Controlling Th isomeric state population in a VUV transparent crystal.

The radioisotope thorium-229 (Th) is renowned for its extraordinarily low-energy, long-lived nuclear first-excited state. This isomeric state can be excited by vacuum ultraviolet (VUV) lasers and Th has been proposed as a reference transition for ultra-precise nuclear clocks. To assess the feasibility and performance of the nuclear clock concept, time-controlled excitation and depopulation of the Th isomer are imperative.

Nuclear Resonance Vibrational Spectroscopy Definition of Peroxy Intermediates in Catechol Dioxygenases: Factors that Determine Extra- versus Intradiol Cleavage.

The extradiol dioxygenases (EDOs) and intradiol dioxygenases (IDOs) are nonheme iron enzymes that catalyze the oxidative aromatic ring cleavage of catechol substrates, playing an essential role in the carbon cycle. The EDOs and IDOs utilize very different Fe and Fe active sites to catalyze the regiospecificity in their catechol ring cleavage products. The factors governing this difference in cleavage have remained undefined.

Nuclear Resonance Vibrational Spectroscopic Definition of the Fe(IV) Intermediate Q in Methane Monooxygenase and Its Reactivity.

Methanotrophic bacteria utilize the nonheme diiron enzyme soluble methane monooxygenase (sMMO) to convert methane to methanol in the first step of their metabolic cycle under copper-limiting conditions. The structure of the sMMO Fe(IV) intermediate Q responsible for activating the inert C-H bond of methane (BDE = 104 kcal/mol) remains controversial, with recent studies suggesting both "open" and "closed" core geometries for its active site. In this study, we employ nuclear resonance vibrational spectroscopy (NRVS) to probe the geometric and electronic structure of intermediate Q at cryogenic temperatures.

Direct coordination of pterin to Fe enables neurotransmitter biosynthesis in the pterin-dependent hydroxylases.

The pterin-dependent nonheme iron enzymes hydroxylate aromatic amino acids to perform the biosynthesis of neurotransmitters to maintain proper brain function. These enzymes activate oxygen using a pterin cofactor and an aromatic amino acid substrate bound to the Fe active site to form a highly reactive Fe = O species that initiates substrate oxidation. In this study, using tryptophan hydroxylase, we have kinetically generated a pre-Fe = O intermediate and characterized its structure as a Fe-peroxy-pterin species using absorption, Mössbauer, resonance Raman, and nuclear resonance vibrational spectroscopies.

Absolute X-ray energy measurement using a high-accuracy angle encoder.

This paper presents an absolute X-ray photon energy measurement method that uses a Bond diffractometer. The proposed system enables the prompt and rapid in situ measurement of photon energies over a wide energy range. The diffractometer uses a reference silicon single-crystal plate and a highly accurate angle encoder called SelfA.

Evolution of Superconductivity with Sr-Deficiency in Antiperovskite Oxide SrSnO.

Bulk superconductivity was recently reported in the antiperovskite oxide SrSnO, with a possibility of hosting topological superconductivity. We investigated the evolution of superconducting properties such as the transition temperature T and the size of the diamagnetic signal, as well as normal-state electronic and crystalline properties, with varying the nominal Sr deficiency x. Polycrystalline SrSnO was obtained up to x = 0:6 with a small amount of SrO impurities.

Superconducting transition temperatures in the electronic and magnetic phase diagrams of SrVFeAsO , a superconductor.

We elucidate the magnetic phases and superconducting (SC) transition temperatures (T ) in SrVFeAsO (21113V), an iron-based superconductor with a thick-blocking layer fabricated from a perovskite-related transition metal oxide. At low temperatures (T  <  37.1 K), 21113V exhibited a SC phase in the range 0.

NRVS Studies of the Peroxide Shunt Intermediate in a Rieske Dioxygenase and Its Relation to the Native Fe O Reaction.

The Rieske dioxygenases are a major subclass of mononuclear nonheme iron enzymes that play an important role in bioremediation. Recently, a high-spin Fe-(hydro)peroxy intermediate (BZDOp) has been trapped in the peroxide shunt reaction of benzoate 1,2-dioxygenase. Defining the structure of this intermediate is essential to understanding the reactivity of these enzymes.

Peroxide Activation for Electrophilic Reactivity by the Binuclear Non-heme Iron Enzyme AurF.

Binuclear non-heme iron enzymes activate O for diverse chemistries that include oxygenation of organic substrates and hydrogen atom abstraction. This process often involves the formation of peroxo-bridged biferric intermediates, only some of which can perform electrophilic reactions. To elucidate the geometric and electronic structural requirements to activate peroxo reactivity, the active peroxo intermediate in 4-aminobenzoate N-oxygenase (AurF) has been characterized spectroscopically and computationally.

61Ni synchrotron radiation-based Mössbauer spectroscopy of nickel-based nanoparticles with hexagonal structure.

We measured the synchrotron-radiation (SR)-based Mössbauer spectra of Ni-based nanoparticles with a hexagonal structure that were synthesised by chemical reduction. To obtain Mössbauer spectra of the nanoparticles without (61)Ni enrichment, we developed a measurement system for (61)Ni SR-based Mössbauer absorption spectroscopy without X-ray windows between the (61)Ni84V16 standard energy alloy and detector. The counting rate of the (61)Ni nuclear resonant scattering in the system was enhanced by the detection of internal conversion electrons and the close proximity between the energy standard and the detector.

