Fluorescence (FL) emission properties, microporous structures, energy‐minimized chain conformations, and lamellar layer structures of the silicon‐containing poly(diphenylacetylene) derivative of p‐PTMSDPA before and after desilylation were investigated. The nitrogen‐adsorption isotherms of p‐PTMSDPA film before and after desilylation were typical of type I, indicating microporous structures. The BET surface area and pore volume of the p‐PTMSDPA film were significantly reduced after the desilylation reaction, simultaneously, its FL emission intensity remarkably decreased. The theoretical calculation on both model compounds of p‐PTMSDPA and its desilylated polymer, PDPA, showed a remarkable difference in chain conformation: The side phenyl rings of p‐PTMSDPA are discontinuously arranged in a zig‐zag pattern, while the PDPA is continuously coiled in a helical manner. The lamellar layer distance (LLD) in the p‐PTMSDPA film significantly decreased after the desilylation reaction.
Well‐defined “smart” block copolymer–protein conjugates were prepared by two consecutive “grafting‐from” reactions via reversible addition–fragmentation chain transfer (RAFT) polymerization. The initiating portion (R‐group) of the RAFT agent was anchored to a model protein such that the thiocarbonylthio moiety was readily accessible for chain transfer with propagating chains in solution. Well‐defined polymer‐protein conjugates of poly(N‐isopropylacrylamide) (PNIPAM) and bovine serum albumin (BSA) were prepared at room temperature in aqueous media. The retained trithiocarbonate moiety on the free end group of the immobilized polymer allowed the homopolymer conjugate to be extended by polymerization of N,N‐dimethylacrylamide. Polyacrylamide gel electrophoresis, size exclusion chromatography, and NMR spectroscopy confirmed the synthesis of the various conjugates and revealed that the polymerizations were well controlled. As expected, the resulting block copolymer–protein conjugates demonstrated thermoresponsive behavior due to the temperature‐sensitivity of the PNIPAM block, as evidenced by turbidity measurements and dynamic light scattering analysis.
The frame associated with a classical point particle is generally noninertial. The point particle may have a nonzero velocity and force with respect to an absolute inertial rest frame. In time–position–energy–momentum-space {t, q, p, e}, the group of transformations between these frames leaves invariant the symplectic metric and the classical line element ds2 = d t2. Special relativity transforms between inertial frames for which the rate of change of momentum is negligible and eliminates the absolute rest frame by making velocities relative but still requires the absolute inertial frame. The Lorentz group leaves invariant the symplectic metric and the line elements and . General relativity for particles under only the influence of gravity avoids the issue of noninertial frames as all particles follow geodesics and hence have locally inertial frames. For other forces, the question of the absolute inertial frame remains.) Born conjectured that the line element should be generalized to the pseudo-orthogonal metric . The group leaving this metrics and the symplectic metric invariant is the pseudo-unitary group of transformations between noninertial frames. We show that these transformations also eliminate the need for an absolute inertial frame by making forces relative and bounded by b and so embodies a relativity that is shape reciprocal in the sense of Born. The inhomogeneous version of this group is naturally the semidirect product of the pseudo-unitary group with the nonabelian Heisenberg group. This is the quaplectic group. 相似文献
