W-band31P-ENDOR on the high-affinity Mn2+ binding site in the minimal and tertiary stabilized hammerhead ribozymes

The catalytic activity of the tertiary stabilized hammerhead ribozyme (tsHHRz) is by three orders of magnitude higher than the one of the long-known minimal construct (mHHRz). This gives rise to the question whether the single high-affinity manganese(II) binding site present in both ribozymes is located closer to the cleavage site and the transition state in the tsHHRz than in the mHHRz, which would make a direct involvement of this metal(II) ion in the bond-breaking step more likely. Here, we used W-band³¹P-Davies-ENDOR (electron-nuclear double resonance) to complement earlier reported¹⁴N-ESEEM/HYSCORE (electron spin echo envelope modulation/hyperfine sublevel correlation) studies. The³¹P-ENDOR spectrum of the mHHRz revealed a doublet with a splitting of 8.4(±0.5) MHz but unresolved hyperfine anisotropy. Such a large splitting indicates an inner-sphere coordination of a phosphate backbone group with a significant amount of spin density on the phosphorous nucleus. This is in good agreement with the³¹P isotropic hyperfine constant,A _iso(³¹P), of +7.8 MHz obtained by density functional theory calculations on the structure of the Mn²⁺ binding site as found in crystals of the same ribozyme. This supports the idea that the structure and location of the binding site in the mHHRz is in frozen buffer similar to that found in the crystal. Since the W-band ENDOR spectrum of the tsHHRz also shows a³¹P splitting of 8.4(±0.5) MHz, the local structures of both binding sites appear to be similar, which agrees with the coincidence of the¹⁴N data. An involvement of the high-affinity Mn²⁺ ion in the catalytic step seems therefore unlikely.     

Magnetic shielding studies on the alkali molecules Na2 and Cs2 by NMR

NMR in the alkali molecules Na₂ and Cs₂ is performed by the atom-molecule exchange optical pumping method. The shielding differences σ(Na)?σ(Na₂)=(29±16)·10^?6 and σ(Cs)?σ(Cs₂)=(221±12)·10^?6 are obtained. The investigation of the contribution of the valence electron to the magnetic shielding is supported by a NMR experiment in free Cs⁺ ions, which yields the shielding difference σ(Cs)?σ(Cs⁺)=(14±12)·10^?6. These measurements allow an estimation of the spin rotation interaction constant in these molecules.     

Transient and pulsed EPR study of17O-substituted methyl-naphthoquinone as radical anion in the A1 binding site of photosystem I and in frozen solution

Quinones have been studied in considerable detail as functional cofactors in membrane-bound protein-cofactor systems, in particular in reaction centers (RCs) of photosynthesis. For both types of RCs, they act primarily as one-electron gates during light-induced charge separation but at very different redox potential. Hydrogen bonding between the RC protein and the two, 1,4-quinone carbonyl groups constitutes a major protein-cofactor interaction in control of function. In contrast to symmetric H-bonding for quinones in isotropic solution, asymmetric H-bonding is a characteristic feature of the quinone binding sites in RC proteins. A simple valence bond model correlates the asymmetry of respective H-bond strength with the asymmetric spin density distribution derived from observable hyperfine couplings of the quinone anion state. Among all quinone-protein systems studied so far, the A₁ acceptor site in photosystem (PS) I exhibits the highest asymmetry. Since the carbonyl groups carry most of the total unpaired electron spin density, isotopic labelling of the carbon (¹³C) and oxygen (¹⁷O) appears to be the proper way to characterize the H-bond asymmetry by hyperfine couplings. Indeed, recent¹³C hyperfine studies, together with data for protons in specific ring substituents, confirm the high asymmetry correlated with only one dominant H-bond in the A₁ site of PS I, which is consistent with the structure model derived from X-ray structure (1JB0) for the ground state of the PS I protein complex.¹⁷O hyperfine tensors measured for the A₁ site of PS I yield high hyperfine coupling constants but very small asymmetry for the two carbonyl groups. The asymmetry is even three times smaller than the already small one observed for the Q_A site of purple bacterial RCs. A small asymmetry is however consistent with previous studies on model systems which showed an insensitivity of the¹⁷O hyperfine coupling to H-bond-induced changes of the unpaired electron spin density. The large¹⁷O hyperfine coupling itself appears to depend on the electrostatics seen by the radical anion. It is slightly larger when A ₁ ^? is part of the functional transient radical ion pair state as compared with the photoaccumulated stable radical anion. Possible explanations and consequences of these results are discussed.     

