Transfer Of Spin Density Research Articles

Noncovalent Hydrogen Isotope Effects in Paramagnetic Molecules

Zero-point energies (ZPE) of intermolecular, non-bonded vibrations and isotope effects, induced by noncovalent interactions, are computed for paramagnetic molecules. They appear to be not significant for complexation of HO2 and oxygen with C–H bonds and results to isotope effect, which deviates from unit by 5–10%. However, ZPE and isotope effects in complexes of HO2 and nitroxyl radicals with water are larger and reach 50–70%. The largest effect, about 12, is found for complexation of hydrogen atom with water. Complexation of nitroxyl and peroxy radicals by hydrogen bonds is accompanied by transfer of spin density of unpaired electron from radical to the ligand molecules and induces high field paramagnetic shifts of the ligand NMR lines. It evidences that the spin transfer via intermolecular bonds occurs by mechanism of spin polarization.

Exchange interaction mechanisms in 1,3,5,7-tetramethyl-2,6-diazaadamantane N,N’-dioxyl biradical

The exchange interaction parameters were calculated and the spin density distribution over the organic skeleton of the 1,3,5,7-tetramethyl-2,6-diazaadamantane N,N’-dioxyl biradical was studied based on the results of quantum chemical modeling of the biradical structure by the DFT method using various hybrid functionals (UB3LYP, LC-wPBE, UCAM-B3LYP, UHSEH1PBE) with the 6-311++G(2d,2p) basis set and by the UHF method with the same basis set. The characteristics of the direct orbital overlap between the N atoms of the two nitroxide groups were determined. The values of the J constant, obtained using different calculation methods, were found to be similar to each other. It was established that there is ferromagnetic exchange interaction between the radical sites in the system in question, which occurs predominantly according to the spin polarization mechanism in the 2,6-diazaadamantane core, and the various spin density transfer pathways through the C atoms of the organic skeleton were found to be nonequivalent. The direct overlap of the upper singly-occupied МОs with localization on the nitroxide groups led to a noticeable additional contribution of the antiferromagnetic exchange interaction. Despite the latter factor, the total contribution of these two mechanisms (spin polarization and direct through-space exchange) resulted in the triplet ground state in the biradical studied.

Synthesis, crystal structure and spin exchange coupling in polynuclear carboxylates with {Li2(VO)2} metal core

Crystals of binuclear complex [(VO)2(µ-OH)(µ-Piv)2(bpy)2](OTf) (1) have been obtained by the reaction of [VO(H2O)5](OTf)2 (OTf=CF3SO3−, Piv=(CH3)3CCO2−) with 2,2′-bipyridine (bpy) and lithium trimethylacetate (pivalate), Li(Piv), in a ratio of 1:1:2 in MeCN. Change of the reagent ratio to 1:1:3 resulted in the bimetallic compound [Li2(VO)2(µ-Piv)6(bpy)2] (2), which was isolated in the form of 2·MeCN and 2·CH2Cl2 solvates. Replacement of Li(Piv) with lithium trifluoroacetate Li(Tfac) (Tfac=CF3CO2−) results in the bimetallic compound [Li2(VO)2(µ-Tfac)6(bpy)2] (3). A similar reaction with lithium trichloroacetate, Li(Tcac) (Tcac=CCl3CO2−), in ethanol gives the mononuclear complex [VO(Tcac)(bpy)2](OTf) (4). The structures of 1–4 were determined by single crystal X-ray diffraction. The magnetic properties (2–300K) and EPR spectra of compounds 1–3 have been studied. Using the ESEEM (electron spin echo envelope modulation) method it has been shown that the mononuclear cation [VO(Tcac)(bpy)2]+ of complex 4 has partial spin density transfer from the VIV atom to donor ligands (in particular, the bpy nitrogen atoms). According to EPR spectroscopy data and quantum-chemical calculations, a similar spin density distribution is observed for 2 and 3, though spin exchange in these compounds is hindered by lithium ions, which contain no spin density and block electron density delocalization in the bridging system between the “magnetic” vanadium ions. Electrochemical properties of compounds 2 and 3 confirm the vanadium(IV) oxidation state.

