No abstract

Colloidal assembly of silica (nano)particles is a powerful method to design functional materials across multiple length scales. Although this method has enabled the fabrication of a wide range of silica‐based materials, attempts to design and synthesize porous materials with a high level of tuneability and control over pore dimensions have remained relatively unsuccessful. Here, the colloidal assembly of silica nanoparticles into mesoporous silica microspheres (MSMs) is reported using a discrete set of silica sols within the confinement of a water‐in‐oil emulsion system. By studying the independent manipulation of different assembly parameters during the sol–gel process, a design strategy is outlined to synthesize MSMs with excellent reproducibility and independent control over pore size and overall porosity, which does not require additional ageing or post‐treatment steps to reach pore sizes as large as 50 nm. The strategy presented here can provide the necessary tools for the microstructural design of the next generation of tailor‐made silica microspheres for use in separation applications and beyond.

No abstract

II,III L(µ-OAc) 2 ]-ClO 4 } has been synthesised, where L is the dianion of 2-{[bis-

By exposing photosystem II (PSII) samples to an incrementing number of excitation flashes at room temperature, followed by freezing, we could compare the Mn-derived multiline EPR signal from the S2 oxidation state as prepared by 1, 5, 10, and 25 flashes of light. While the S2 multiline signals exhibited by these samples differed very little in spectral shape, a significant increase of the relaxation rate of the signal was detected in the multiflash samples as compared to the S2-state produced by a single oxidation. A similar relaxation rate increase was observed for the EPR signal from Y(D*). The temperature dependence of the multiline spin-lattice relaxation rate is similar after 1 and 5 flashes. These data are discussed together with previously reported phenomena in terms of a light-adaptation process of PSII, which commences on the third flash after dark-adaptation and is completed after 10 flashes. At room temperature, the fast-relaxing, light-adapted state falls back to the slow-relaxing, dark-adapted state with t(1/2) = 80 s. We speculate that light-adaptation involves changes necessary for efficient continuous water splitting. This would parallel activation processes found in many other large redox enzymes, such as Cytochrome c oxidase and Ni-Fe hydrogenase. Several mechanisms of light-adaptation are discussed, and we find that the data may be accounted for by a change of the PSII protein matrix or by the light-induced appearance of a paramagnetic center on the PSII donor side. At this time, no EPR signal has been detected that correlates with the increase of the relaxation rates, and the nature of such a new paramagnet remains unclear. However, the relaxation enhancement data could be used, in conjunction with the known Mn-Y(D) distance, to estimate the position of such an unknown relaxer. If positioned between Y(D) and the Mn cluster, it would be located 7-8 A from the spin center of the S2 multiline signal.