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Zhiyuan Zhu

Publications and source records attributed to Zhiyuan Zhu.

5 recordsLinked to original sources

Stabilization of catanionic vesicles via polymerization.

Polymerizable cationic surfactant methacryloyloxyoctyl trimethylammonium bromide (MOTB) and anionic surfactant sodium 4-(omega-methacryloyloxyoctyl)oxy benzene sulfonate (MOBS) were synthesized. Stable catanionic vesicles can spontaneously form upon mixing the two oppositely charged surfactants in aqueous solution, which was further permanently fixed by polymerization. Surface tensiometry, nuclear magnetic resonance (NMR), static and dynamic laser light scattering (LLS), and cryogenic transmission electron microscopy (cryo-TEM) were used in combination to characterize the catanionic vesicles before and after polymerization. The kinetics of formation and breakdown of unpolymerized catanionic vesicles were studied in detail employing stopped-flow light scattering. In contrast to unpolymerized vesicles, the polymerized ones exhibit permanent stability under external perturbations such as dilution or adding excess MOTB. A tentative explanation is proposed about why free radical polymerization can successfully fix the catanionic vesicles, the structure of which is well-known to be in dynamic equilibrium exchange with unimers.

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Phase transition behavior of unimolecular micelles with thermoresponsive poly(N-isopropylacrylamide) coronas.

This paper describes the double phase transition behavior of a thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) brush at the surface of a hydrophobic core. Reversible addition-fragmentation transfer (RAFT) polymerization of N-isopropylacrylamide (NIPAM) was conducted by using a hyperbranched polyester (Boltorn H40) based macroRAFT agent. The resultant multiarm star block copolymer (H40-PNIPAM) exists as unimolecular micelles with hydrophobic H40 as the core, densely grafted PNIPAM brush as the shell. A combination of laser light scattering (LLS) and microdifferential scanning calorimetry (micro-DSC) studies of H40-PNIPAM in aqueous solution reveals double phase transitions of the PNIPAM corona, which is in contrast to the fact that free PNIPAM homopolymer in aqueous solution exhibits a lower critical solution temperature (LCST) at approximately 32 degrees C. The first phase transition takes place in the broad temperature range 20-30 degrees C, which can be tentatively ascribed to the n-cluster-induced collapse of the inner region of the PNIPAM brush close to the H40 core; the second phase transition occurs above 30 degrees C, which can be ascribed to the outer region of PNIPAM brush. Employing the RAFT chain extension technique, the inner and outer part of PNIPAM brush were then selectively labeled with pyrene derivatives, respectively; temperature-dependent excimer fluorescence measurements further support the conclusion that the inner part of PNIPAM brush collapses first at lower temperatures, followed by the collapse of the outer part at higher temperatures.

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Far-infrared characteristics of ZnS nanoparticles measured by terahertz time-domain spectroscopy.

The optical and dielectric properties of ZnS nanoparticles are studied by use of terahertz time-domain spectroscopy (THz-TDS) over the frequency range from 0.3 to 3.0 THz. The effective medium approach combined with the pseudo-harmonic model of the dielectric response, where nanoparticles are embedded in the host medium, provides a good fit on the experimental results. The extrapolation of the measured data indicates that the absorption is dominated by the transverse optical mode localized at 11.6+/-0.2 THz. Meanwhile, the low-frequency phonon resonance of ZnS nanoparticles is compared with the single-crystal ZnS. The THz-TDS clearly reveals the remarkable distinction in the low-frequency phonon resonances between ZnS nanoparticles and single-crystal ZnS. The results demonstrate that the acoustic phonons become confined in small-size nanoparticles.

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Polymerization of anionic wormlike micelles.

Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles.

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First observation of two-stage collapsing kinetics of a single synthetic polymer chain.

Using a narrowly distributed poly(N-isoporpylacrylamide) (PNIPAM) chain with a degree of polymerization (N) of 3100, randomly labeled with pyrene, we have, for the first time, observed the two-stage kinetics of the coil-to-globule transition. Two characteristic relaxation times, tau(fast) for the crumpling of a random coil (approximately 12 ms) and tau(slow) for the collapsing of the crumpled chain to a compact globule (approximately 270 ms), were measured. To our knowledge, this is the first experimental evidence supporting the two-stage collapsing kinetics of single synthetic polymer chain previously proposed by de Gennes, Dawson, and Grosberg.

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