Characterizing X-Ray and Solution State Conformations for a Model Qubit System: {CrNi} Ring Rotaxanes on a Mixed Metal Triangle.

The synthesis of a series of [4]rotaxanes, each consisting of three [2]rotaxanes joined via a central {CrNi} triangular linker, is reported. The resultant four [4]rotaxanes were characterized by single crystal X-ray diffraction and electron paramagnetic resonance (EPR) spectroscopy. Orientation-selective 4-pulse double electron-electron resonance (DEER) measurements between the three {CrNi} rings incorporated in each [4]rotaxane reveal that each system is conformationally fluxional in solution, with the most abundant conformations found to differ significantly from the crystal structure geometry for each compound.

IBODIPY as a new photoswitchable spin label for light-induced pulsed EPR dipolar spectroscopy exploiting magnetophotoselection.

Electron paramagnetic resonance (EPR) pulsed dipolar spectroscopy (PDS) using triplet states of organic molecules is a growing area of research due to the favourable properties that these transient states may afford over stable spin centers, such as switchability, increased signal intensity when the triplet is formed in a non-Boltzmann distribution and the triplet signal is used for detection, and high orientation selection, when the triplet signal is probed by microwave pulses. This arises due to the large spectral width at low fields, a result of the large zero field splitting, and limited bandwidth of microwave pulses used. Here we propose the triplet state of a substituted BODIPY moiety as a spin label in light induced PDS, coupled to a nitroxide, in a model peptide with a rigid structure.

Weak Exchange Interactions in Multispin Systems: EPR Studies of Metalloporphyrins Decorated with {CrNi} Rings.

Both metalloporphyrins and heterometallic {CrNi} rings are of significant research interest due to their proposed roles in quantum information processing devices. In this study, we present a series of complexes in which [CrNiF(Etglu)(OCBu)] (-EtgluH = -ethyl-dglucamine) heterometallic rings are coordinated to metalloporphyrin linkers: the symmetric [M(TPyP)] for M = Cu, VO, and HTPyP = 5,10,15,20-tetra(4-pyridyl)porphyrin; and the asymmetric [{VO}(TrPPyP)] for H(TrPPyP) = 5,10,15-(triphenyl)-20-(4-pyridyl)porphyrin. The magnetic interactions present in these complexes are unraveled using the continuous wave (CW) electron paramagnetic resonance (EPR) technique.

Determining and controlling conformational information from orientationally selective light-induced triplet-triplet electron resonance spectroscopy for a set of bis-porphyrin rulers.

We recently reported a new technique, light-induced triplet-triplet electron resonance (LITTER) spectroscopy, which allows quantification of the dipolar interaction between the photogenerated triplet states of two chromophores. Here we carry out a systematic LITTER study, considering orientation selection by the detection pulses, of a series of bis-porphyrin model peptides with different porphyrin-porphyrin distances and relative orientations. Orientation-dependent analysis of the dipolar datasets yields conformational information of the molecules in frozen solution which is in good agreement with density functional theory predictions.

Simple and effective sample illumination for electron paramagnetic resonance.

Illumination into an electron paramagnetic resonance (EPR) spectrometer is commonly carried out through the optical window, perpendicular to the sample and magnetic field. Here we show that significant improvements can be obtained by using the walls of the EPR tube as a light guide, with the light scattered only around the sample-containing area.

Title: experimental realisation of multi-qubit gates using electron paramagnetic resonance.

Quantum information processing promises to revolutionise computing; quantum algorithms have been discovered that address common tasks significantly more efficiently than their classical counterparts. For a physical system to be a viable quantum computer it must be possible to initialise its quantum state, to realise a set of universal quantum logic gates, including at least one multi-qubit gate, and to make measurements of qubit states. Molecular Electron Spin Qubits (MESQs) have been proposed to fulfil these criteria, as their bottom-up synthesis should facilitate tuning properties as desired and the reproducible production of multi-MESQ structures.

Direct Comparison between Förster Resonance Energy Transfer and Light-Induced Triplet-Triplet Electron Resonance Spectroscopy.

To carry out reliable and comprehensive structural investigations, the exploitation of different complementary techniques is required. Here, we report that dual triplet-spin/fluorescent labels enable the first parallel distance measurements by electron spin resonance (ESR) and Förster resonance energy transfer (FRET) on exactly the same molecules with orthogonal chromophores, allowing for direct comparison. An improved light-induced triplet-triplet electron resonance method with 2-color excitation is used, improving the signal-to-noise ratio of the data and yielding a distance distribution that provides greater insight than the single distance resulting from FRET.

Hexanuclear Ln L Complex Formation by Using an Unsymmetric Ligand.