Tuning the Ti3+ and Al3+ Synergy in an Al2O3/TiClx Catalyst To Modulate the Grade of the Produced Polyethylene

A multitechnique approach (comprising in situ Fourier transform infrared, diffuse reflectance ultraviolet–visible, and advanced electron paramagnetic resonance spectroscopies, coupled with differential scanning calorimetry analysis) was employed to investigate the local structure and the activation of a heterogeneous ethylene polymerization catalyst obtained by grafting TiCl4 onto a transitional alumina. The activation procedure was found to affect the electronic structure and the coordinative environment of the reduced Ti sites, as well as their interaction with the Al3+ sites, measured in terms of spin density transfer from Ti3+ to nearby Al3+ ions. It was found that the extent of interaction between the two metal sites correlates with the microstructures of the obtained polyethylene. Tuning the synergy between the Ti3+ and Al3+ Lewis acid sites is proposed as an efficient way to modulate the polyethylene microstructure, switching from a high-density polyethylene to a highly branched polyethylene.

Elucidating the Structures of the Low- and High-pH Mo(V) Species in Respiratory Nitrate Reductase: A Combined EPR, 14,15N HYSCORE, and DFT Study.

Respiratory nitrate reductases (Nars), members of the prokaryotic Mo/W-bis Pyranopterin Guanosine dinucleotide (Mo/W-bisPGD) enzyme superfamily, are key players in nitrate respiration, a major bioenergetic pathway widely used by microorganisms to cope with the absence of dioxygen. The two-electron reduction of nitrate to nitrite takes place at their active site, where the molybdenum ion cycles between Mo(VI) and Mo(IV) states via a Mo(V) intermediate. The active site shows two distinct pH-dependent Mo(V) electron paramagnetic resonance (EPR) signals whose structure and catalytic relevance have long been debated. In this study, we use EPR and HYSCORE techniques to probe their nuclear environment in Escherichia coli Nar (EcNar). By using samples prepared at different pH and through different enrichment strategies in 98Mo and 15N nuclei, we demonstrate that each of the two Mo(V) species is coupled to a single nitrogen nucleus with similar quadrupole characteristics. Structure-based density functional theory calculations allow us to propose a molecular model of the low-pH Mo(V) species consistent with EPR spectroscopic data. Our results show that the metal ion is coordinated by a monodentate aspartate ligand and permit the assignment of the coupled nitrogen nuclei to the Nδ of Asn52, a residue located ∼3.9 Å to the Mo atom in the crystal structures. This is confirmed by measurements on selectively 15N-Asn labeled EcNar. Further, we propose a Mo-O(H)···HN structure to account for the transfer of spin density onto the interacting nitrogen nucleus deduced from HYSCORE analysis. This work provides a foundation for monitoring the structure of the molybdenum active site in the presence of various substrates or inhibitors in Nars and other molybdenum enzymes.

Structure, Stability, and Properties of Boron Encapsulated Complexes of C60, C59B, and C59N.

Density functional studies are performed for the boron atom encapsulated complexes of C60, C59B, and C59N using B3LYP and B3LYP-GD2 functionals with 6-311G* basis set. The study shows that the complexes B@C59B and B@C59N can exist in different forms which differ in their structure as well as electronic and magnetic properties. The nature of interaction between the guest and the host is analyzed based on the stabilization energies of complexes for their different spin states. The electronic properties such as vertical electron affinity (VEA), vertical ionization energy (VIE), and energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the complexes are calculated. The transfer of electron spin density and spin-spin coupling of electrons between the guest and the host are examined. The study reveals that ferromagnetic core@shell spin coupling occurs between the host and the guest species of the complexes B@C59B and B@C59N in their triplet state without any transfer of spin density. The values of hyperfine coupling constant (hfcc) for the heteroatom of the cage and for the encapsulated boron atom of the complexes are analyzed, and it indicates that the value of hfcc for the encapsulated boron decreases significantly due to confinement.

Spin-Spin Coupling in Nitrogen Atom Encapsulated C60, C59N, and Their Respective Dimers.

