Effective photolytic regeneration of the NAD(P)H cofactor in enzymatic reductions is an important and elusive goal in biocatalysis. It can, in principle, be achieved using a near-infrared light (NIR) driven artificial photosynthesis system employing H₂O as the sacrificial reductant. To this end we utilized TiO₂/reduced graphene quantum dots (r-GQDs), combined with a novel rhodium electron mediator, to continuously supply NADPH in situ for aldo-keto reductase (AKR) mediated asymmetric reductions under NIR irradiation. This upconversion system, in which the Ti-O-C bonds formed between r-GQDs and TiO₂ enabled efficient interfacial charge transfer, was able to regenerate NADPH efficiently in 64 % yield in 105 min. Based on this, the pharmaceutical intermediate (R)-1-(3,5-bis(trifluoromethyl)phenyl)ethan-1-ol was obtained, in 84 % yield and 99.98 % ee, by reduction of the corresponding ketone. The photo-enzymatic system is recyclable with a polymeric electron mediator, which maintained 66 % of its original catalytic efficiency and excellent enantioselectivity (99.9 % ee) after 6 cycles.

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A structure-based modelling framework was established to simulate the three-dimensional autogenous shrinkage of cement paste. A cement hydration model, HYMOSTRUC3D-E, was used to obtain the microstructures and ionic concentrations of the cement paste. A lattice fracture model based on the effective stress and effective modulus was used to consider the elastic and creep parts of autogenous shrinkage. For Portland cement pastes with water-to-cement ratios of 0.3 and 0.4 (where the time zero of autogenous shrinkage was set as the time of the drop in internal relative humidity), the simulated linear elastic autogenous shrinkage was respectively −188 and −79 μm/m at 160 h. The obtained linear total autogenous shrinkage including elastic and creep deformations was respectively −501 and −236 μm/m at 160 h. These values of the elastic autogenous shrinkage and total autogenous shrinkage are close to the predications of poromechanical models and experimental data obtained using a corrugated tube.

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Non-uniform stresses, strains and microcracking of the concretes with three coarse aggregate sizes (5–10 mm, 10–16 mm, 16–20 mm) dried under 40% relative humidity (RH) for 60 days were quantified using digital image correlation and lattice fracture modelling. The influencing mechanism of coarse aggregate size on the drying-induced microcracking of concrete was clarified: (1) As the coarse aggregate size decreases, propagation paths of microcracking are increased, which increase the number of small microcracks and release the drying shrinkage force from mortar phase. (2) Tensile stress shells surrounding the coarse aggregates become thinner, thereby decreasing the area of large microcracks. As the coarse aggregate size decreased from 16-20 mm to 5–10 mm, the average thickness of tensile stress shells decreased from 2.13 mm to 1.09 mm at the beginning of drying, and the area of the microcracks >5 μm in width decreased from 796.6 mm²/m² to 340.2 mm²/m² at 60 days since drying.

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Concrete generally deforms and cracks in a non-uniform manner under drying-induced stress. This study used the lattice fracture model to simulate the drying-induced non-uniform deformations, stresses, and micro-crack propagation in concrete. Experiments were designed to validate the lattice fracture model, wherein the drying-induced non-uniform deformations and micro-crack patterns in concrete were measured using a digital image correlation technique and a fluorescent epoxy impregnation method, respectively. It was found that the simulated non-uniform deformations and micro-crack patterns were close to the experimental observations. The interaction mechanism between drying-induced non-uniform stresses and micro-cracks was analysed based on the validated lattice fracture model. The micro-cracks were found to cause stress concentration both in coarse aggregate and the mortar that covered coarse aggregate, which could lead to high micro-cracking risk as drying continues.@en

To assess the effect of relative humidity (RH) on drying-induced damage in concrete, the non-uniform strains and microcracks in concrete under different RH conditions were obtained using the digital image correlation (DIC) technique and lattice fracture model. The simulated non-uniform displacements were consistent with those captured using DIC. A new damage index was proposed by considering all the subsets with equivalent strain larger than the threshold tensile strength. The calculated damage index showed good correlation with the microcracks' total area and indicated that RH equal or lower than 55% could cause relatively high cracking risk. This work provides an attractive method for quantifying drying-induced damage in concrete using the DIC technique.

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