Multinuclear, self-assembled lanthanide complexes present clear opportunities as sensors and imaging agents. Despite the widely acknowledged potential of this class of supramolecule, synthetic and characterization challenges continue to limit systematic studies into their self-assembly restricting the number and variety of lanthanide architectures reported relative to their transition metal counterparts. Here we present the first study evaluating the effect of ligand backbone symmetry on multinuclear lanthanide complex self-assembly.

Fullerene Complexation in a Hydrogen-Bonded Porphyrin Receptor via Induced-Fit: Cooperative Action of Tautomerization and C-H···π Interactions.

A supramolecular chiral hydrogen-bonded tetrameric aggregate possessing a large cavity and tetraarylporphyrin substituents was assembled using alternating 4H- and 2H-bonds between ureidopyrimidinone and isocytosine units, respectively. The aggregation mode was rationally shifted from social to narcissistic self-sorting by changing urea substituent size only. The H-bonded tetramer forms a strong complex with C guest, at the same time undergoing remarkable structural changes.

Magnetic and Electronic Structural Properties of the S State of Nature's Water Oxidizing Complex: A Combined Study in ELDOR-Detected Nuclear Magnetic Resonance Spectral Simulation and Broken-Symmetry Density Functional Theory.

ELDOR-detected nuclear magnetic resonance (EDNMR) spectral simulations combined with broken-symmetry density functional theory (BS-DFT) calculations are used to obtain and to assign the Mn hyperfine coupling constants (hfcs) for modified forms of the water oxidizing complex in the penultimate S state of the water oxidation cycle. The study shows that an open cubane form of the core MnCaO cluster explains the magnetic properties of the dominant = 3 species in all cases studied experimentally with no need to invoke a closed cubane intermediate possessing a distorted pentacoordinate Mn ion as recently suggested. EDNMR simulations found that both the experimental bandwidth and multinuclear transitions may alter relative EDNMR peak intensities, potentially leading to incorrect assignment of hfcs.

Modelling Conformational Flexibility in a Spectrally Addressable Molecular Multi-Qubit Model System.

Dipolar coupled multi-spin systems have the potential to be used as molecular qubits. Herein we report the synthesis of a molecular multi-qubit model system with three individually addressable, weakly interacting, spin centres of differing g-values. We use pulsed Electron Paramagnetic Resonance (EPR) techniques to characterise and separately address the individual electron spin qubits; Cu , Cr Ni ring and a nitroxide, to determine the strength of the inter-qubit dipolar interaction.

Light-induced pulsed dipolar EPR spectroscopy for distance and orientation analysis.

Measuring distances in biology at the molecular level is of great importance for understanding the structure and function of proteins, nucleic acids and other biological molecules and their complexes. Pulsed Dipolar Spectroscopy (PDS) offers advantages with respect to other methods as it is uniquely sensitive and specific to electronic spin centers and allows measurements in near-native conditions, comprising the in-cell environment. PDS methods measure the electron spin-spin dipolar interaction, therefore they require the presence of at least two paramagnetic centers, which are often stable radicals.

Lessons for Uptake and Engagement of a Smartphone App (SURE Recovery) for People in Recovery From Alcohol and Other Drug Problems: Interview Study of App Users.

Background: Mobile health apps promoting health and well-being have substantial potential but low uptake and engagement. Barriers common to addiction treatment app uptake and engagement include poor access to mobile technology, Wi-Fi, or mobile data, plus low motivation among non-treatment-seeking users to cut down or quit. Working with people who used substances, we had previously designed and published an app to support recovery from alcohol and other drug problems.

Solvent-Dependent Reactivity and Photochemistry of Dinuclear and Mononuclear Platinum(IV) Azido Triazaolato Complexes.

Reaction between the platinum(IV) azido complex ,-[Pt(py)(N)(OH)] () and 1,4-diphenyl-2-butyne-1,4-dione in MeCN produces the intermediate peroxide-bridged dimeric platinum(IV) azido triazolato species (), which has been characterised by X-ray crystallography. However, if the reaction between and is conducted in MeOH it results in decomposition. Over time in MeCN, dimer () converts into mononuclear complexes ,-[Pt(py)(N)(triazole)(OH)] (/), which are in dynamic exchange.

Orientation-Selective and Frequency-Correlated Light-Induced Pulsed Dipolar Spectroscopy.

We explore the potential of orientation-resolved pulsed dipolar spectroscopy (PDS) in light-induced versions of the experiment. The use of triplets as spin-active moieties for PDS offers an attractive tool for studying biochemical systems containing optically active cofactors. Cofactors are often rigidly bound within the protein structure, providing an accurate positional marker.

Light-Induced Triplet-Triplet Electron Resonance Spectroscopy.

We present a new technique, light-induced triplet-triplet electron resonance spectroscopy (LITTER), which measures the dipolar interaction between two photoexcited triplet states, enabling both the distance and angular distributions between the two triplet moieties to be determined on a nanometer scale. This is demonstrated for a model bis-porphyrin peptide that renders dipolar traces with strong orientation selection effects. Using simulations and density functional theory calculations, we extract distance distributions and relative orientations of the porphyrin moieties, allowing the dominant conformation of the peptide in a frozen solution to be identified.