Density functional theoretical calculations were performed to study the stability and magnetic properties of nitrogen-encapsulated C60, C59N, and their respective dimers at B3LYP/6-311G* and B3LYP-GD2/6-311G* levels of theory. For the most stable spin state of each of the above complexes, spin density transfer and spin-spin coupling between different components are investigated. The nature of bonding between the guest and the host is analyzed based on the highest occupied molecular orbital-lowest unoccupied molecular orbital energy gap and the respective molecular orbital diagrams. The analysis of spin density showed that the encapsulated nitrogen retained its atomic state in N@C60 and N@C59N. Depending on the multiplicity of N@C59N, the unpaired electrons of the encapsulated nitrogen are coupled with those of the cage anti-ferromagnetically or ferromagnetically. The present study also showed that the complex (N@C60)2 can exist in two isoenergetic spin states, namely, (7)[(N@C60)2] and (1)[(N@C60)2]. In the former, the encapsulated nitrogens are ferromagnetically coupled, whereas they are coupled anti-ferromagnetically in the latter. A similar coupling between the guest species occurs in the nitrogen analogues (7)[(N@C59N)2] and (1)[(N@C59N)2]. The stabilization energy of the endohedral nitrogen complexes indicated that the interaction between the guest and the host cage is purely noncovalent.

Comparative Study of the Magnetic Structure of BaFe2As2 Doped with Co or Ni

We present a comparative study of the electronic structure of pure, Co-doped, and Ni-doped BaFe2As2. The calculations were performed by the embedded cluster method at the electron correlation level (ECM-MP2). The orbital population analysis reveals that doping with Co or Ni introduces, in both cases, a considerable transfer of charge from cations toward the anions and a transfer of spin density in the opposite direction that reflects an independence of spin and charge in non-relativistic approach. In both doping, we note the presence of spinless electron on the 3d orbitals. On the other hand, both doping cases differ in the local magnetic order: Co induces a local antiferromagnetic order along the b axis of the crystalline structure, while Ni maintains the ferromagnetic order along this axis. In the Co-doped compound, the frustration of magnetic state and formation of spinless electrons correspond to some properties of the Anderson RVB model of superconductivity.

B, N- and P, N-doped graphene as highly active catalysts for oxygen reduction reactions in acidic media

Graphene has been highlighted recently as a promising material for energy conversion due to its unique properties deriving from a two-dimensional layered structure of sp2-hybridized carbon. Herein, N-doped graphene (NGr) is developed for its application in oxygen reduction reactions (ORRs) in acidic media, and additional doping of B or P into the NGr is attempted to enhance the ORR performance. The NGr exhibits an onset potential of 0.84 V and a mass activity of 0.45 mA mg−1 at 0.75 V. However, the B, N- (BNGr) and P, N-doped graphene (PNGr) show onset potentials of 0.86 and 0.87 V, and mass activities of 0.53 and 0.80 mA mg−1, respectively, which are correspondingly 1.2 and 1.8 times higher than those of the NGr. Moreover, an additional doping of B or P effectively reduces the production of H2O2 in the ORRs, and shows much higher stability than that of Pt/C in acidic media. It is proposed that the improvement in the ORR activity results from the enhanced asymmetry of the spin density or electron transfer on the basal plane of the graphene, and the decrease in the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the graphene through additional doping of B or P.

Dissection of Hydrogen Bond Interaction Network around an Iron–Sulfur Cluster by Site-Specific Isotope Labeling of Hyperthermophilic Archaeal Rieske-Type Ferredoxin

