J Fluorescence

The scope of this paper is to illustrate the need for an improved quality assurance in fluorometry. For this purpose, instrumental sources of error and their influences on the reliability and comparability of fluorescence data are highlighted for frequently used photoluminescence techniques ranging from conventional macro- and microfluorometry over fluorescence microscopy and flow cytometry to microarray technology as well as in vivo fluorescence imaging. Particularly, the need for and requirements on fluorescence standards for the characterization and performance validation of fluorescence instruments, to enhance the comparability of fluorescence data, and to enable quantitative fluorescence analysis are discussed. Special emphasis is dedicated to spectral fluorescence standards and fluorescence intensity standards

From Simplicity to Complexity via Subcomponent Self-Assembly

Subcomponent self-assembly allows the construction of complex architectures from simple building blocks via the formation of covalent bonds around metal templates. Since both covalent and coordinative bonds are formed reversibly, a wealth of rearrangement reactions are possible involving substitution at both intraligand and metal–ligand bonds. If the possibilities latent within a set of subcomponents and metal ions are understood, one may also select specific structures from among dynamic libraries of products. The parallel preparation of structures from mixtures of subcomponents is also possible, as is the direction of subcomponents to specific sites within product structures

Different Modes of Anion Response Cause Circulatory Phase Transfer of a Coordination Cage with Controlled Directionality

Controlled directional transport of molecules is essential to complex natural systems, exemplified by cellular transport up to organismal circulatory systems. In contrast to these natural systems, synthetic systems that enable transport of molecules between several spatial locations on the macroscopic scale, when external stimuli are applied, remain to be explored. Here we report the transfer of a supramolecular cage with controlled directionality between three phases, based on the cage that responds reversibly in two distinct ways to different anions. Notably, circulatory phase transfer of the cage was demonstrated based on a system where the three layers of solvent are arranged within a circular track. The direction of circulation between solvent phases depended upon the order of addition of anions.European Research Council (695009), UK Engineering and Physical Sciences Research Council (EPSRC, EP/P027067/1

Utility of photochemical traits as diagnostics of thermal tolerance amongst great barrier reef corals

© 2018 Nitschke, Gardner, Goyen, Fujise, Camp, Ralph and Suggett. Light availability is considered a key factor regulating the thermal sensitivity of reef building corals, where excessive excitation of photosystem II (PSII) further exacerbates pressure on photochemical pathways already compromised by heat stress. Coral symbionts acclimate to changes in light availability (photoacclimation) by continually fine-tuning the photochemical operating efficiency of PSII. However, how this process adjusts throughout the warmest months in naturally heat-tolerant or sensitive species is unknown, and whether this influences the capacity to tolerate transient heat stress is untested. We therefore examined the PSII photophysiology of 10 coral species (with known thermal tolerances) from shallow reef environments at Heron Island (Great Barrier Reef, Australia), in spring (October-November, 2015) vs. summer (February-March, 2016). Corals were maintained in flow-through aquaria and rapid light curve (RLC) protocols using pulse amplitude modulated (PAM) fluorometry captured changes in the PSII photoacclimation strategy, characterized as the minimum saturating irradiance (Ek), and the extent of photochemical ([1-C], operating efficiency) vs. non-photochemical ([1-Q]) energy dissipation. Values of Ek across species were > 2-fold higher in all coral species in spring, consistent with a climate of higher overall light exposure (i.e., higher PAR from lower cloud cover, rainfall and wind speed) compared with summer. Summer decreases in Ek were combined with a shift toward preferential photochemical quenching in all species. All coral species were subsequently subjected to thermal stress assays. An equivalent temperature-ramping profile of 1°C increase per day and then maintenance at 32°C was applied in each season. Despite the significant seasonal photoacclimation, the species hierarchy of thermal tolerance [maximum quantum yields of PSII (Fv/Fm), monitored at dawn and dusk] did not shift between seasons, except for Pocillopora damicornis (faster declines in summer) and Stylophora pistillata (total mortality in spring). Furthermore, the strategy for dealing with light energy (i.e., preferential photochemical vs. non-photochemical quenching) was unchanged for thermally tolerant species across seasons, whereas thermally sensitive species switched between preferential [1-Q] and [1-C] from spring to summer. We discuss how such traits can potentially be used as a diagnostic of thermal tolerance under non-stressed conditions

Multisite Binding of Drugs and Natural Products in an Entropically Favorable, Heteroleptic Receptor.

