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81.
The order in a single layer of spherical domains of a block copolymer melt is investigated as a function of distance from the edges of the 15 microm wide, 30 nm deep wells that confine it along a substrate. At 255 degrees C the edge induces the formation of a hexatic phase whose orientational and translational order decreases slowly away from the edge until in the center of the well the block copolymer spheres have liquidlike order. 相似文献
82.
Botta M Aime S Barge A Bobba G Dickins RS Parker D Terreno E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(9):2102-2109
The (1)H and (17)O NMR relaxometric properties of two cationic complexes formed by Gd(III) with a macrocyclic heptadentate triamide ligand, L(1), and its Nmethylated analogue, L(2), have been investigated in aqueous media as a function of pH, temperature and magnetic field strength. The complexes possess two water molecules in their inner coordination sphere for which the rate of exchange has been found to be sensibly faster for the Nmethylated derivative and explained in terms of electronic effects (decrease of the charge density at the metal center) and perturbation of the network of hydrogen-bonded water molecules in the outer hydration sphere. The proton relaxivity shows a marked dependence from pH and decreases of about six units in the pH range 6.5 to 9.0. This has been accounted for by the displacement of the two water molecules by dissolved carbonate which acts as a chelating anion. The formation of ternary complexes with lactate, malonate, citrate, acetate, fluoride and hydrogenphosphate has been monitored by (1)H NMR relaxometric titrations at 20 MHz and pH 6.3 and the value of the affinity constant, K, and of the relaxivity of the adducts could be obtained. Lactate, malonate and citrate interact strongly with the complexes (log K > or =3.7) and coordinate in a bidendate mode by displacing both water molecules. Larger affinity constants have been measured for GdL(2). Acetate, fluoride and hydrogenphosphate form monoaqua ternary complexes which were investigated in detail with regard to their relaxometric properties. The NMR dispersion (NMRD) profiles indicate a large contribution to the relaxivity of the adducts from water molecules belonging to the second hydration shell of the complexes and hydrogen-bonded to the anion. A VT (17)O NMR study has shown a marked increase of the rate of water exchange upon binding which is explained by coordination of the anion in an equatorial site, thus leaving the water molecule in an apical position, more accessible for interactions with the solvent molecules of the second hydration shell which facilitate the exchange process. 相似文献
83.
Eann A. Patterson Erwin Hack Philippe Brailly Richard L. Burguete Qasim Saleem Thorsten Siebert Rachel A. Tomlinson Maurice P. Whelan 《Optics and Lasers in Engineering》2007,45(5):550
The design and testing of a reference material for the calibration of optical systems for strain measurement is described, together with the design and testing of a standardized test material that allows the evaluation and assessment of fitness for purpose of the most sophisticated optical system for strain measurement. A classification system for the steps in the measurement process is also proposed and allows the development of a unified approach to diagnostic testing of components or sub-systems in an optical system for strain measurement based on any optical technique. The results described arise from a European study known as SPOTS whose objectives were to begin to fill the gap caused by a lack of standards. 相似文献
84.
85.
Drisko GL Chee Kimling M Scales N Ide A Sizgek E Caruso RA Luca V 《Langmuir : the ACS journal of surfaces and colloids》2010,26(22):17581-17588
A simple and engineering friendly one-step process has been used to prepare zirconium titanium mixed oxide beads with porosity on multiple length scales. In this facile synthesis, the bead diameter and the macroporosity can be conveniently controlled through minor alterations in the synthesis conditions. The precursor solution consisted of poly(acrylonitrile) dissolved in dimethyl sulfoxide to which was added block copolymer Pluronic F127 and metal alkoxides. The millimeter-sized spheres were fabricated with differing macropore dimensions and morphology through dropwise addition of the precursor solution into a gelation bath consisting of water (H(2)O beads) or liquid nitrogen (LN(2) beads). The inorganic beads obtained after calcination (550 °C in air) had surface areas of 140 and 128 m(2) g(-1), respectively, and had varied pore architectures. The H(2)O-derived beads had much larger macropores (5.7 μm) and smaller mesopores (6.3 nm) compared with the LN(2)-derived beads (0.8 μm and 24 nm, respectively). Pluronic F127 was an important addition to the precursor solution, as it resulted in increased surface area, pore volume, and compressive yield point. From nonambient XRD analysis, it was concluded that the zirconium and titanium were homogeneously mixed within the oxide. The beads were analyzed for surface accessibility and adsorption rate by monitoring the uptake of uranyl species from solution. The macropore diameter and morphology greatly impacted surface accessibility. Beads with larger macropores reached adsorption equilibrium much faster than the beads with a more tortuous macropore network. 相似文献
86.