Magnetic structure of low-dimensional LiCu2O2 multiferroic according to 63,65Cu and 7Li NMR studies

The complex NMR study of the magnetic structure of LiCu₂O₂ multiferroic has been performed. It has been shown that the spin spirals in LiCu₂O₂ are beyond the ab, bc, and ac crystallographic planes. The external magnetic field applied along the c axis of the crystal does not change the spatial orientation of spirals in Cu²⁺ chains. A magnetic field of H ₀ = 94 kOe applied along the a and b axes rotates the planes of spin spirals in chains, tending to orient the normal n of spirals along the external magnetic field. The rotation angle of the planes of the magnetic moments are maximal at H ₀ ?? b.     

Electronic Structure And Magnetism of Novel Diluted Magnetic Semiconductors CdGeP 2 : Mn and ZnGeP 2 : Mn

Chalcopyrite II-IV-V 2 semiconductors CdGeP 2 : Mn and ZnGeP 2 : Mn are new types of diluted magnetic semiconductors (DMSs). Since their ferromagnetic Curie temperatures are much higher than room temperature, these DMSs are good candidates for materials to be used in spintronics devices. Their electronic and magnetic structures have been investigated using the first-principles calculations based on the Korringa-Kohn-Rostoker coherent-potential-approximation and local-density-approximation (KKR-CPA-LDA) methods. When Cd or Zn atoms are substituted by Mn atoms, the ground state magnetic structure is spinglass-like. On the other hand, if Mn atoms substitute Ge atoms, the system becomes ferromagnetic through the double-exchange mechanism. However, the calculation of the formation energies shows that this system is not energetically favorable. Instead, the system with vacancies (Cd, Vc, Mn)GeP 2 or a non-stoichiometric (Cd, Ge, Mn)GeP 2 are also ferromagnetic and, moreover, energetically stable. We conclude that either of these variants possess a ferromagnetic phase of the kind CdGeP 2 : Mn. Similar conclusions are obtained for ZnGeP 2 : Mn.     

Studies on Electronic Structure and Magnetic Properties of an Organic Magnet with Metallic Mn^2＋ and Cu^2＋ Ions

The electronic structure and the magnetic properties of the non-pure organic ferromagnetic compound MnCu(pbaOH)(H2O)3 with pbaOH=2-hydroxy-1, 3-propylenebis (oxamato) are studied by using the density-functional theory with local-spin-density approximation. The density of states, total energy, and the spin magnetic moment are calculated. The calculations reveal that the compound MnCu(pbaOH)(H2O)3 has a stable metal-ferromagnetic ground state, and the spin magnetic moment per molecule is 2.208 μa, and the spin magnetic moment is mainly from Mn ionand Cu ion. An antiferromagnetic order is expected and the antiferromagnetic exchange interaction of d-electrons of Cu and Mn passes through the antiferromagnetic interaction between the adjacent O, 0, and N atoms along the path linking the atoms Cu and Mn.     

Observation of magnetic Mn sites in cubic and hexagonal HoMn2: 55Mn NMR study

⁵⁵Mn nuclear magnetic resonance has been measured for both cubic C15 and hexagonal C14 HoMn₂. In the ordered state, we found a high-frequency signal, which can be assigned to magnetic Mn atoms, for both C15 and C14 phases together with a low-frequency signal from non-magnetic Mn atoms. The results of the spin-spin relaxation time T₂ in the ordered state and the NMR spectra in the paramagnetic state are also given to discuss the magnetic instability and the magnetic structure.     