The cavities of artificial receptors are defined by how their components fit together. The encapsulation of specific molecules can thus be engineered by considering geometric principles; however, intermolecular interactions and steric fit scale with receptor size, such that the ability to bind multiple guests from a specific class of compounds remains a current challenge. By employing metal-organic self-assembly, we have prepared a triangular prism from two different ligands that is capable of binding more than 20 different natural products, drugs, and steroid derivatives within its prolate cavity. Encapsulation inflates the host, enhancing its ability to bind other guests in peripheral pockets and thus enabling our system to bind combinations of different drug and natural product cargoes in different locations simultaneously. This new mode of entropically favorable self-assembly thus enables central encapsulation to amplify guest-binding events around the periphery of an artificial receptor.This work was supported by the UK Engineering and Physical Sciences Research Council (EPSRC EP/P027067/1) and the European Research Council (695009). We thank Cambridge Australia Scholarships (FJR) and the European Union’s Horizon 2020 research and innovation program, Marie Sklodowska-Curie Grant 642192 (JPC) for Ph.D. funding

Post-assembly Modification of Phosphine Cages Controls Host-Guest Behavior.

We report the design, synthesis, and post-assembly modification of a new phosphine-paneled supramolecular cage framework, the anion binding ability of which can be modified rationally through selective post-assembly functionalization. The parent phosphine-paneled cage can be modified in situ through oxidation, methylation, or auration. These covalent and coordinative modifications to the exterior of the cage strongly influence the guest-binding properties of the host.European Research Council (695009), UK Engineering and Physical Sciences Research Council (EPSRC, EP/P027067/1

Pathway-Dependent Post-assembly Modification of an Anthracene-Edged MII4L6 Tetrahedron

FeII4L6 tetrahedral cage 1 undergoes post-assembly modification (PAM) via a Diels–Alder cycloaddition of the anthracene panels of the cage with tetracyanoethylene (TCNE). The modified cage 2 possesses an enclosed cavity suitable for encapsulation of the fullerene C60, whereas original cage 1 forms a unique covalent adduct through a Diels–Alder cycloaddition of three of its anthracene ligands with C60. This adduct undergoes further PAM via reaction of the remaining three ligands with TCNE, enabling the isolation of two distinct products depending on the order of addition of C60 and TCNE. Modified cage 2 was also able to bind an anionic guest, [Co(C2B9H11)2]−, which was not encapsulated by the original cage, demonstrating the potential of PAM for tuning the binding properties of supramolecular hosts

Enantiopure water-soluble [Fe4L6] cages: host-guest chemistry and catalytic activity.

This is the author accepted manuscript. The final version is available from Wiley via http://dx.doi.org/10.1002/anie.20130213

Otherwise Unstable Structures Self-Assemble in the Cavities of Cuboctahedral Coordination Cages.

We present a method for the directed self-assembly of interlocked structures and coordination complexes in a set of metal-organic hosts. New homo- and heteroleptic metal complexes-species that cannot be prepared outside-form within the cavities of cuboctahedral coordination cages. When linear bidentate guests and macrocycles are sequentially introduced to the host, a rotaxane is threaded internally; the resulting ternary host-guest complex is a new kind of molecular gyroscope. Tetradentate guests segregate the cavities of these cages into distinct spaces, promoting new stoichiometries and modes of ligand binding to metal ions. The behaviors of bound complexes were observed to alter markedly as a result of confinement: In situ oxidations and spin transitions, neither of which occur ex situ, were both observed to proceed. By providing a tailored space for new modes of coordination-driven self-assembly, the inner phases of cuboctahedral coordination cages provide a new medium for synthetic coordination chemistry.UK Engineering and Physical Sciences Research Council (EPSRC EP/P027067/1) and the European Research Council (ERC 695009)