Heterometallic Titanium-Organic Frameworks as Dual Metal Catalysts for Synergistic Non-Buffered Hydrolysis of Nerve Agent Simulants

Heterometallic metal-organic frameworks (MOFs) can offer important advantages over their homometallic counterparts to enable targeted modification of their adsorption, structural response, electronic structure, or chemical reactivity. However, controlling metal distribution in these solids still remains a challenge. The family of mesoporous titanium-organic frameworks, MUV-101(M), displays heterometallic TiM2 nodes assembled from direct reaction of Ti(IV) and M(II) salts. We use the degradation of nerve agent simulants to demonstrate that only TiFe2 nodes are capable of catalytic degradation in non-buffered conditions. By using an integrative experimental-computational approach, we rationalize how the two metals influence each other, in this case, for a synergistic mechanism reminiscent of bimetallic enzymes. Our results highlight the importance of controlling metal distribution at an atomic level to span the interest of heterometallic MOFs to a broad scope of cascade or tandem reactions. Summary Mixed-metal or heterometallic metal-organic frameworks (MOFs) are gaining importance as a route to produce materials with increasing chemical and functional complexities. We report a family of heterometallic titanium frameworks, MUV-101(M), and use them to exemplify the advantages of controlling metal distribution across the framework in heterogeneous catalysis by exploring their activity toward the degradation of a nerve agent simulant of Sarin gas. MUV-101(Fe) is the only pristine MOF capable of catalytic degradation of diisopropyl-fluorophosphate (DIFP) in non-buffered aqueous media. This activity cannot be explained only by the association of two metals, but to their synergistic cooperation, to create a whole that is more efficient than the simple sum of its parts. Our simulations suggest a dual-metal mechanism reminiscent of bimetallic enzymes, where the combination of Ti(IV) Lewis acid and Fe(III)–OH Brönsted base sites leads to a lower energy barrier for more efficient degradation of DIFP in absence of a base.Financial support for this work was provided by the Marie Skłodowska-Curie Global Fellowships (749359-EnanSET, N.M.P) within the European Union research and innovation framework programme (2014-2020

Matching microscopic and macroscopic responses in glasses

We first reproduce on the Janus and Janus II computers a milestone experiment that measures the spin-glass coherence length through the lowering of free-energy barriers induced by the Zeeman effect. Secondly we determine the scaling behavior that allows a quantitative analysis of a new experiment reported in the companion Letter [S. Guchhait and R. Orbach, Phys. Rev. Lett. 118, 157203 (2017)]. The value of the coherence length estimated through the analysis of microscopic correlation functions turns out to be quantitatively consistent with its measurement through macroscopic response functions. Further, non-linear susceptibilities, recently measured in glass-forming liquids, scale as powers of the same microscopic length.Comment: 6 pages, 4 figure

The Mpemba effect in spin glasses is a persistent memory effect

The Mpemba effect occurs when a hot system cools faster than an initially colder one, when both are refrigerated in the same thermal reservoir. Using the custom built supercomputer Janus II, we study the Mpemba effect in spin glasses and show that it is a non-equilibrium process, governed by the coherence length \xi of the system. The effect occurs when the bath temperature lies in the glassy phase, but it is not necessary for the thermal protocol to cross the critical temperature. In fact, the Mpemba effect follows from a strong relationship between the internal energy and \xi that turns out to be a sure-tell sign of being in the glassy phase. Thus, the Mpemba effect presents itself as an intriguing new avenue for the experimental study of the coherence length in supercooled liquids and other glass formers.Comment: Version accepted for publication in PNAS. 6 pages, 7 figure

The three dimensional Ising spin glass in an external magnetic field: the role of the silent majority

We perform equilibrium parallel-tempering simulations of the 3D Ising Edwards-Anderson spin glass in a field. A traditional analysis shows no signs of a phase transition. Yet, we encounter dramatic fluctuations in the behaviour of the model: Averages over all the data only describe the behaviour of a small fraction of it. Therefore we develop a new approach to study the equilibrium behaviour of the system, by classifying the measurements as a function of a conditioning variate. We propose a finite-size scaling analysis based on the probability distribution function of the conditioning variate, which may accelerate the convergence to the thermodynamic limit. In this way, we find a non-trivial spectrum of behaviours, where a part of the measurements behaves as the average, while the majority of them shows signs of scale invariance. As a result, we can estimate the temperature interval where the phase transition in a field ought to lie, if it exists. Although this would-be critical regime is unreachable with present resources, the numerical challenge is finally well posed.Comment: 42 pages, 19 figures. Minor changes and added figure (results unchanged

