Rational Design of Iron Spin-Crossover Complexes Using Heteroscorpionate Chelates.

The optical, structural, and magnetic properties of iron(II,III) sandwich complexes, Fe(Tp')2n+ (Tp' = bis(3,5-dimethylpyrazolyl)benzotriazolylborate), are described. The intensely colored FeII(Tp')2 (orange) and FeIII(Tp')2+ (purple) show strong MLCT bands. Geometric isomerism for M(Tp')2 is established crystallographically in the racemate of chiral cis-Fe(Tp')2. For the first time, paramagnetic 11B NMR describes solution-phase low-spin (LS, S = 0) to high-spin (HS, S = 2) crossover behavior in Fe(Tp')2. Thermochemical parameters for solution-phase SCO of Fe(Tp')2 demonstrate the endothermic LS to HS conversion and entropic preference of the HS state. Entropy changes for both Fe(Tp')2 isomers are significantly larger than for the majority of iron scorpionate SCO systems. Solid-state magnetic and thermochemical measurements show cis-Fe(Tp')2 to be thermally stable up to 520 K, allowing experimental investigation of a solid-state SCO magnetic hysteresis of over 45 K. A large solution vs solid-state SCO difference was observed: cis-Fe(Tp')2 shows Tc ≈ 270 K (solution) and Tc ≈ 385 K (solid), with the remarkably wide ΔTc ≈ 115 K; trans-Fe(Tp')2 shows Tc ≈ 278 K (solution) and Tc ≈ 372 K (solid). Solid-state Tc values are among the highest seen for iron(II) molecular systems. The large solution/solid ΔTc difference is explained by "anchoring" intermolecular interactions in the solid state that prevent thermal expansion of the LS iron(II) coordination sphere in its transition to the HS state. DFT calculations, validated against LS cis-Fe(Tp')2 crystallography and LS to HS SCO thermochemical parameters, demonstrate the role the benzotriazole rings play in its structural and optical properties. The Lewis basicity of M(Tp')2 is shown with the structural characterization of the air-stable tin(II) adduct [cis-Fe(Tp')2-SnCl2]; tin(II) coordination does not alter the iron(II) spin state. The Tp' chelate adds functionality (asymmetry, chirality, chemical reactivity) to the array of iron SCO materials for potential incorporation into nanoscale magnetic switches and spintronic devices.

Hydration and Charge-Transfer Effects of Alkaline Earth Metal Ions Binding to a Carboxylate Anion, Phosphate Anion, and Guanine Nucleobase.

To investigate the ability of alkaline earth metal ions to tune ion-mediated DNA adsorption, hydrated Mg2+, Ca2+, Sr2+, and Ba2+ ions bound to a carboxylate anion, phosphate anion, and guanine nucleobase were modeled using density functional theory (DFT) and a combined explicit and continuum solvent model. The large first solvation shell of Ba2+ requires a larger solute cavity defined by a solvent-accessible surface, which is used to model all hydrated ions. Alkaline earth metal ions bind indirectly or directly to each binding site. DFT binding energies decrease with increasing ion size, which is likely due to ion size and hydration structure, rather than quantum effects such as charge transfer. However, charge transfer explains weaker ion binding to guanine compared to phosphate or carboxylate. Overall, carboxylate and phosphate anions are expected to compete equally for hydrated Mg2+, Ca2+, Sr2+, and Ba2+ ions and larger alkaline earth metal ions may induce weaker ion-mediated adsorption. The ion size and hydration structure of alkaline earth metal ions may effectively tune ion-mediated adsorption processes, such as DNA adsorption to functionalized surfaces.

The data-driven future of high-energy-density physics.

High-energy-density physics is the field of physics concerned with studying matter at extremely high temperatures and densities. Such conditions produce highly nonlinear plasmas, in which several phenomena that can normally be treated independently of one another become strongly coupled. The study of these plasmas is important for our understanding of astrophysics, nuclear fusion and fundamental physics-however, the nonlinearities and strong couplings present in these extreme physical systems makes them very difficult to understand theoretically or to optimize experimentally. Here we argue that machine learning models and data-driven methods are in the process of reshaping our exploration of these extreme systems that have hitherto proved far too nonlinear for human researchers. From a fundamental perspective, our understanding can be improved by the way in which machine learning models can rapidly discover complex interactions in large datasets. From a practical point of view, the newest generation of extreme physics facilities can perform experiments multiple times a second (as opposed to approximately daily), thus moving away from human-based control towards automatic control based on real-time interpretation of diagnostic data and updates of the physics model. To make the most of these emerging opportunities, we suggest proposals for the community in terms of research design, training, best practice and support for synthetic diagnostics and data analysis.