The electronic structure and geometry of redox-active metal cofactors in proteins are tuned by the pattern of hydrogen bonding with the backbone peptide matrix. In this study we developed a method for selective amino acid labeling of a hyperthermophilic archaeal metalloprotein with engineered Escherichia coli auxotroph strains, and we applied this to resolve the hydrogen bond interactions with the reduced Rieske-type [2Fe-2S] cluster by two-dimensional pulsed electron spin resonance technique. Because deep electron spin-echo envelope modulation of two histidine (14)N(δ) ligands of the cluster decreased non-coordinating (15)N signal intensities via the cross-suppression effect, an inverse labeling strategy was employed in which (14)N amino acid-labeled archaeal Rieske-type ferredoxin samples were examined in an (15)N-protein background. This has directly identified Lys45 N(α) as providing the major pathway for the transfer of unpaired electron spin density from the reduced cluster by a "through-bond" mechanism. All other backbone peptide nitrogens interact more weakly with the reduced cluster. The extension of this approach will allow visualizing the three-dimensional landscape of preferred pathways for the transfer of unpaired spin density from a paramagnetic metal center onto the protein frame, and will discriminate specific interactions by a "through-bond" mechanism from interactions which are "through-space" in various metalloproteins.

Analysis of the 7Li NMR signals in the Monoclinic Li3Fe2(PO4)3 and Li3V2(PO4)3 Phases

The monoclinic Li3Fe2(PO4)3 and Li3V2(PO4)3 phosphates are materials for positive electrodes in Li-ion batteries. They also have interesting structures to test and improve the understanding of Li NMR signals in paramagnetic compounds. The position of such signals is governed by the transfer of electron spin density from the transition metal ion to the Li nucleus. These mechanisms are based on delocalization and polarization effects which induce positive and negative Fermi contact shifts, respectively. We have characterized Li3Fe2(PO4)3 by Li NMR. To understand the signals observed, we have analyzed the electron spin density transfer mechanisms (i) by considering the different Li environments, (ii) by using DFT calculations. We compare our analysis to the one very recently reported by Davis et al. These analyses have been extended to Li3V2(PO4)3 studied by NMR by Cahill et al.

Trapping and spectroscopic characterization of an FeIII-superoxo intermediate from a nonheme mononuclear iron-containing enzyme

Fe(III)-O(2)*(-) intermediates are well known in heme enzymes, but none have been characterized in the nonheme mononuclear Fe(II) enzyme family. Many steps in the O(2) activation and reaction cycle of Fe(II)-containing homoprotocatechuate 2,3-dioxygenase are made detectable by using the alternative substrate 4-nitrocatechol (4NC) and mutation of the active site His200 to Asn (H200N). Here, the first intermediate (Int-1) observed after adding O(2) to the H200N-4NC complex is trapped and characterized using EPR and Mössbauer (MB) spectroscopies. Int-1 is a high-spin (S(1) = 5/2) Fe(III) antiferromagnetically (AF) coupled to an S(2) = 1/2 radical (J ≈ 6 cm(-1) in ). It exhibits parallel-mode EPR signals at g = 8.17 from the S = 2 multiplet, and g = 8.8 and 11.6 from the S = 3 multiplet. These signals are broadened significantly by hyperfine interactions (A((17)O) ≈ 180 MHz). Thus, Int-1 is an AF-coupled species. The experimental observations are supported by density functional theory calculations that show nearly complete transfer of spin density to the bound O(2). Int-1 decays to form a second intermediate (Int-2). MB spectra show that it is also an AF-coupled Fe(III)-radical complex. Int-2 exhibits an EPR signal at g = 8.05 arising from an S = 2 state. The signal is only slightly broadened by (< 3% spin delocalization), suggesting that Int-2 is a peroxo-Fe(III)-4NC semiquinone radical species. Our results demonstrate facile electron transfer between Fe(II), O(2), and the organic ligand, thereby supporting the proposed wild-type enzyme mechanism.

Characterization of the Semiquinone Radical Stabilized by the Cytochrome aa3-600 Menaquinol Oxidase of Bacillus subtilis

