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Adaptive hydrogels, often termed smart materials, are macromolecules whose structure adjusts to external stimuli. Responsive micro- and nanogels are particularly interesting because the small length scale enables very fast response times. Chemical cross-links provide topological constraints and define the three-dimensional structure of the microgels, whereas their porous structure permits fast mass transfer, enabling very rapid structural adaption of the microgel to the environment. The change of microgel structure involves a unique transition from a flexible, swollen finite-size macromolecular network, characterized by a fuzzy surface, to a colloidal particle with homogeneous density and a sharp surface. In this contribution, we determine, for the first time, the structural evolution during the microgel-to-particle transition. Time-resolved small-angle x-ray scattering experiments and computer simulations unambiguously reveal a two-stage process: In a first, very fast process, collapsed clusters form at the periphery, leading to an intermediate, hollowish core-shell structure that slowly transforms to a globule. This structural evolution is independent of the type of stimulus and thus applies to instantaneous transitions as in a temperature jump or to slower stimuli that rely on the uptake of active molecules from and/or exchange with the environment. The fast transitions of size and shape provide unique opportunities for various applications as, for example, in uptake and release, catalysis, or sensing., Science Advances, 4 (4), ISSN:2375-2548

Platinum nanoparticles ( d Pt = 1.0–1.2 nm) supported on single CeO 2 and La 2 O 3 metal oxides and Ce 0.8 La 0.2 O 2− δ solid solution were prepared to investigate for the first time the effect of La 3+ -doping of ceria on important mechanistic and kinetic aspects of the water-gas shift (WGS) reaction, namely: (i) the concentration and chemical structure of active adsorbed reaction intermediates present in the C-path and H-path of WGS at 250 and 300 °C, (ii) the chemical nature of inactive species formed during WGS, and (iii) the prevailing mechanistic path among “redox” and “associative” both proposed in the literature. For this, steady-state isotopic transient kinetic analysis (SSITKA) experiments coupled with in situ DRIFTS and mass spectrometry were performed to follow the H-path (use of D 2 O) and C-path (use of 13 CO) of the WGS. In addition, other transient isotopic experiments using operando methodology (use of DRFTS and mass spectrometry) were designed to follow with time on stream the reactivity toward water of the various adsorbed species formed under WGS. It is proposed that on Pt/Ce 1− x La x O 2− δ ( x = 0.0, 0.2 and 1.0) the WGS reaction follows both the “redox” and “associative” mechanisms but the extent of participation of each mechanism to the overall WGS reaction rate depends on the support chemical composition. The WGS kinetic rate (μmol CO g −1 s −1 ) increased by a factor of 2.0 and 2.8 at 300 °C on 0.5 wt% Pt supported on Ce 0.8 La 0.2 O 2− δ compared to CeO 2 and La 2 O 3 , respectively. This was explained by (i) the larger concentration of active surface intermediates formed around each Pt nanoparticle (larger extent of reactive zone) and (ii) the higher reactivity of sites ( k , s −1 ) responsible for CO 2 and H 2 formation on Pt/Ce 0.8 La 0.2 O 2− δ compared to Pt/CeO 2 and Pt/La 2 O 3 . Active OH groups is suggested to be formed on defect sites (Ce 3+ □ s ) of Ce 0.8 La 0.2 O 2− δ as a consequence of the introduction of La 3+ into the ceria lattice, the latter enhancing the concentration of labile oxygen and its surface mobility, important characteristics of the “redox” mechanism.

Ruthenium monoterpyridine complexes with the tridentate 2,6-bis(benzimidazol-2-yl)pyridine (LH2), [Ru(trpy)(LH2)](2+), [1](2+) and [Ru(trpy)(L2-)], 2 (trpy = 2,2':6',2 ''-terpyridine) have been synthesized. The complexes have been authenticated by elemental analyses, UV-Vis, FT-IR, H-1 NMR spectra and their single crystal X-ray structures. Complexes [1](2+) and 2 exhibit strong MLCT band near 475 and 509 nm, respectively, and are found to be very much dependent on solution pH. The successive pH dependent dissociations of the N-H protons of benzimidazole moiety of LH2 in [1](2+) lead to the formation of 2. The proton induced inter-convertibility of [1](2+) and 2 has been monitored via UV-Vis spectroscopy and redox features. The two pK(a) values, 5.75 and 7.70, for complex [1](2+) have been determined spectroscopically. (C) 2008