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A near-infrared fluorescent probe (AH+) has been prepared by incorporating an oxazolidine switch into a near-infrared hemicyanine dye. The probe shows fast and sensitive responses to pH from an oxazolidine switch to the hemicyanine dye upon pH decreases from 10.0 to 5.0. The probe shows good photostability, low cytotoxicity, and reversible fluorescence responses to pH changes with a pKa value of 7.6. It has been successfully used to determine pH changes in mitochondria.We consider the propagation of tension along specific filaments of a semiflexible filament network in response to the application of a point force using a combination of numerical simulations and analytic theory. We find the distribution of force within the network is highly heterogeneous, with a small number of fibers supporting a significant fraction of the applied load over distances of multiple mesh sizes surrounding the point of force application. We suggest that these structures may be thought of as tensile force chains, whose structure we explore via simulation. We develop self-consistent calculations of the point-force response function and introduce a transfer matrix approach to explore the decay of tension (into bending) energy and the branching of tensile force chains in the network.Proton-coupled electron transfer (PCET) reactions are ubiquitous natural processes at the heart of energy conversion reactions in photosynthesis and respiration, DNA repair, and diverse enzymatic reactions. Theoretical formulation and computational method developments have eyed modeling of thermal and photoinduced PCET for the last three decades. The accumulation of these studies, collected in dozens of reviews, accounts, and perspectives, has firmly established the influence of quantum effects, including non-adiabatic electronic transitions, vibrational relaxation, zero-point energy, and proton tunneling, on the rate and mechanism of PCET reactions. Here, we focus on some recently-developed methods, spanning the last eight years, that can quantitatively capture these effects in the PCET context and provide efficient means for their qualitative description in complex systems. The theoretical background of each method and their accuracy with respect to exact results are discussed and the results of relevant PCET simulations based on each method are presented.A quasi-two-dimensional electron gas (2DEG) evolved at the LaAlO3 (LAO)/SrTiO3 (STO) interface has attracted significant attention, because the insertion of perovskite titanates can tune the 2DEG conductivity. However, this depends on the Ti-O-Ti bonding angle and structural symmetry. In this study, we controlled the octahedral tilt of the LAO/CaTiO3 (CTO) interface by heterostructuring it with CTO grown on STO substrates of various thicknesses. The 2DEG was maintained when the thickness of CTO was below the critical thickness of 5 unit cells (uc); however, it was suppressed when the CTO thickness was above the critical thickness. High-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) combined with integrated differential phase contrast (iDPC) STEM imaging was used to visualize the TiO6 octahedral tilt propagation and symmetry of the 5 uc and 24 uc CTO films. The symmetry of the 5 uc CTO film resembled that of the STO substrate, whereas the octahedral tilt propagated in the 24 uc CTO film due to the structural relaxation. These results show that the interface engineering of the octahedral tilt can enable or suppress the formation of the 2DEG in perovskite oxides.Hydrogels have had a profound impact in the fields of tissue engineering, drug delivery, and materials science as a whole. Due to the network architecture of these materials, imbibement with water often results in uniform swelling and isotropic expansion which scales with the degree of cross-linking. However, the development of internal stresses during swelling can have dramatic consequences, leading to surface instabilities as well as rupture or bursting events. selleck chemical To better understand hydrogel behavior, macroscopic mechanical characterization techniques (e.g. tensile testing, rheometry) are often used, however most commonly these techniques are employed on samples that are in two distinct states (1) unswollen and without any solvent, or (2) in an equilibrium swelling state where the maximum amount of water has been imbibed. Rarely is the dynamic process of swelling studied, especially in samples where rupture or failure events are observed. To address this gap, here we focus on rupture events in poly(ethylene glycol)-based networks that occur in response to swelling with water. Rupture events were visualized using high-speed imaging, and the influence of swelling on material properties was characterized using dynamic mechanical analysis. We find that rupture events follow a three-stage process that includes a waiting period, a slow fracture period, and a final stage in which a rapid increase in the velocity of crack propagation is observed. We describe this fracture behavior based on changes in material properties that occur during swelling, and highlight how this rupture behavior can be controlled by straight-forward modifications to the hydrogel network structure.Polyelectrolytes such as polyaspartic acid (PAsp) are critical in biomimetic mineralization as stabilizers of amorphous calcium phosphate (ACP) precursors and as nucleation inhibitors similar to non-collagenous proteins (NCPs). Nevertheless, the application of polyelectrolyte-calcium complexes as a pre-precursor, such as PAsp-Ca complexes, in the mineralization of collagen is unexplored. Herein, we propose a polyelectrolyte-Ca complex pre-precursor (PCCP) process for collagen mineralization. By combining three-dimensional (3D) STORM, potential measurements, and cryogenic transmission electron microscopy with molecular dynamics simulations, we show that liquid-like electropositive PAsp-Ca complexes along with free calcium ions infiltrate electronegative collagen fibrils. The PAsp-Ca complexes are immobilized within the fibrils via chelation and hydrogen bonds, and outward movement of free calcium ions is prevented while phosphate and hydroxide are recruited through electrostatic attractions. Afterwards, ACP instantly forms and gradually crystallizes.

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