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

Estimation of GCM Temperature Trends for Different Emission Scenarios with the help of the Integrated Model to Assess the Greenhouse Effect (IMAGE)

How useful are General Circulation Models (GCMs) for policy makers? Of course, they are considered to be the most powerful models that are presently available for predicting future climates and for carrying out research. Their disadvantage is that they are very time-consuming and very expensive to run for any greenhouse gas emission or concentration scenario. For that reason, GCMs have been run only for a small number of scenarios. However, policy makers are interested in being able to analyze a large number of scenarios. The Integrated Model to Assess the Greenhouse Effect (IMAGE) developed by the National Institute for Public Health and Environmental Protection (RIVM) in the Netherlands is a scientifically based, policy oriented model that can calculate the effect of different greenhouse gas emissions on global surface air temperature and sea level rise. The major advantage of IMAGE is its quick turnaround time. Its disadvantage is that it gives only global values of surface temperature and sea level rise, which have insufficient spatial resolution to estimate ecological impacts on a regional basis. We propose a methodology for combining the fast turnaround time and time-dependent surface temperature results of IMAGE with the spatial resolution of GCMs to provide a linkage between IMAGE and models of ecological change that could provide policy-makers with valuable information about the consequences of different levels of reduction of greenhouse gas emissions

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

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

Sequence-Dependent Guest Release Triggered by Orthogonal Chemical Signals.

Three Zn(II)4L4 coordination cages, assembled from trisiminopyridine ligands, exhibit differences in their guest-binding selectivities and reactivity with tris(2-aminoethyl)amine (tren), which enabled the design of a molecular network that responded in distinct ways to different chemical signals. When two of these cages were present in solution together, one of them was observed to selectively encapsulate chloroform, and the other was observed to selectively encapsulate cyclohexane. The two guests could be released sequentially, in a specified order defined by the input of two separate chemical signals: tren and perrhenate. Furthermore, the observed reactivity of tren with the initial cage mixture provided control over the uptake and release of perrhenate within the third cage formed in situ. One of these tetrahedral cages has been identified as a tight (K(a) > 10(7) M(-1)) and selective host for perrhenate, an anion of great physicochemical similarity to pertechnetate, both having uses in nuclear medicine.This work was supported by the European Research Council. We thank Diamond Light Source (UK) for synchrotron beamtime on I19 (MT8464) and Dr. Rana A. Bilbeisi for a preliminary screening of guests for cage 1.This is the author accepted manuscript. The final version is available from the American Chemical Society via http://dx.doi.org/10.1021/jacs.5b1301

Improved Acid Resistance of a Metal-Organic Cage Enables Cargo Release and Exchange between Hosts.

The use of di(2-pyridyl)ketone in subcomponent self-assembly is introduced. When combined with a flexible triamine and zinc bis(trifluoromethanesulfonyl)imide, this ketone formed a new Zn4 L4 tetrahedron 1 bearing twelve uncoordinated pyridyl units around its metal-ion vertices. The acid stability of 1 was found to be greater than that of the analogous tetrahedron 2 built from 2-formylpyridine. Intriguingly, the peripheral presence of additional pyridine rings in 1 resulted in distinct guest binding behavior from that of 2, affecting guest scope as well as binding affinities. The different stabilities and guest affinities of capsules 1 and 2 enabled the design of systems whereby different cargoes could be moved between cages using acid and base as chemical stimuli.European Research Council (695009), UK Engineering and Physical Sciences Research Council (EPSRC EP/P027067/1

Stacking Interactions Drive Selective Self-Assembly and Self-Sorting of Pyrene-Based M(II)4L6 Architectures.

Subcomponent self-assembly of two isomeric bis(3-aminophenyl)pyrenes, 2-formylpyridine and the metal ions Fe(II), Co(II), and Zn(II) led to the formation of two previously unidentified structure types: a C2-symmetric M(II)4L6 assembly with meridionally coordinated metal centers, and a C3-symmetric self-included M(II)4L6 assembly with facially coordinated metal centers. In both structures the meta linkages within the ligands facilitate π-stacking between the pyrene panels of the ligands. A C2h-symmetric M(II)2L2 box was also obtained, which was observed to selectively bind electron-deficient aromatic guests between two parallel pyrene subunits. Similar donor-acceptor interactions drove the selective self-assembly of a singular M(II)4L4L'2 architecture incorporating both a pyrene-containing diamine and an electron-deficient NDI-based diamine. This heteroleptic architecture was shown to be thermodynamically favored over the corresponding homoleptic M(II)4L6 and M(II)4L'6 complexes, which were nonetheless stable in each others' absence. By contrast, an isomeric pyrene-based diamine was observed to undergo narcissistic self-sorting in the presence of the NDI-based diamine.This work was supported by the UK Engineering and Physical Sciences Research Council (EPSRC). D.A.R. acknowledges the Gates Cambridge Trust for Ph.D. funding (Gates Cambridge Scholarship). We thank the EPSRC Mass Spectrometry Service at Swansea for carrying out the high resolution mass spectrometry and Diamond Light Source (UK) for synchrotron beamtime on I19 (MT8464). We also thank the NMR service team at the Department of Chemistry, University of Cambridge for performing some NMR experiments.This is the final version of the article. It first appeared from the American Chemical Society via http://dx.doi.org/10.1021/jacs.5b0992

Anion Pairs Template a Trigonal Prism with Disilver Vertices.

Here we describe the formation of a trigonal prismatic cage, utilizing 2-formyl-1,8-naphthyridine subcomponents to bind pairs of silver(I) ions in close proximity. This cage is the first example of a new class of subcomponent self-assembled polyhedral structures having bimetallic vertices, as opposed to the single metal centers that typically serve as structural elements within such cages. Our new cage self-assembles around a pair of anionic templates, which are shown by crystallographic and solution-phase data to bind within the central cavity of the structure. Many different anions serve as competent templates and guests. Elongated dianions, such as the strong oxidizing agent peroxysulfate, also serve to template and bind within the cavity of the prism. The principle of using subcomponents that have more than one spatially close, but nonchelating, binding site may thus allow access to other higher-order structures with multimetallic vertices.European Research Council (695009) and the UK Engineering and Physical Sciences Re‐ search Council (EPSRC, EP/P027067/1). European Union's Horizon 2020 research and innovation program, Marie Sklodowska‐Curie Grant (642192)

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