Molecular Details on Multiple Cofactor Containing Redox Metalloproteins Revealed by Infrared and Resonance Raman Spectroscopies

Vibrational spectroscopy and in particular, resonance Raman (RR) spectroscopy, can provide molecular details on metalloproteins containing multiple cofactors, which are often challenging for other spectroscopies. Due to distinct spectroscopic fingerprints, RR spectroscopy has a unique capacity to monitor simultaneously and independently different metal cofactors that can have particular roles in metalloproteins. These include e.g., (i) different types of hemes, for instance hemes c, a and a3 in caa3-type oxygen reductases, (ii) distinct spin populations, such as electron transfer (ET) low-spin (LS) and catalytic high-spin (HS) hemes in nitrite reductases, (iii) different types of Fe-S clusters, such as 3Fe-4S and 4Fe-4S centers in di-cluster ferredoxins, and (iv) bi-metallic center and ET Fe-S clusters in hydrogenases. IR spectroscopy can provide unmatched molecular details on specific enzymes like hydrogenases that possess catalytic centers coordinated by CO and CN− ligands, which exhibit spectrally well separated IR bands. This article reviews the work on metalloproteins for which vibrational spectroscopy has ensured advances in understanding structural and mechanistic properties, including multiple heme-containing proteins, such as nitrite reductases that house a notable total of 28 hemes in a functional unit, respiratory chain complexes, and hydrogenases that carry out the most fundamental functions in cells.

Thermodynamic properties of spin-imbalance harmonically trapped one-dimensional attractive 6Li atomic gas

The thermodynamic properties of 6Li atomic gas system, with imbalanced spin populations trapped in one-dimension, were systematically investigated using the Static Fluctuation Approximation. The two-body interaction used is an attractive contact potential. The effects of gas parameter [Formula: see text] and spin polarization [Formula: see text], on the thermodynamic properties and effective magnetic field were investigated. We observed a decrease in [Formula: see text] and an enhancement in [Formula: see text] and [Formula: see text] with increasing [Formula: see text]. At strong interaction and at [Formula: see text], the behavior of entropy with [Formula: see text] indicated two different phases. At small spin polarization [Formula: see text], the system could be in Fulde–Ferrell–Larkin Ovchinnikov (FFLO) state, while above [Formula: see text], the system might be in normal state. In addition, we found a clear decrease in both [Formula: see text] and [Formula: see text] and an enhancement in [Formula: see text] with the increase of the interaction strength. Our results are consistent with the reported results obtained by the mean-field Bogoliubov–de Gennes method, the Bardeen–Cooper–Schrieffer (BCS) approximation and Nozieres–Schmitt–Rink (NSR) theory.

Excited State Character of Cibalackrot-Type Compounds Interpreted in Terms of Hückel-Aromaticity: A Rational for Singlet Fission Chromophore Design

The exact energies of the lowest singlet and triplet excited states in organic chromophores are crucial to their performance in optoelectronic devices. The possibility of utilizing singlet fission to enhance the performance of photovoltaic devices has resulted in a wide demand for tuneable, stable organic chromophores with wide S₁ – T₁ energy gaps (>1 eV). Cibalackrot-type compounds were recently considered to have favorably positioned excited state energies for singlet fission, and they were found to have a degree of aromaticity in the lowest triplet excited state (T₁). This work reports on a revised and deepened theoretical analysis taking into account the excited state Hückel-aromatic (instead of Baird-aromatic) as well as diradical characters, with the aim to design new organic chromophores based on this scaffold in a rational way starting from qualitative theory. We demonstrate that the substituent strategy can effectively adjust the spin populations on the chromophore moieties and thereby manipulate the excited state energy levels. Additionally, the improved understanding of the aromatic characters enables us to demonstrate a feasible design strategy to vary the excited state energy levels by tuning the number and nature of Hückel-aromatic units in the excited state. Finally, our study elucidates the complications and pitfalls of the excited state aromaticity and antiaromaticity concepts, highlighting that quantitative results from quantum chemical calculations of various aromaticity indices must be linked with qualitative theoretical analysis of the character of the excited states.

