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Shaofei Song Jingjie Jiang Ehsan Nikbin Jane Y. Howe Ian Manners Mitchell A. Winnik 《Chemical science》2022,13(2):396
Self-assembly of crystalline-coil block copolymers (BCPs) in selective solvents is often carried out by heating the mixture until the sample appears to dissolve and then allowing the solution to cool back to room temperature. In self-seeding experiments, some crystallites persist during sample annealing and nucleate the growth of core-crystalline micelles upon cooling. There is evidence in the literature that the nature of the self-assembled structures formed is independent of the annealing time at a particular temperature. There are, however, no systematic studies of how the rate of cooling affects self-assembly. We examine three systems based upon poly(ferrocenyldimethylsilane) BCPs that generated uniform micelles under typical conditions where cooling took pace on the 1–2 h time scale. For example, several of the systems generated elongated 1D micelles of uniform length under these slow cooling conditions. When subjected to rapid cooling (on the time scale of a few minutes or faster), branched structures were obtained. Variation of the cooling rate led to a variation in the size and degree of branching of some of the structures examined. These changes can be explained in terms of the high degree of supersaturation that occurs when unimer solutions at high temperature are suddenly cooled. Enhanced nucleation, seed aggregation, and selective growth of the species of lowest solubility contribute to branching. Cooling rate becomes another tool for manipulating crystallization-driven self-assembly and controlling micelle morphologies.In the self-assembly of crystalline-coil block copolymers in solution, heating followed by different cooling rates can lead to different structures. 相似文献
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Ian Macmillan Ward 《Macromolecular Symposia》1995,100(1):1-14
Recent progress in basic science and technological innovation is described for three areas of research in the IRC at Leeds University; melt spun high modulus polyethylene fibres, hydrostatic extrusion and die drawing. 相似文献
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Ian A. Maxwell Bradley R Morrison Robert G Gilbert David F Sangster Donald H Napper 《Macromolecular Symposia》1992,53(1):233-242
Measurements of the rate coefficients characterising the entry of free radicals into seed particles in styrene emulsion polymerizations has allowed the rate determining step for entry to be identified. This was found to be the rate of production of oligomeric species in the aqueous phase by monomer addition to the primary free radicals. Once formed the subsequent diffusion of these species to the latex particles (and their incorporation within these particles) is relatively fast, contrary to the assumptions of the previous diffusion controlled theories. The experimental results imply that the entering free radicals contain only two or three monomer units. Thermodynamic considerations show that such species should be both water soluble and surface active. Similar conclusions have been reached for other sparingly water soluble monomers, such as butyl acrylate and butyl methacrylate. 相似文献
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Since the work of Ebbesen et al. [Nature (London) 391, 667 (1998)], there has been immense interest in the optical properties of subwavelength holes in metal layers. While the enhanced transmission observed is generally associated with surface plasmon polaritons (SPPs), theoretical predictions suggest a similar response with perfectly conducting materials. However, Pendry et al. [Science 305, 847 (2004)] proposed that, if textured on a subwavelength scale, even perfect conductors support surface modes. Here, using microwave radiation incident upon an array of metal waveguides, we observe peaks in the transmissivity below cutoff and confirm the crucial role of these SPP-like modes in the mechanism responsible. 相似文献
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Radunsky AS Williams EM Walmsley IA Wasylczyk P Wasilewski W U'Ren AB Anderson ME 《Optics letters》2006,31(7):1008-1010
We propose and demonstrate a novel implementation of spectral-shearing interferometry (SSI) for reconstructing the electric field of ultrashort pulses by utilizing asymmetric group velocity matching in a long nonlinear crystal. The proposed configuration eliminates the requirement for a linearly chirped auxiliary pulse that is in common in all existing SSI methods, relying on nonlinear conversion to produce a spectral shear. 相似文献
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Lai C. Chan Brian G. Cox Ian C. Jones Simone Tomasi 《Journal of Physical Organic Chemistry》2011,24(9):751-763
A detailed kinetic analysis and computational study of an SNAr reaction between 2,5,6‐trifluoronicotinonitrile, 2 , and the ambident 3‐isopropoxy‐1H‐pyrazol‐5‐amine, 3 , is presented. The selectivity with respect to the reaction at the primary amino group of 2 , to give the desired product, 2,5‐difluoro‐6‐[(3‐isopropoxy‐1H‐pyrazol‐5‐yl)amino]nicotinonitrile, 1 , is strongly dependent upon reaction conditions. Reaction is found to proceed via both uncatalysed and base catalysed routes, and selectivity towards 1 is strongly enhanced in the presence of the base diazabicyclo[2,2,2]octane (DABCO). Computational studies in tetrahydrofuran solution at the B3LYP/6‐31G* level of theory have provided valuable insight into alternative kinetically indistinguishable reaction pathways. The results suggest that for reaction at the primary amino group, proton removal by DABCO accompanying amine addition allows avoidance of a high‐energy, zwitterionic Meisenheimer intermediate. Reactions at the alternative pyrazole nitrogen atoms are less sensitive to the presence of base because of stabilisation of the Meisenheimer zwitterions by intramolecular hydrogen bonding. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献