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With increasing barriers, an asymmetric but still concerted rearrangement becomes energetically more favorable than the fully symmetric transformation. The material-dependence of the transition can be correlated with the melting point of the bulk metals.Chemical representations derived from deep learning are emerging as a powerful tool in areas such as drug discovery and materials innovation. Currently, this methodology has three major limitations - the cost of representation generation, risk of inherited bias, and the requirement for large amounts of data. We propose the use of multi-task learning in tandem with transfer learning to address these limitations directly. In order to avoid introducing unknown bias into multi-task learning through the task selection itself, we calculate task similarity through pairwise task affinity, and use this measure to programmatically select tasks. We test this methodology on several real-world data sets to demonstrate its potential for execution in complex and low-data environments. Finally, we utilise the task similarity to further probe the expressiveness of the learned representation through a comparison to a commonly used cheminformatics fingerprint, and show that the deep representation is able to capture more expressive task-based information.An aggregation-induced emission (AIE) based smart singlet oxygen (1O2) generation system has been successfully fabricated based on supramolecular host-guest assembly. The controllable 1O2 generation can be achieved by conveniently changing the molar ratio between the macrocyclic host (WP5) and the guest molecule (TPEPY). Moreover, reversible control of 1O2 generation and fluorescence emission of supramolecular nanoassemblies can be achieved via adding Fe3+ and EDTA, which allows qualitatively monitoring the singlet oxygen generation efficiency by the naked eye.Global and local descriptors of the properties of intermolecular bonding, formally derived from independent methodologies (QTAIM, NCI, NBO, density differences) afford a highly complex picture of the bonding interactions responsible for microsolvation of monoatomic cations. In all cases, the dominant factor dictating geometries and interaction strengths is the electrophilic power of the metal cation. The formal charge disrupts the hydrogen bonding network otherwise present in pristine water clusters, making the hydrogen bonds considerably stronger, even inducing some degree of covalency. All MO interactions are highly ionic, with strengths than in some cases approach that of the reference LiCl bond. Accumulation of electron density in the region connecting MO is observed, thus, ionic bonding in the microsolvation of monoatomic cations is not as simple as an electrostatic interaction between opposing charges.A class of CN molecules support excitons with a well-defined quasi-angular momentum. Cofacial arrangements of these molecules can be engineered so that quantum cutting produces a pair of excitons with angular momenta that are maximally entangled. The Bell state constituents can subsequently travel in opposite directions down molecular chains as ballistic wave packets. https://www.selleckchem.com/GSK-3.html This is a direct excitonic analog to the entangled polarization states produced by the spontaneous parametric down-conversion of light. As in optical settings, the ability to produce Bell states should enable foundational experiments and technologies based on non-local excitonic quantum correlation. The idea is elucidated with a combination of quantum electrodynamics theory and numerical simulation.Among the large number of structurally diverse alkaloids, 2,6-disubstituted piperidine and its analogs have often been targeted when exploiting new synthetic techniques perhaps because of their strong pharmacological properties. This review outlines synthetic strategies to build the 2,6-disubstituted piperidine structural motif with a focus on stereochemical control of two substituents at C2 and C6. The key reactions in this process are then classified on the basis of how the piperidine rings were built with specific examples of natural products that control the stereochemical outcomes and their transition states.Covalent grafting of poly(p-phenylenediamine) (PPD)-phosphomolybdic acid (PMo12) on rGO (PPD-PMo12@rGO) has been realized within 1 minute. PPD-PMo12@rGO shows a characteristic covalently linked dual network structure that can significantly enhance its specific capacitance and cycling stability for supercapacitor applications.Nanoparticle-cell-nanoparticle communication by stigmergy was demonstrated using two capped nanodevices. The first community of nanoparticles (i.e. S(RA)IFN) is loaded with 9-cis-retinoic acid and capped with interferon-γ, whereas the second community of nanoparticles (i.e. S(sulf)PIC) is loaded with sulforhodamine B and capped with poly(IC). The uptake of S(RA)IFN by SK-BR-3 breast cancer cells enhanced the expression of TLR3 receptor facilitating the subsequent uptake of S(sulf)PIC and cell killing.The effect of nanoscale confinement of a salt on its ionic conductivity was studied for [NEt4][TFSI] melt-loaded in three isoreticular zirconium-based MOFs UiO-66, UiO-67, and PCN-56. Conductivity of the MOF-salt composites was up to a factor of 50 higher than the pure salt, and maximized with slightly less than full loading of the MOFs.We demonstrate that, in analogy to transition-metal carbene chemistry, [(OC)5Mo[double bond, length as m-dash]BN(SiMe3)2] facilitates intermolecular transfer of the borylene [BN(SiMe3)2], which ultimately undergoes insertion into C-H bonds under very mild conditions. The one-pot multiple functionalization of the cyclopentadienyl rings of tungstenocene dihydride is demonstrated using this approach.Pulp treatment techniques such as pulp capping, pulpotomy and pulp regeneration are all based on the principle of preserving vital pulp. However, specific dental restorative materials that can simultaneously protect pulp vitality and repair occlusal morphology have not been developed thus far. Traditional pulp capping materials cannot be used as dental restorative materials due to their long-term solubility and poor mechanical behavior. Titanium (Ti) is used extensively in dentistry and is regarded as a promising material for pulp sealing because of its favorable biocompatibility, processability and mechanical properties. Originally, we proposed the concept of "odontointegration", which represents direct dentin-like mineralization contact between pulp and the surface of the pulp sealing material; herein, we report the fabrication of a novel antibacterial and dentino-inductive material via micro-arc oxidation (MAO), incorporating self-assembled graphene oxide (GO) for Ti surface modification. The hierarchical micro/nanoporous structure of the MAO coating provides a suitable microenvironment for odontogenic differentiation of human dental pulp stem cells, and GO loading contributes to antibacterial activity.
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