Cytochrome aa(3)-600 is one of the principle respiratory oxidases from Bacillus subtilis and is a member of the heme-copper superfamily of oxygen reductases. This enzyme catalyzes the two-electron oxidation of menaquinol and the four-electron reduction of O(2) to 2H(2)O. Cytochrome aa(3)-600 is of interest because it is a very close homologue of the cytochrome bo(3) ubiquinol oxidase from Escherichia coli, except that it uses menaquinol instead of ubiquinol as a substrate. One question of interest is how the proteins differ in response to the differences in structure and electrochemical properties between ubiquinol and menaquinol. Cytochrome bo(3) has a high affinity binding site for ubiquinol that stabilizes a ubi-semiquinone. This has permitted the use of pulsed EPR techniques to investigate the protein interaction with the ubiquinone. The current work initiates studies to characterize the equivalent site in cytochrome aa(3)-600. Cytochrome aa(3)-600 has been cloned and expressed in a His-tagged form in B. subtilis. After isolation of the enzyme in dodecylmaltoside, it is shown that the pure enzyme contains 1 eq of menaquinone-7 and that the enzyme stabilizes a mena-semiquinone. Pulsed EPR studies have shown that there are both similarities as well as significant differences in the interactions of the mena-semiquinone with cytochrome aa(3)-600 in comparison with the ubi-semiquinone in cytochrome bo(3). Our data indicate weaker hydrogen bonds of the menaquinone in cytochrome aa(3)-600 in comparison with ubiquinone in cytochrome bo(3). In addition, the electronic structure of the semiquinone cyt aa(3)-600 is more shifted toward the anionic form from the neutral state in cyt bo(3).

Muon spin spectroscopy of the discotic liquid crystal HAT6

Avoided level crossing muon spin resonance (ALC-muSR) has been used to study the cyclohexadienyl-type radicals produced by the addition of muonium (Mu) to the discotic liquid crystal HAT6 (2,3,6,7,10,11-hexahexyloxytriphenylene) in the crystalline (Cr) phase, the hexagonal columnar mesophase (Col(h)) and isotropic (I) phase. In the Cr phase unpaired electron spin density can be transferred from the radical to neighboring HAT6 molecules depending on the overlap of their pi-systems and hence on the relative orientation of the triphenylene rings. The two Delta(1) resonances in the ALC-muSR spectra of the Cr phase indicate that the neighboring HAT6 molecules have two preferred orientations with respect to the radical: one which results in negligible spin density transfer and a second where 17% of the unpaired spin density is transferred. The ALC-muSR spectra in Col(h) and I phases are substantially different from those of the Cr phase in that there are two narrow resonances superimposed on an extremely broad and intense resonance. The narrow resonances are due to highly mobile radicals located in the aliphatic region between the columns and the broad resonance is due to radicals incorporated within the columns of HAT6 molecules. The large width and amplitude of this resonance indicates that the radicals within the columns are undergoing rapid electron spin relaxation but the mechanism that causes this relaxation is unknown.

Methane activation by V3PO10˙+ and V4O10˙+ clusters: A comparative study

A series of vanadium and phosphorus heteronuclear oxide cluster cations (V(x)P(y)O(z)(+)) are prepared by laser ablation and the reactions of V(3)PO(10)˙(+) and V(4)O(10)˙(+) with methane in a fast flow reactor under the same conditions are studied. A time of flight mass spectrometer is used to detect the cluster distribution before and after reactions. In addition to previously identified reaction of V(4)O(10)˙(+) + CH(4)→ V(4)O(10)H(+) + CH(3)˙, the observation of hydrogen atom pickup cluster V(3)PO(10)H(+) suggests the reaction: V(3)PO(10)˙(+) + CH(4)→ V(3)PO(10)H(+) + CH(3)˙. The rate of the reaction of V(4)O(10)˙(+) with CH(4) is approximately 2.5 times faster than that of V(3)PO(10)˙(+) with CH(4). Density functional theory (DFT) calculations predict that structure of V(3)PO(10)˙(+) is topologically similar to that of V(4)O(10)˙(+), as well as that of P(4)O(10)˙(+), which is very similar to V(4)O(10)˙(+) in terms of methane activation in previous studies. The facile methane activation by the homo- and hetero-nuclear oxide clusters can all be attributed to the presence of an oxygen-centered radical (O˙) in these clusters. Further theoretical study indicates that the O˙ radical (or spin density of the cluster) can transfer within the high symmetry V(4)O(10)˙(+) and P(4)O(10)˙(+) clusters quite easily, and CH(4) molecule further enhances the rate of intra-cluster spin density transfer. In contrast, the intra-cluster spin density transfer within low symmetry V(3)PO(10)˙(+) is thermodynamically forbidden. The experimentally observed reactivity difference is consistent with the theoretical consideration of the intra-cluster spin density transfer.

