Self-sorting of two imine-based metal complexes: Balancing kinetics and thermodynamics in constitutional dynamic networks

A major hurdle in the development of complex constitutional dynamic networks (CDNs) is the lack of strategies to simultaneously control the output of two (or more) interconnected dynamic processes over several species, namely reversible covalent imine bond formation and dynamic metal–ligand coordination. We have studied in detail the self-sorting process of 11 constitutional dynamic libraries containing two different amines, aldehydes and metal salts into two imine-based metal complexes, having no overlap in terms of their compositions. This study allowed us to determine the factors influencing the fidelity of this process (concentration, electronic and steric parameters of the organic components, and nature of the metal cations). In all 11 systems, the outcome of the process was primarily determined by the ability of the octahedral metal ion to select its pair of components from the initial pool of components, with the composition of the weaker tetrahedral complex being imposed by the components rejected by the octahedral metal ions. Different octahedral metal ions required different levels of precision in the “assembling instructions” provided by the organic components of the CDN to guide it towards a sorted output. The concentration of the reaction mixture, and the electronic and steric properties of the initial components of the library were all found to influence the lifetime of unwanted metastable intermediates formed during the assembling of the two complexes

Triple Self-Sorting in Constitutional Dynamic Networks: Parallel Generation of Imine-Based CuI, FeII, and ZnII Complexes

Three imine‐based metal complexes, having no overlap in terms of their compositions, have been simultaneously generated from the self‐sorting of a constitutional dynamic library (CDL) containing three amines, three aldehydes, and three metal salts. The hierarchical ordering of the stability of the three metal complexes assembled and the leveraging of the antagonistic and agonistic relationships existing between the constituents within the constitutional dynamic network corresponding to the CDL were pivotal in achieving the sorting. Examination of the process by NMR spectroscopy showed that the self‐sorting of the FeII and ZnII complexes depended on an interplay between the thermodynamic driving forces and a kinetic trap involved in their assembly. These results also exemplify the concept of “simplexity”—the fact that the output of a self‐assembling system may be simplified by increasing its initial compositional complexity—as the two complexes could self‐sort only in the presence of the third pair of organic components, those of the CuI complex

Proceedings of the Spacecraft Charging Technology Conference: Executive Summary

Aerospace environments are reviewed in reference to spacecraft charging. Modelling, a theoretical scheme which can be used to describe the structure of the sheath around the spacecraft and to calculate the charging currents within, is discussed. Materials characterization is considered for experimental determination of the behavior of typical spacecraft materials when exposed to simulated geomagnetic substorm conditions. Materials development is also examined for controlling and minimizing spacecraft charging or at least for distributing the charge in an equipotential manner, using electrical conductive surfaces for materials exposed to space environment

Strengthening the Cohomological Crepant Resolution Conjecture for Hilbert-Chow morphisms

Given any smooth toric surface S, we prove a SYM-HILB correspondence which relates the 3-point, degree zero, extended Gromov-Witten invariants of the n-fold symmetric product stack [Sym^n(S)] of S to the 3-point extremal Gromov-Witten invariants of the Hilbert scheme Hilb^n(S) of n points on S. As we do not specialize the values of the quantum parameters involved, this result proves a strengthening of Ruan's Cohomological Crepant Resolution Conjecture for the Hilbert-Chow morphism from Hilb^n(S) to Sym^n(S) and yields a method of reconstructing the cup product for Hilb^n(S) from the orbifold invariants of [Sym^n(S)].Comment: Revised versio

Communication: part 2 - delivering findings and advice to the patient

The outcome and consequences of results from examination tests need to be communicated in a way that can be easily understood by the patient, encouraging them to follow the advice that has been given by the practitioner. For a number of reasons, the delivery of findings and advice to the patient is a highly complex communicative activity. The content of information given can vary widely in length and seriousness. In addition, patients can vary in their capacity to understand information delivered and in their ability to cope with ‘bad news’. Finally, the ways in which findings and advice are communicated can have a significant impact on patient adherence and compliance with management recommendations

Communication: part 1 - soliciting information from the patient

Soliciting information from the patient is a key part of the consultation. Successful clinical outcomes are reliant on the practitioner asking questions to gather relevant information regarding, for instance, the patient’s history and symptoms and their responses to examination tests. This information needs to be gathered in a time efficient manner and in a way that encourages the patient to feel relaxed and fully engage with the eye examination. Practitioners often report that soliciting relevant information can be made difficult by over-talkative patients who take up valuable time giving lengthy, perhaps irrelevant, answers. Alternatively, patients may provide insufficient detail due to discomfort, anxiety or a lack of understanding. Finally, patients can at times appear overly concerned with providing the ‘correct’ answer to certain questions. This article describes some ways to optimise the complex process of soliciting information from the patient focusing on selection of question type, question wording and the role of eye contact. Examples given are based upon research analysis of video-recorded optometric consultations

Topological properties of punctual Hilbert schemes of almost-complex fourfolds (I)

In this article, we study topological properties of Voisin's punctual Hilbert schemes of an almost-complex fourfold $X$. In this setting, we compute their Betti numbers and construct Nakajima operators. We also define tautological bundles associated with any complex bundle on $X$, which are shown to be canonical in $K$-theory