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91.
To enable utilization of the broad potential of copper isotopes in nuclear medicine, rapid and robust chelation of the copper is required. Bowl adamanzanes (bicyclic tetraaza ligands) can form kinetically stable copper complexes, but they are usually formed at low rates unless high pH values and high temperatures are applied. We have investigated the effects of the variation in the pH, different anions, and UV irradiation on the chelation rate. UV spectra of mixtures of Cu(2+) and [2(4).3(1)]adz in water show the existence of a long-lived two-coordinated copper(II) intermediate (only counting coordinated amine groups) at pH above 6. These findings are supported by pH titrations of mixtures of Cu(2+) and [2(4).3(1)]adz in water. Irradiation of this complex in the ligand-to-metal charge-transfer (LMCT) band by a diode-array spectrophotometer leads to photodeprotonation and subsequently to formation of the four-coordinated copper(II) complex at a rate up to 7800-fold higher at 25 °C than in the dark. Anions in the solution were found to have three major effects: competitive inhibition due to Cu(II) binding anions, inhibition of the photoinduced transchelation from UV-absorbing anions, and photoredox inhibition from acido ligands capable of acting as electron donors in LMCT reactions. Dissolved O(2) was also found to result in photoredox inhibition. 相似文献
92.
Theory and experiment demonstrate that Coulombic repulsion plays a dominant role in the strength of binding a second cation to a rigid, ditopic host. 相似文献
93.
Nanocelluloses: a new family of nature-based materials 总被引:2,自引:0,他引:2
Klemm D Kramer F Moritz S Lindström T Ankerfors M Gray D Dorris A 《Angewandte Chemie (International ed. in English)》2011,50(24):5438-5466
Cellulose fibrils with widths in the nanometer range are nature-based materials with unique and potentially useful features. Most importantly, these novel nanocelluloses open up the strongly expanding fields of sustainable materials and nanocomposites, as well as medical and life-science devices, to the natural polymer cellulose. The nanodimensions of the structural elements result in a high surface area and hence the powerful interaction of these celluloses with surrounding species, such as water, organic and polymeric compounds, nanoparticles, and living cells. This Review assembles the current knowledge on the isolation of microfibrillated cellulose from wood and its application in nanocomposites; the preparation of nanocrystalline cellulose and its use as a reinforcing agent; and the biofabrication of bacterial nanocellulose, as well as its evaluation as a biomaterial for medical implants. 相似文献
94.
Sjöqvist J Linares M Lindgren M Norman P 《Physical chemistry chemical physics : PCCP》2011,13(39):17532-17542
CHARMM force field parameter values for a class of oligothiophene derivatives have been derived with reference to density functional theory/B3LYP potential energy surfaces. The force field parametrization of these luminescent conjugated polyelectrolytes includes the electronic ground state as well as the strongly light absorbing first excited state. In conjunction with quantum chemical response theory calculations of transition state properties, a molecular dynamical model of the Stokes shift is obtained. The theoretical model is benchmarked against experimental data recorded at room temperature which refer to sodium salts of p-HTAA and p-FTAA with distilled water as a solvent. For p-HTAA the theoretically predicted Stokes shift of 112 nm is in good agreement with the experimental result of 124 nm, given the approximations about exciton localization that were introduced to obtain a force field for the excited state. 相似文献
95.
de Campo L Varslot T Moghaddam MJ Kirkensgaard JJ Mortensen K Hyde ST 《Physical chemistry chemical physics : PCCP》2011,13(8):3139-3152
Triphilic star-polyphiles are short-chain oligomeric molecules with a radial arrangement of hydrophilic, hydrocarbon and fluorocarbon chains linked to a common centre. They form a number of liquid crystalline structures when mixed with water. In this contribution we focus on a hexagonal liquid crystalline mesophase found in star-polyphiles as compared to the corresponding double-chain surfactant to determine whether the hydrocarbon and fluorocarbon chains are in fact demixed in these star-polyphile systems, or whether both hydrocarbon and fluorocarbon chains are miscible, leading to a single hydrophobic domain, making the star-polyphile effectively amphiphilic. We report SANS contrast variation data that are compatible only with the presence of three distinct immiscible domains within this hexagonal mesophase, confirming that these star-polyphile liquid crystals are indeed hydrophilic/oleophilic/fluorophilic 3-phase systems. Quantitative comparison with scattering simulations shows that the experimental data are in very good agreement with an underlying 2D columnar (12.6.4) tiling. As in a conventional amphiphilic hexagonal mesophase, the hexagonally packed water channels (dodecagonal prismatic domains) are embedded in a hydrophobic matrix, but that matrix is split into oleophilic hexagonal prismatic domains and fluorophilic quadrangular prismatic domains. 相似文献
96.