Variation of reaction dynamics for OH hydrogen abstraction from glycine between ab initio levels of theory

The variation in reaction dynamics of OH hydrogen abstraction from glycine between HF, MP2, CCSD(T), M05-2X, BHandHLYP, and B3LYP levels was demonstrated. The abstraction mode shows distinct patterns between these five levels and determines the barrier height, and the spin density transfer between OH radical and glycine. These differences are mainly resulted from the spin density distribution and geometry of the alpha carbon during the abstraction. The captodative effect which is commonly believed as one of the major factors to stabilize the caron-centered radical can only be observed in DFT levels but not in HF and MP2 levels. Difference in the abstraction energy were found in these calculation levels, by using the result of CCSD(T) as reference, B3LYP, BHandHLYP, and M05-2X underestimated the reaction barrier about 5.1, 0.1, and 2.4 kcal mol(-1), while HF and MP2 overestimated 19.1 kcal mol(-1) and 1.6 kcal mol(-1), respectively. These differences can be characterized by the vibration mode of imaginary frequency of transition states, which indicates the topology around transition states and determines reaction barrier height. In this model system, BHandHLYP provides the best prediction of the energy barrier among those tested methods.

Aspects of structure and bonding in copper-amino acid complexes revealed by single-crystal EPR/ENDOR spectroscopy and density functional calculations.

This work deduces from a series of well-defined copper-doped amino acid crystals, relationships between structural features of the copper complexes, and ligand-bound proton hyperfine parameters. These were established by combining results from electron paramagnetic resonance (EPR)/electron-nuclear double resonance (ENDOR) studies, crystallography, and were further assessed by quantum mechanical (QM) calculations. A detailed evaluation of previous studies on Cu(2+) doped into alpha-glycine, triglycine sulfate, alpha-glycylglycine, and L-alanine crystals reveal correlations between geometric features of the copper sites and proton hyperfine couplings from amino-bound and carbon-bound hydrogens. Experimental variations in proton isotropic hyperfine coupling values (a(iso)) could be fit to cosine-square dependences on dihedral angles, namely, for C(alpha)-bound hydrogens, a(iso) = -1.09 + 8.21 cos(2) theta MHz, and for amino hydrogens, a(iso) = -6.16 + 4.15 cos(2) phi MHz. For the C(alpha) hydrogens, this dependency suggests a hyperconjugative-like mechanism for transfer of spin density into the hydrogen 1s orbital. In the course of this work, it was also necessary to reanalyze the ENDOR measurements from Cu(2+)-doped alpha-glycine because the initial study determined the (14)N coupling parameters without holding its nuclear quadrupole tensor traceless. This new treatment of the data was needed to correctly align the (14)N hyperfine tensor principal directions in the molecular complex. To provide a theoretical basis for the coupling variations, QM calculations performed at the DFT level were used to compute the proton hyperfine tensors in the four crystal complexes as well as in a geometry-optimized Cu(2+)(glycine)(2) model. These theoretical calculations confirmed systematic changes in couplings with dihedral angles but greatly overestimated the experimental geometric sensitivity to the amino hydrogen isotropic coupling.