Predominance of covalency in water-vapor-responsive MMX-type chain complexes revealed by (129)I Mössbauer spectroscopy.

(129)I Mössbauer spectroscopy was applied to water-vapor-responsive MMX-type quasi-one-dimensional iodide-bridged Pt complexes (MMX chains) in order to investigate their electronic state quantitatively. Two sets of octuplets observed in K2(H3NC3H6NH3)[Pt2(pop)4I]·4H2O (2·4H2O) and one octuplet observed in K2(cis-H3NCH2CH=CHCH2NH3)[Pt2(pop)4I]·4H2O (1·4H2O) and dehydrated complexes (1 and 2) indicate a unique alternating charge-polarization + charge-density-wave (ACP + CDW) electronic state and a charge-density-wave (CDW) electronic state, respectively. These spectra correspond to their crystal structure and the change of electronic states upon dehydration.

A porous coordination polymer with a reactive diiron paddlewheel unit.

A pillared-layer type porous coordination polymer containing a diiron paddlewheel unit has been synthesized and exhibits permanent porosity as confirmed by gas sorption analysis.

Geometric and electronic structure of the Mn(IV)Fe(III) cofactor in class Ic ribonucleotide reductase: correlation to the class Ia binuclear non-heme iron enzyme.

The class Ic ribonucleotide reductase (RNR) from Chlamydia trachomatis (Ct) utilizes a Mn/Fe heterobinuclear cofactor, rather than the Fe/Fe cofactor found in the β (R2) subunit of the class Ia enzymes, to react with O2. This reaction produces a stable Mn(IV)Fe(III) cofactor that initiates a radical, which transfers to the adjacent α (R1) subunit and reacts with the substrate. We have studied the Mn(IV)Fe(III) cofactor using nuclear resonance vibrational spectroscopy (NRVS) and absorption (Abs)/circular dichroism (CD)/magnetic CD (MCD)/variable temperature, variable field (VTVH) MCD spectroscopies to obtain detailed insight into its geometric/electronic structure and to correlate structure with reactivity; NRVS focuses on the Fe(III), whereas MCD reflects the spin-allowed transitions mostly on the Mn(IV).

Elucidation of the Fe(IV)=O intermediate in the catalytic cycle of the halogenase SyrB2.

Mononuclear non-haem iron (NHFe) enzymes catalyse a broad range of oxidative reactions, including halogenation, hydroxylation, ring closure, desaturation and aromatic ring cleavage reactions. They are involved in a number of biological processes, including phenylalanine metabolism, the production of neurotransmitters, the hypoxic response and the biosynthesis of secondary metabolites. The reactive intermediate in the catalytic cycles of these enzymes is a high-spin S = 2 Fe(IV)=O species, which has been trapped for a number of NHFe enzymes, including the halogenase SyrB2 (syringomycin biosynthesis enzyme 2).

Slow processes in supercooled o-terphenyl: relaxation and decoupling.

We mapped the relaxation times of inter- and intramolecular correlations in o-terphenyl by a quasielastic scattering method using nuclear resonant scattering of synchrotron radiation. From the obtained map, we found that the slow β process is decoupled from the α process at 278 K, and this temperature is clearly below the previous decoupling temperature of 290 K, at which the α-relaxation dynamics changes. Then, it was also concluded that sufficient solidlike condition achieved by further cooling from 290 K is required to decouple the slow β process from the α process and, due to the difference of the length scales between the α and the slow β processes, these two averaged relaxation times <τ> are concluded not to cross as an extrapolation assumed so far.

(129)I Mössbauer spectroscopic study of a metallic MMX chain system.

One-dimensional iodide-bridged mixed-valence binuclear platinum complexes (the so-called "MMX chains") and their Pt(III) dimer precursors were investigated with (129)I Mossbauer spectroscopy. Spectra consisting of two sets of octuplets were observed at low temperatures for a neutral MMX chain complex, Pt(2)(dtp)(4)I (dtp = C(2)H(5)CS(2)(-)), with various charge-ordering states at the Pt dimers, indicating that the charge-ordering state is in an alternate-charge-polarization phase (ACP: ..

Synchrotron-radiation-based Mössbauer spectroscopy.

We have developed a new method that yields Mössbauer absorption spectra using synchrotron radiation (SR); this method is applicable for almost all Mössbauer nuclides including those that cannot be measured by previous methods using radioisotope (RI) sources. The Mössbauer spectrum of the 68.752 keV excited state of 73Ge, which cannot be measured using a RI source, was measured using SR.

Site-specific phonon density of states discerned using electronic states.

We have performed the measurement of the site-specific phonon densities of states (PDOS) discerned using electronic states. As far as we know, no general method could give the site-specific PDOS, although oscillating properties of the individual atoms in nonequivalent positions are not necessarily equivalent. However, the combination of the energy and time domain measurements of the nuclear resonant scattering of synchrotron radiation allows the identification of site-specific PDOS.