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

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)

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

Subtle Ligand Modification Inverts Guest Binding Hierarchy in M(II)8L6 Supramolecular Cubes.

Zinc(II), a dimolybdenum(II) paddlewheel tetramine A, and 2-formylpyridine self-assembled to generate a cubic Zn(II)8(L(A))6 assembly. The paddlewheel faces of this assembly exhibited two distinct conformations, whereas the analogous Fe(II)8(L(A))6 framework displayed no such perturbation to its structure. This variation in behavior is attributed to the subtle difference in ligand rotational freedom between the Zn(II)- and Fe(II)-cornered cubes. The incorporation of a fluorinated Mo(II)2 paddlewheel, B, into analogous Zn(II)8(L(B))6 and Fe(II)8(L(B))6 structures resulted in changes to the rotational dynamics of the ligands. These differing dynamics perturbed the energies of the frontier orbitals of these structures, as determined through spectroscopic and electrochemical methods. The result of these perturbations was an inversion of the halide binding preference of the Zn(II)8(L(B))6 host as compared to its Zn(II)8(L(A))6 congener, whereas the Fe(II)8(L(B))6 host maintained a similar binding hierarchy to Fe(II)8(L(A))6.Seventh Framework ProgrammeThis is the final version of the article. It first appeared from the American Chemical Society via http://dx.doi.org/10.1021/jacs.6b0385

Mapping canopy nitrogen-scapes to assess foraging habitat for a vulnerable arboreal folivore in mixed-species Eucalyptus forests

Herbivore foraging decisions are closely related to plant nutritional quality. For arboreal folivores with specialized diets, such as the vulnerable greater glider (Petauroides volans), the abundance of suitable forage trees can influence habitat suitability and species occurrence. The ability to model and map foliar nitrogen would therefore enhance our understanding of folivore habitat use at finer scales. We tested whether high-resolution multispectral imagery, collected by a lightweight and low-cost commercial unoccupied aerial vehicle (UAV), could be used to predict total and digestible foliar nitrogen (N and digN) at the tree canopy level and forest stand-scale from leaf-scale chemistry measurements across a gradient of mixed-species Eucalyptus forests in southeastern Australia. We surveyed temperate Eucalyptus forests across an elevational and topographic gradient from sea level to high elevation (50–1200 m a.s.l.) for forest structure, leaf chemistry, and greater glider occurrence. Using measures of multispectral leaf reflectance and spectral indices, we estimated N and digN and mapped N and favorable feeding habitat using machine learning algorithms. Our surveys covered 17 Eucalyptus species ranging in foliar N from 0.63% to 1.92% dry matter (DM) and digN from 0.45% to 1.73% DM. Both multispectral leaf reflectance and spectral indices were strong predictors for N and digN in model cross-validation. At the tree level, 79% of variability between observed and predicted measures of nitrogen was explained. A spatial supervised classification model correctly identified 80% of canopy pixels associated with high N concentrations (≥1% DM). We developed a successful method for estimating foliar nitrogen of a range of temperate Eucalyptus species using UAV multispectral imagery at the tree canopy level and stand scale. The ability to spatially quantify feeding habitat using UAV imagery allows remote assessments of greater glider habitat at a scale relevant to support ground surveys, management, and conservation for the vulnerable greater glider across southeastern Australia

Temperature Controls Guest Uptake and Release from Zn4L4 Tetrahedra.

We report the preparation of triazatruxene-faced tetrahedral cage 1, which exhibits two diastereomeric configurations (T1 and T2) that differ in the handedness of the ligand faces relative to that of the octahedrally coordinated metal centers. At lower temperatures, T1 is favored, whereas T2 predominates at higher temperatures. Host-guest studies show that T1 binds small aliphatic guests, whereas T2 binds larger aromatic molecules, with these changes in binding preference resulting from differences in cavity size and degree of enclosure. Thus, by a change in temperature the cage system can be triggered to eject one bound guest and take up another.This work was supported by the European Research Council (695009) and the UK Engineering and Physical Sciences Research Council (EPSRC EP/M008258/1). The authors thank the Department of Chemistry NMR Facility at the University of Cambridge for performing some NMR experiments and the EPSRC UK National Mass Spectrometry Facility at Swansea University for carrying out high-resolution mass spectrometry. D.Z. acknowledges a Herchel Smith Research Fellowship from the University of Cambridge. J.D.T. acknowledges the Rashkind Family Endowment and the Chenery Endowment from Randolph-Macon College