Selinsky RS Han JH Morales Pérez EA Guzei IA Jin S 《Journal of the American Chemical Society》2010,132(45):15997-16005
EuS nanocrystals (NCs) were doped with Gd resulting in an enhancement of their magnetic properties. New EuS and GdS single source precursors (SSPs) were synthesized, characterized, and employed to synthesize Eu(1-x)Gd(x)S NCs by decomposition in oleylamine and trioctylphosphine at 290 °C. The doped NCs were characterized using X-ray diffraction, transmission electron microscopy, and scanning transmission electron microscopy, which support the uniform distribution of Gd dopants through electron energy loss spectroscopy (EELS) mapping. X-ray absorption spectroscopy (XAS) revealed the dopant ions in Eu(1-x)Gd(x)S NCs to be predominantly Gd(3+). NCs with a variety of doping ratios of Gd (0 ≤ x < 1) were systematically studied using vibrating sample magnetometry and the observed magnetic properties were correlated with the Gd doping levels (x) as quantified with ICP-AES. Enhancement of the Curie temperature (T(C)) was observed for samples with low Gd concentrations (x ≤ 10%) with a maximum T(C) of 29.4 K observed for NCs containing 5.3% Gd. Overall, the observed T(C), Weiss temperature (θ), and hysteretic behavior correspond directly to the doping level in Eu(1-x)Gd(x)S NCs and the trends qualitatively follow those previously reported for bulk and thin film samples. 相似文献
87.
Rachel J. White 《Tetrahedron letters》2010,51(5):800-218
A selective, versatile, robust methodology for bifunctionalization of β-cyclodextrin is achieved allowing the attachment of peptides in varying C- and/or N-terminal combinations on resin using Fmoc SPPS. Two linkers are attached to cyclodextrin enabling selective binding to the resin (or a peptide attached to the resin). Continuation of peptide growth and/or cleavage from the resin follows, thus various combinations of peptide-cyclodextrin species are achieved. A model peptide (Gly-Ala) is used in this study to illustrate the potential of this system for attaching one or more bioactive peptides for drug transport and release purposes. 相似文献
88.
Nathan A. Lacher Rachel K. Roberts Yan He Holly Cargill Katrina M. Kearns Heidi Holovics Margaret N. Ruesch 《Journal of separation science》2010,33(2):218-227
Capillary gel electrophoresis (CGE) methods with UV detection were developed for reduced and non‐reduced mAb analysis. These methods can be used to evaluate mAb purity, offering more reproducible quantitation compared with that of traditional SDS‐PAGE methods. These CGE methods have been utilized as platform technology for bioprocess development, formulation development, mAb characterization, drug substance/drug product release testing as well as a required methodology for stability testing. We have found these CGE methods to be applicable across a platform of mAbs in preclinical and clinical development, with the majority of mAbs requiring no modification to the method conditions. This methodology has been ICH validated and transferred to several supporting organizations. The data presented herein describes the development of CGE methodology, platform application to mAb purity analysis, ICH validation, reliability metrics, and considerations on technology enhancement for improved performance and throughput. 相似文献
89.
Nathan A. Lacher Qian Wang Rachel K. Roberts Heidi J. Holovics Serdar Aykent Michael R. Schlittler Melissa R. Thompson Charles W. Demarest 《Electrophoresis》2010,31(3):448-458
A CGE method for monitoring the disulfide isomer distribution characteristic of IgG2 MAbs is presented. Disulfide heterogeneity of MAbs has been studied using various chromatographic and electrophoretic methods. Although CGE operates using a different selectivity mechanism from that of sorption chromatographic techniques, similar trends are present in the data, which allow the CGE method to be used as a complementary method for studying disulfide isomer distribution. This article focuses on the optimization of a capillary‐based gel electrophoresis method that can be used to support antibody development including bioprocess optimization, antibody characterization, release, and formulation stability assessment. 相似文献
90.
Jonathan T. Husband Yujie Xie Thomas R. Wilks Louise Male Miquel Torrent-Sucarrat Vasilios G. Stavros Rachel K. O'Reilly 《Chemical science》2021,12(31):10550
Fluorescent dyes that exhibit high solid state quantum yields and sensitivity to the mechanical properties of their local environment are useful for a wide variety of applications, but are limited in chemical diversity. We report a trityl-functionalised maleimide that displays rigidochromic behaviour, becoming highly fluorescent when immobilised in a solid matrix, while displaying negligible fluorescence in solution. Furthermore, the dye''s quantum yield is shown to be sensitive to the nature of the surrounding matrix. Computational studies reveal that this behaviour arises from the precise tuning of inter- and intramolecular noncovalent interactions. This work expands the diversity of molecules exhibiting solid state environment sensitivity, and provides important fundamental insights into their design.In this study, by systematic tuning of imide substituent a maleimides dye with sensitivity to its solid-state environment was investigated. 相似文献