Miroslav Kuchta Kent‐Andre Mardal Mikael Mortensen 《Numerical Methods for Partial Differential Equations》2019,35(1):375-393
Multiscale or multiphysics problems often involve coupling of partial differential equations posed on domains of different dimensionality. In this work, we consider a simplified model problem of a 3d‐1d coupling and the main objective is to construct algorithms that may utilize standard multilevel algorithms for the 3d domain, which has the dominating computational complexity. Preconditioning for a system of two elliptic problems posed, respectively, in a three‐dimensional domain and an embedded one dimensional curve and coupled by the trace constraint is discussed. Investigating numerically the properties of the well‐defined discrete trace operator, it is found that negative fractional Sobolev norms are suitable preconditioners for the Schur complement of the system. The norms are employed to construct a robust block diagonal preconditioner for the coupled problem. 相似文献
97.
Eu3+-, Tb3+- and Er3+-cored dendrimer complexes were prepared by self-assembly of three fluorinated dendrons, each with a carboxylate anion focal point, around the lanthanide ion. Energy transfer from the peripheral fluorinated phenyl moieties of the dendrons to the lanthanide cation was evidenced spectroscopically for Eu3+- and Tb3+-cored dendrimer complexes in solution. The excitation of perfluorinated aromatic groups was found to decay with ca. 0.7 ns and a longer decay time 10-13 ns was related to the coordination at the Ln3+ focal point. Luminescence from the lanthanide core decays with lifetime in the range 1-1.5 ms over a wide concentration range (μM-mM), similar to the luminescence decay time of the corresponding acetate ion complexes in D2O. The main quenching mechanism of the lanthanide emission appears to be due to vibrations among surrounding C-H bonds of the intermediate shell of the flexible dendrimer scaffold. Antenna effect and energy harvesting from the surface of the dendrimer and transfer to the core was the main mechanism for luminescecnce in the dendrimer complexes with lanthanide cations. 相似文献
98.
Mikael Rönnqvist 《Mathematical Programming》2003,97(1-2):267-284
Optimization models and methods have been used extensively in the forest industry. In this paper we describe the general
wood-flow in forestry and a variety of planning problems. These cover planning periods from a fraction of a second to more
than one hundred years. The problems are modelled using linear, integer and nonlinear models. Solution methods used depend
on the required solution time and include for example dynamic programming, LP methods, branch & bound methods, heuristics
and column generation. The importance of modelling and qualitative information is also discussed.
Received: January 15, 2003 / Accepted: April 24, 2003
Published online: May 28, 2003
Key words. Forestry – modelling – routing – transportation – production planning
Mathematics Subject Classification (2000): 20E28, 20G40, 20C20 相似文献
99.
We prove that Gleason parts in uniform distinguished Fréchet algebras are open and closed in the weak topology. 相似文献
100.
Jesper L. Mortensen Alan McWilliam Christopher G. Leburn Peter Tidemand-Lichtenberg Morten Thorhauge Jirí Janousek Christian T.A. Brown Alexander A. Lagatsky Preben Buchhave Wilson Sibbett 《Optics Communications》2006,260(2):637-640
Efficient generation of continuous-wave (CW) tunable light in the yellow region is reported. The method is based on sum-frequency mixing of a tunable Cr4+:forsterite laser with a Nd:YVO4 laser. A periodically poled lithium niobate crystal was placed intra-cavity in a Nd:YVO4 laser, and the Cr4+:forsterite laser was single-passed through the non-linear media. With this setup, it was possible to generate up to 3 mW of yellow light smoothly tunable from 573 to 587 nm. This is the highest output demonstrated to date for a tunable diode pumped solid-state CW laser in this wavelength region. The ways to improve the efficiency further are discussed. 相似文献