Measurement of the proton NMR field shift in aqueous solutions containing Cu2+, Cr3+, Fe3+ and Mn2+ ions

There are presented measurements of the NMR field shifts for aqueous protons in aqueous solutions containing paramagnetic inorganic compounds of Cu²⁺, Cr³⁺, Fe³⁺ and Mn²⁺ ions. The measurements have been performed on samples in the form of transversally magnetized long cylinders using both the internal and external NMR standards. The experimentally determined shifts are related to the NMR field position of protons in pure water. The results for demagnetizing shifts are compared with the data which were computed from the magnetic susceptibility values (measured by magnetostatic method), the chemical shifts are compared with the results of other authors. Results of measurements indicate a small chemical shift of internal standards in some solutions.     

Ab initio and crystal field studies of the Mn4+-doped Ba2LaNbO6 double-perovskite

A detailed study using the ab initio DFT-based calculations of the electronic and optical properties of pure and Mn⁴⁺ doped Ba₂LaNbO₆ is presented in this paper. Comparison of the calculated electronic bands structure, density of states diagrams, and dielectric functions for the pure and doped crystal reveals the changes induced by the Mn⁴⁺ impurity ions. In addition, the energy levels of the Mn⁴⁺ ion in the ordered perovskite Ba₂LaNbO₆ are calculated by the exchange charge model (ECM) of crystal field theory and compared with the experimental data that has been presented in the literature. The calculated Mn⁴⁺ energy levels are in good agreement with the experimental spectra. Additionally, the excitation band shapes of the ⁴A_2g(⁴F)–⁴T_2g(⁴F) and ⁴A_2g(⁴F)–⁴T_1g(⁴F) transitions are modeled to estimate the zero-phonon lines (ZPL) positions and the effective number of phonons, which are involved in the corresponding excitation transition. The results of our calculations yield the crystal field parameter of Dq=1780 cm^?1 and Racah parameters B=670 and C=3290 cm^?1, with C/B=4.9 for the Mn⁴⁺ ion in the double-perovskite Ba₂LaNbO₆.     

ZnS:Mn2+/聚苯乙烯核壳及ZnS:Mn2+中空球的制备和光谱性质

采用超声化学沉积法制备了ZnS:Mn2+/聚苯乙烯核壳结构和ZnS:Mn2+空心球.产物分别用透射电镜、X射线衍射仪和光致发光谱进行了表征.透射电镜结果表明,在聚苯乙烯胶体微球表面覆盖了平均尺寸为9nm的ZnS:Mn2+纳米颗粒,X射线衍射结果进一步验证了这个结论.将核壳粒子在500℃灼烧除去PS核后,可以得到空心的ZnS:Mn2+微球,Mn2+的发射谱的峰位在540nm,与体相材料相比,蓝移了45nm,这可能是由于壳层结构引起Mn-O八面体畸变,进而导致能带结构变化引起的.     

Proton NMR of isomorphous paramagnetic and diamagnetic monohydrates MeSO4.1 H2O Me = Mn2+, Fe2+, Ni2+ AND Mg2+

Nuclear magnetic resonance of protons of crystallization water in isomorphous paramagnetic and diamagnetic monohydrates MeSO₄. 1 H₂O with Me = Mn²⁺, Fe²⁺, Ni²⁺ and Mg²⁺ is studied in the present paper. Proton NMR spectra in paramagnetic hydrates are asymmetric and their second moments, M₂, depend linearly on the square of the induction of the external magnetic field B₀. NMR spectrum of diamagnetic hydrate MgSO₄. 1 H₂O is symmetric and its shape and the second moment do not change with B₀. The parameters M₂₀ andK which characterize nuclear dipole-dipole interaction of protons and interaction of protons and paramagnetic ions, respectively, are derived from experimentally obtained dependences M₂ vs B ₀ ² and on the other hand, they are calculated by means of crystallographic data for substances studied. Calculations were realized in approximation where two nearest neighbour ions Me²⁺ to each water molecule are considered. The influence of the demagnetizing magnetic field of the sample was neglected.     