Nature of the spin-glass phase at experimental length scales

We present a massive equilibrium simulation of the three-dimensional Ising spin glass at low temperatures. The Janus special-purpose computer has allowed us to equilibrate, using parallel tempering, L=32 lattices down to T=0.64 Tc. We demonstrate the relevance of equilibrium finite-size simulations to understand experimental non-equilibrium spin glasses in the thermodynamical limit by establishing a time-length dictionary. We conclude that non-equilibrium experiments performed on a time scale of one hour can be matched with equilibrium results on L=110 lattices. A detailed investigation of the probability distribution functions of the spin and link overlap, as well as of their correlation functions, shows that Replica Symmetry Breaking is the appropriate theoretical framework for the physically relevant length scales. Besides, we improve over existing methodologies to ensure equilibration in parallel tempering simulations.Comment: 48 pages, 19 postscript figures, 9 tables. Version accepted for publication in the Journal of Statistical Mechanic

Critical parameters of the three-dimensional Ising spin glass

We report a high-precision finite-size scaling study of the critical behavior of the three-dimensional Ising Edwards-Anderson model (the Ising spin glass). We have thermalized lattices up to L=40 using the Janus dedicated computer. Our analysis takes into account leading-order corrections to scaling. We obtain Tc = 1.1019(29) for the critical temperature, \nu = 2.562(42) for the thermal exponent, \eta = -0.3900(36) for the anomalous dimension and \omega = 1.12(10) for the exponent of the leading corrections to scaling. Standard (hyper)scaling relations yield \alpha = -5.69(13), \beta = 0.782(10) and \gamma = 6.13(11). We also compute several universal quantities at Tc.Comment: 9 pages, 5 figure

Circular Polarization in Pulsar Integrated Profiles: Updates

We update the systematic studies of circular polarization in integrated pulse profiles by Han et al (1998). Data of circular polarization profiles are compiled. Sense reversals can occur in core or cone components, or near the intersection between components. The correlation between the sense of circular polarization and the sense of position angle variation for conal-double pulsars is confirmed with a much large database. Circular polarization of some pulsars has clear changes with frequency. Circular polarization of millisecond pulsars is marginally different from that of normal pulsars.Comment: 10 pages, 6 figures, accepted and will be published soon by Chinese Journal of Astronomy and Astrophysics (ChJAA

Thermodynamic glass transition in a spin glass without time-reversal symmetry

Spin glasses are a longstanding model for the sluggish dynamics that appears at the glass transition. However, spin glasses differ from structural glasses for a crucial feature: they enjoy a time reversal symmetry. This symmetry can be broken by applying an external magnetic field, but embarrassingly little is known about the critical behaviour of a spin glass in a field. In this context, the space dimension is crucial. Simulations are easier to interpret in a large number of dimensions, but one must work below the upper critical dimension (i.e., in d<6) in order for results to have relevance for experiments. Here we show conclusive evidence for the presence of a phase transition in a four-dimensional spin glass in a field. Two ingredients were crucial for this achievement: massive numerical simulations were carried out on the Janus special-purpose computer, and a new and powerful finite-size scaling method.Comment: 10 pages, 6 figure

Critical Behavior of Three-Dimensional Disordered Potts Models with Many States

We study the 3D Disordered Potts Model with p=5 and p=6. Our numerical simulations (that severely slow down for increasing p) detect a very clear spin glass phase transition. We evaluate the critical exponents and the critical value of the temperature, and we use known results at lower $p$ values to discuss how they evolve for increasing p. We do not find any sign of the presence of a transition to a ferromagnetic regime.Comment: 9 pages and 9 Postscript figures. Final version published in J. Stat. Mec

Stars and dark matter in the spiral gravitational lens 2237+0305

We construct a mass model for the spiral lens galaxy 2237+0305, at redshift z_l=0.04, based on gravitational-lensing constraints, HI rotation, and new stellar-kinematic information, based on data taken with the ESI spectrograph on the 10m Keck-II Telescope. High resolution rotation curves and velocity dispersion profiles along two perpendicular directions, close to the major and minor axes of the lens galaxy, were obtained by fitting the Mgb-Fe absorption line region. The stellar rotation curve rises slowly and flattens at r~1.5" (~1.1 kpc). The velocity dispersion profile is approximately flat. A combination of photometric, kinematic and lensing information is used to construct a mass model for the four major mass components of the system -- the dark matter halo, disc, bulge, and bar. The best-fitting solution has a dark matter halo with a logarithmic inner density slope of gamma=0.9+/-0.3 for rho_DM propto r^-gamma, a bulge with M/L_B=6.6+/-0.3 Upsilon_odot, and a disc with M/L_B =1.2+/-0.3 Upsilon_odot, in agreement with measurements of late-type spirals. The bulge dominates support in the inner regions where the multiple images are located and is therefore tightly constrained by the observations. The disc is sub-maximal and contributes 45+/-11 per cent of the rotational support of the galaxy at 2.2r_d. The halo mass is (2.0+/-0.6) x 10^12 M_odot, and the stellar to virial mass ratio is 7.0+/-2.3 per cent, consistent with typical galaxies of the same mass.Comment: 14 pages, 6 figures, MNRAS, in pres