Excited State Character of Cibalackrot-Type Compounds Interpreted in Terms of Hückel-Aromaticity: A Rational for Singlet Fission Chromophore Design

The exact energies of the lowest singlet and triplet excited states in organic chromophores are crucial to their performance in optoelectronic devices. The possibility of utilizing singlet fission to enhance the performance of photovoltaic devices has resulted in a wide demand for tuneable, stable organic chromophores with wide S₁ – T₁ energy gaps (>1 eV). Cibalackrot-type compounds were recently considered to have favorably positioned excited state energies for singlet fission, and they were found to have a degree of aromaticity in the lowest triplet excited state (T₁). This work reports on a revised and deepened theoretical analysis taking into account the excited state Hückel-aromatic (instead of Baird-aromatic) as well as diradical characters, with the aim to design new organic chromophores based on this scaffold in a rational way starting from qualitative theory. We demonstrate that the substituent strategy can effectively adjust the spin populations on the chromophore moieties and thereby manipulate the excited state energy levels. Additionally, the improved understanding of the aromatic characters enables us to demonstrate a feasible design strategy to vary the excited state energy levels by tuning the number and nature of Hückel-aromatic units in the excited state. Finally, our study elucidates the complications and pitfalls of the excited state aromaticity and antiaromaticity concepts, highlighting that quantitative results from quantum chemical calculations of various aromaticity indices must be linked with qualitative theoretical analysis of the character of the excited states.

Time-Resolved XUV Absorption Spectroscopy and Magnetic Circular Dichroism at the Ni M2,3-Edges

Ultrashort optical pulses can trigger a variety of non-equilibrium processes in magnetic thin films affecting electrons and spins on femtosecond timescales. In order to probe the charge and magnetic degrees of freedom simultaneously, we developed an X-ray streaking technique that has the advantage of providing a jitter-free picture of absorption cross-section changes. In this paper, we present an experiment based on this approach, which we performed using five photon probing energies at the Ni M2,3-edges. This allowed us to retrieve the absorption and magnetic circular dichroism time traces, yielding detailed information on transient modifications of electron and spin populations close to the Fermi level. Our findings suggest that the observed absorption and magnetic circular dichroism dynamics both depend on the extreme ultraviolet (XUV) probing wavelength, and can be described, at least qualitatively, by assuming ultrafast energy shifts of the electronic and magnetic elemental absorption resonances, as reported in recent work. However, our analysis also hints at more complex changes, highlighting the need for further experimental and theoretical studies in order to gain a thorough understanding of the interplay of electronic and spin degrees of freedom in optically excited magnetic thin films.

The relationship between antioxidant activity, first electrochemical oxidation potential, and spin population of flavonoid radicals

I have shown that by averaging antioxidant activity (AA) values measured by different methods it is possible to obtain an excellent correlation (R2=0.960) between the first electrochemical oxidation potential, Ep1, and AA. Separate correlations using the AA values obtained with each of the four methods [R2 were 0.561 for diphenyl-1-picrylhydrazyl (DPPH), 0.849 for Folin Ciocalteu reagent (FCR), 0.848 for the ferric-reducing ability of plasma (FRAP), and 0.668 for the Trolox equivalent antioxidant capacity (TEAC)] were all worse, and in some cases not useful at all, such as the one for DPPH. Also, the sum of atomic orbital spin populations on the carbon atoms in the skeleton of radicals ( s(C) Σ AOSPRad), calculated with the semi-empirical parameterisation method 6 (PM6) in water, was used to correlate both Ep1 and AA, yielding R2=0.926 and 0.950, respectively. This showed to be a much better variable for the estimation of Ep1 and AA than the bond dissociation energy (BDE), R2=0.854 and 0.901 for Ep1 and AA, respectively, and especially the ionisation potential (IP), R2=0.445 and 0.435 for Ep1 and AA, respectively.

How to understand very weak Cr–Cr double bonds and negative spin populations in trinuclear Cr complexes: theoretical insight

Trinuclear Cr(ii) complex [Cr3(dpa)4Cl2] (Hdpa = dipyridylamine) has two Cr–Cr double bonds linked with each other but [Cr3(dpa)4(N3)2] has one Cr–Cr quadruple bond. CASCF/CASPT2 studies provide understanding of these Cr–Cr bonds and β-spin population on the center Cr.

The dependence of oxygen sensitivity on the molecular structures of Ir(iii) complexes and their application for photostable and reversible luminescent oxygen sensing

The delocalization of spin populations (DSPs) could be used to describe the dependence of oxygen sensitivity on the molecular structures of Ir(iii) complexes. And excellent operational stability of an Ir(iii) oxygen sensing film is presented.