above T g previously observed in OICs of unfunctionalized organic polymers such as PVAc with acid catalyzed in-situ polymerized tetraalkoxysilane was not observed when the tetraalkoxysilane was replaced with PhTEOS. Although both systems are optically transparent and both exhibit a high degree of hydrogen bonding between the carbonyl of PVAc and the residual hydroxyls of the silicate, the polymerization of the alkoxide is different. The tetra-functional alkoxide polymerizes to form a load-supporting silicate network, leading to a high plateau in the tensile modulus above T g, whereas the trifunctional alkoxide reacts to form primarily low molecular weight oligomers. These increase the T g of the PVAc but do not provide mechanical reinforcement. 相似文献
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