Conformational Flexibility of Hybrid [3]- and [4]-Rotaxanes.

The synthesis, structures, and properties of [4]- and [3]-rotaxane complexes are reported where [2]-rotaxanes, formed from heterometallic {CrNi} rings, are bound to a fluoride-centered {CrNi} triangle. The compounds have been characterized by single-crystal X-ray diffraction and have the formulas [CrNi(F)(OCBu)]{(H)[CrNiF(OCBu)]} () and [CrNi(F)(OCBu)(THF)]{(H)[CrNiF(OCBu)]} (), where = py-CHCHNHCHCHSCH. The [4]-rotaxane is an isosceles triangle of three [2]-rotaxanes bound to the central triangle while the [3]-rotaxane contains only two [2]-rotaxanes bound to the central triangle.

A visible-light photoactivatable di-nuclear Pt triazolato azido complex.

A novel PtIV triazolato azido complex [3]-[N1,N3] has been synthesised via a strain-promoted double-click reaction (SPDC) between a PtIV azido complex (1) and the Sondheimer diyne (2). Photoactivation of [3]-[N1,N3] with visible light (452 nm) in the presence of 5'-guanosine monophosphate (5'-GMP) produced both PtIV and PtII 5'-GMP species; EPR spectroscopy confirmed the production of both azidyl and hydroxyl radicals. Spin-trapping of photogenerated radicals - particularly hydroxyl radicals - was significantly reduced in the presence of 5'-GMP.

An NMR and MD study of complexes of bacteriophage lambda lysozyme with tetra- and hexa-N-acetylchitohexaose.

The X-ray structure of lysozyme from bacteriophage lambda (λ lysozyme) in complex with the inhibitor hexa-N-acetylchitohexaose (NAG6) (PDB: 3D3D) has been reported previously showing sugar units from two molecules of NAG6 bound in the active site. One NAG6 is bound with four sugar units in the ABCD sites and the other with two sugar units in the E'F' sites potentially representing the cleavage reaction products; each NAG6 cross links two neighboring λ lysozyme molecules. Here we use NMR and MD simulations to study the interaction of λ lysozyme with the inhibitors NAG4 and NAG6 in solution.

Binding of tetracycline to its aptamer determined by 2D-correlated Mn hyperfine spectroscopy.

The tetracycline-binding RNA aptamer (TC-aptamer) binds its cognate ligand the antibiotic tetracycline (TC) via a Mg or Mn ion with high affinity at high divalent metal ion concentrations (K=800pM, ⩾10 mM). These concentrations lie above the physiological divalent metal ion concentration of ca. 1 mM and it is known from literature, that the binding affinity decreases upon decreasing the divalent metal ion concentration.

A novel Pt(iv) mono azido mono triazolato complex evolves azidyl radicals following irradiation with visible light.

The platinum(iv) azido complex trans,trans,trans-[PtIV(N3)2(OH)2(py)2] (1) undergoes cycloaddition with 1,4-diphenyl-2-butyne-1,4-dione (2) under mild, catalyst-free conditions, affording a number of mono and bis click products. The major mono click product (3) exists in MeCN as an equilibrium mixture between two species; 3a and 3b rapidly interconvert through nucleophilic attack of the axial Pt-OH group at the adjacent Ph-CO group. The kinetic and thermodynamic parameters for this interconversion have been measured by selective saturation-transfer NMR spectroscopic experiments and are consistent with cyclisation at the Pt centre.

Light-Induced Pulsed EPR Dipolar Spectroscopy on a Paradigmatic Hemeprotein.

Light-induced pulsed EPR dipolar spectroscopic methods allow the determination of nanometer distances between paramagnetic sites. Here we employ orthogonal spin labels, a chromophore triplet state and a stable radical, to carry out distance measurements in singly nitroxide-labeled human neuroglobin. We demonstrate that Zn-substitution of neuroglobin, to populate the Zn(II) protoporphyrin IX triplet state, makes it possible to perform light-induced pulsed dipolar experiments on hemeproteins, extending the use of light-induced dipolar spectroscopy to this large class of metalloproteins.

A Structural Model of a P450-Ferredoxin Complex from Orientation-Selective Double Electron-Electron Resonance Spectroscopy.

Cytochrome P450 (CYP) monooxygenases catalyze the oxidation of chemically inert carbon-hydrogen bonds in diverse endogenous and exogenous organic compounds by atmospheric oxygen. This C-H bond oxy-functionalization activity has huge potential in biotechnological applications. Class I CYPs receive the two electrons required for oxygen activation from NAD(P)H via a ferredoxin reductase and ferredoxin.