The batch synthesis of inorganic clusters can be both time consuming and limited by a lack of reproducibility. Flow-system approaches, now common in organic synthesis, have not been utilized widely for the synthesis of clusters. Herein we combine an automated flow process with multiple batch crystallizations for the screening and scale up of syntheses of polyoxometalates and manganese-based single-molecule magnets. Scale up of the synthesis of these architectures was achieved by programming a multiple-pump reactor system to vary reaction conditions sequentially, and thus explore a larger parameter space in a shorter time than conventionally possible. Also, the potential for using the array as a discovery tool is demonstrated. Successful conditions for product isolation were identified easily from the array of reactions, and a direct route to 'scale up' was then immediately available simply by continuous application of these flow conditions. In all cases, large quantities of phase-pure material were obtained and the time taken for the discovery, repetition and scale up decreased.
We present a systematic study of the interaction between a silicon tip and a reconstructed Si(100)2×1 surface by means of total energy calculations using Density Functional Theory. We perform geometry optimisation to obtain the reconstructed Si surface using the Local Density Approximation and the Generalized Gradient Approximation methods and compare our results with those obtained experimentally.We then study the effects of the tip of a scanning probe of an Atomic Force Microscope (AFM) on the behaviour of atoms on the reconstructed surface when the tip translates at distances close to it. Our results show that at certain positions of the tip relative to the surface and depending on the direction of the scan, the Si dimer on the surface flips, resulting to a local reconstruction of the surface into p(2×2) or c(4×2) configurations. These configurations exhibit energy lower by 0.05 eV/dimer compared to the Si(100)2×1 structure.
Long-term (2004–2020) studies showed yearly summer/autumn blooms in the NE Black Sea dominated by large (cell volume > 5000 μm3) diatoms (Pseudosolenia calcar-avis and Proboscia alata). This phenomenon is characterized by high (>250 W m−2 photosynthetically active radiation, PAR) insolation, and low phosphorus concentrations (to analytical zero). These diatoms contained >100 chloroplasts per cell, which at low irradiance are evenly distributed throughout the cell. As light increases (to 1000 μmol photons m−2 s−1 PAR), chloroplasts aggregate within 20 min, usually to the center of the cell. In consequence, the light absorption coefficient is decreased by >3 fold. At elevated photon flux density (PFD), P. calcar-avis also shows a “conveyor” of chloroplasts moving from the aggregate to the cell periphery and back. This mechanism enables a continuous fine-tuning of the cells’ ability to absorb light, likely also facilitating photo-damage repair. This rapid photoacclimation mechanism allows large diatoms to minimize photodamage at high PFD and acclimate well to low PFD. We hypothesize that competitive success of large diatoms in conditions of high light gradients is aided by this short-term rapid photoacclimation enhancing growth rate while minimizing chloroplast repair costs, aided by the ability of large cells to accumulate nutrients for chloroplast synthesis.
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