Solvation of a Hydrogen Isotope in Aqueous Methanol, NaCl, and KCl Solutions

The muon hyperfine coupling constant (hfc) of the light hydrogen isotope muonium (Mu) was measured in aqueous methanol, NaCl, and KCl solutions with varying concentrations, in deuterated water, and in deuterated methanol. The muon hfc is shown to be sensitive to the size and composition of the primary solvation shell, and the three-dimensional harmonic oscillator model of Roduner et al. (J. Chem. Phys. 1995, 102, 5989) has been modified to account for dependence of the muon hfc on the methanol or salt concentration. The muon hfc of Mu in the aqueous methanol solutions decreases with increasing methanol concentration up to a mole fraction (chiMeOH) of approximately 0.4, above which the muon hfc is approximately constant. The concentration dependence of the muon hfc is due to hydrophobic nature of Mu. It is preferentially solvated by the methyl group of methanol, and the proportion of methanol molecules in the primary solvation shell is greater than that in the bulk solution. Above chiMeOH approximately 0.4, Mu is completely surrounded by methanol. The muon hfc decreases with increasing methanol concentration because more unpaired electron spin density is transferred from Mu to methanol than to water. The unpaired electron spin density is transferred from Mu to the solvent by collisions that stretch one of the solvents bonds. The amount of spin density transferred is likely inversely related to the activation barrier for abstraction from the solvent, which accounts for the larger muon hfc in the deuterated solvents. The muon hfc of Mu in electrolyte solution decreases with increasing concentration of NaCl or KCl. We suggest that the decrease of the muon hfc is due to the amount of spin density transferred from Mu to its surroundings being dependent on the average orientation of the water molecules in the primary solvation shell, which is influenced by both Mu and the ions in solution, and spin density transfer to the ions themselves.

Hydrogen Bonds between Nitrogen Donors and the Semiquinone in the Qi-site of the bc1 Complex

The ubisemiquinone stabilized at the Qi-site of the bc1 complex of Rhodobacter sphaeroides forms a hydrogen bond with a nitrogen from the local protein environment, tentatively identified as ring N from His-217. The interactions of 14N and 15N have been studied by X-band (approximately 9.7 GHz) and S-band (3.4 GHz) pulsed EPR spectroscopy. The application of S-band spectroscopy has allowed us to determine the complete nuclear quadrupole tensor of the 14N involved in H-bond formation and to assign it unambiguously to the Nepsilon of His-217. This tensor has distinct characteristics in comparison with H-bonds between semiquinones and Ndelta in other quinone-processing sites. The experiments with 15N showed that the Nepsilon of His-217 was the only nitrogen carrying any considerable unpaired spin density in the ubiquinone environment, and allowed calculation of the isotropic and anisotropic couplings with the Nepsilon of His-217. From these data, we could estimate the unpaired spin density transferred onto 2s and 2p orbitals of nitrogen and the distance from the nitrogen to the carbonyl oxygen of 2.38+/-0.13A. The hyperfine coupling of other protein nitrogens with semiquinone is <0.1 MHz. This did not exclude the nitrogen of the Asn-221 as a possible hydrogen bond donor to the methoxy oxygen of the semiquinone. A mechanistic role for this residue is supported by kinetic experiments with mutant strains N221T, N221H, N221I, N221S, N221P, and N221D, all of which showed some inhibition but retained partial turnover.

The Structure of the Hydrated Electron. Part 1. Magnetic Resonance of Internally Trapping Water Anions: A Density Functional Theory Study

Density functional theory is used to rationalize magnetic parameters of hydrated electron trapped in alkaline glasses as observed using electron paramagnetic resonance (EPR) and electron spin echo envelope modulation (ESEEM) spectroscopies. To this end, model water cluster anions (n=4-8 and n=20, 24) that localize the electron internally are examined. It is shown that hyperfine coupling tensors of H/D nuclei in the water molecules are defined mainly by the cavity size and the coordination number of the electron; the water molecules in the second solvation shell play a relatively minor role. An idealized model of the hydrated electron (that is usually attributed to L. Kevan) in which six hydroxyl groups arranged in an octahedral pattern point toward the common center is shown to provide the closest match to the experimental parameters, such as isotropic and anisotropic hyperfine coupling constants for the protons (estimated from ESEEM), the second moment of the EPR spectra, and the radius of gyration. The salient feature is the significant transfer (10-20%) of spin density into the frontal O 2p orbitals of water molecules. Spin bond polarization involving these oxygen orbitals accounts for small, negative hyperfine coupling constants for protons in hydroxyl groups that form the electron-trapping cavity. In Part 2, these results are generalized for more realistic geometries of core anions obtained using a dynamic one-electron mixed quantum/classical molecular dynamics model.