A measurement of the equation of state of carbon envelopes of white dwarfs.

White dwarfs represent the final state of evolution for most stars1-3. Certain classes of white dwarfs pulsate4,5, leading to observable brightness variations, and analysis of these variations with theoretical stellar models probes their internal structure. Modelling of these pulsating stars provides stringent tests of white dwarf models and a detailed picture of the outcome of the late stages of stellar evolution6. However, the high-energy-density states that exist in white dwarfs are extremely difficult to reach and to measure in the laboratory, so theoretical predictions are largely untested at these conditions. Here we report measurements of the relationship between pressure and density along the principal shock Hugoniot (equations describing the state of the sample material before and after the passage of the shock derived from conservation laws) of hydrocarbon to within five per cent. The observed maximum compressibility is consistent with theoretical models that include detailed electronic structure. This is relevant for the equation of state of matter at pressures ranging from 100 million to 450 million atmospheres, where the understanding of white dwarf physics is sensitive to the equation of state and where models differ considerably. The measurements test these equation-of-state relations that are used in the modelling of white dwarfs and inertial confinement fusion experiments7,8, and we predict an increase in compressibility due to ionization of the inner-core orbitals of carbon. We also find that a detailed treatment of the electronic structure and the electron degeneracy pressure is required to capture the measured shape of the pressure-density evolution for hydrocarbon before peak compression. Our results illuminate the equation of state of the white dwarf envelope (the region surrounding the stellar core that contains partially ionized and partially degenerate non-ideal plasmas), which is a weak link in the constitutive physics informing the structure and evolution of white dwarf stars9.

Molecular dynamics simulations of alkaline earth metal ions binding to DNA reveal ion size and hydration effects.

The identity of metal ions surrounding DNA is key to its biological function and materials applications. In this work, we compare atomistic molecular dynamics simulations of double strand DNA (dsDNA) with four alkaline earth metal ions (Mg2+, Ca2+, Sr2+, and Ba2+) to elucidate the physical interactions that govern DNA-ion binding. Simulations accurately model the ion-phosphate distance of Mg2+ and reproduce ion counting experiments for Ca2+, Sr2+, and Ba2+. Our analysis shows that alkaline earth metal ions prefer to bind at the phosphate backbone compared to the major groove and negligible binding occurs in the minor groove. Larger alkaline earth metal ions with variable first solvation shells (Ca2+, Sr2+, and Ba2+) show both direct and indirect binding, where indirect binding increases with ion size. Mg2+ does not fit this trend because the strength of its first solvation shell predicts indirect binding only. Ions bound to the phosphate backbone form fewer contacts per ion compared to the major groove. Within the major groove, metal ions preferentially bind to guanine-cystosine base pairs and form simultaneous contacts with the N7 and O6 atoms of guanine. Overall, we find that the interplay among ion size, DNA-ion interaction, and the size and flexibility of the first solvation shell are key to predicting how alkaline earth metal ions interact with DNA.

Bistetrazine-Cyanines as Double-Clicking Fluorogenic Two-Point Binder or Crosslinker Probes.

Fluorogenic probes can be used to minimize the background fluorescence of unreacted and nonspecifically adsorbed reagents. The preceding years have brought substantial developments in the design and synthesis of bioorthogonally applicable fluorogenic systems mainly based on the quenching effects of azide and tetrazine moieties. The modulation power exerted by these bioorthogonal motifs typically becomes less efficient on more conjugated systems; that is, on probes with redshifted emission wavelength. To reach efficient quenching, that is, fluorogenicity, even in the red range of the spectrum, we present the synthesis, fluorogenic, and conjugation characterization of bistetrazine-cyanine probes with emission maxima between 600 and 620 nm. The probes can bind to genetically altered proteins harboring an 11-amino acid peptide tag with two appending cyclooctyne motifs. Moreover, we also demonstrate the use of these bistetrazines as fluorogenic, covalent cross-linkers between monocyclooctynylated proteins.