Magnetic measurements and microstructure studies of highly oriented Bi2Sr2Ca2Cu3O8 bulks

A highly oriented structure for Bi₂Sr₂Ca₂Cu₃O₈ bulk superconductors was successfully made by hot-forging. The J_c values were closely related to the degree of orientation. Microstructure observations and magnetization measurements revealed that the properties of the highly oriented BSCCO reflected the two-dimensionality in this layered structure material.     

Theory studies of the local lattice distortions and the EPR parameters for Cu2+, Mn2+ and Fe3+ centres in ZnWO4

The local lattice distortions and the electron paramagnetic resonance (EPR) parameters (g factors, hyperfine structure constants and zero-field splittings) for Cu²⁺, Mn²⁺ and Fe³⁺ in ZnWO₄ are theoretically studied based on the perturbation calculations for rhombically elongated octahedral 3d⁹ and 3d⁵ complexes. The impurity centres on Zn²⁺ sites undergo the local elongations of 0.01, 0.002 and 0.013 Å along the C₂ axis and the planar bond angle variations of 8.1°, 8.0° and 8.6° for Cu²⁺, Mn²⁺ and Fe³⁺, respectively, due to the Jahn–Teller effect and size and charge mismatch. In contrast to the host Zn²⁺ site with obvious axial elongation (～0.31 Å) and perpendicular (angular) rhombic distortion, all the impurity centres demonstrate more regular octahedral due to the above local lattice distortions. The copper centre exhibits significant Jahn–Teller reductions for the spin-orbit coupling and orbital angular momentum interactions, characterised by the Jahn–Teller reduction factor J (≈0.29 ? 1). The calculated EPR parameters agree well with the experimental results. The local structures of the impurity centres are analysed in view of the corresponding lattice distortions.     

Magnetic circularly polarized emission and magnetic circular dichroism of resolved vibronic lines in Cs2GeF6: Mn4+

Magnetic circularly polarized emission (M.C.P.E.) and magnetic circular dichroism (M.C.D.) techniques have been used to study at low temperatures resolved vibronic lines of the ⁴ A _2g ?² E_g transition in octahedral Mn⁴⁺(3d³) in the cubic host Cs₂GeF₆. Measurements have been made with applied magnetic field (and light propagation) along the [001] (F-Mn-F bond) and [111] directions. Though the Zeeman energy patterns are isotropic, the intensity patterns are not, and U′(Γ₈) eigenvectors for arbitrary field orientation have been derived. These have been used to calculate Zeeman intensity patterns for the [001] and [111] crystallographic directions, and the observed intensity variations with orientation are found to provide useful information about intensity mechanisms. In the case of the magnetic dipole origin, the intensity patterns as a function of orientation can be well accounted for by a first-order mechanism which, however, does not predict the small positive M.C.D. observed at the zero-field energy in the [111] orientation. A detailed analysis of this feature and previously measured energy spacings suggest that ζ_3d(Mn⁴⁺) should have a value of ～360 cm^-1 rather than the value 240 cm^-1 usually assumed. Electric dipole vibronic sidebands have been observed corresponding to v ₆(t _2u ), v ₄(t _1u ), v ₃(t _1u ), v ₄(t _1u ) + v ₅(t _2g ) and v ₂(e_g ) + v ₆(t _2u ). Using a U′→U′ vibronic intensity mechanism with spin-orbit mixing (Appendix A), the M.C.P.E. and total emission patterns for the first two of these regions can be quite well accounted for quantitatively. The corresponding M.C.D. in both cases, while in qualitative agreement with the M.C.P.E., shows much more complicated splitting patterns which are not explicable in terms of a simple k = 0 model. The other three vibronic regions can be accounted for qualitatively. In Appendix B a formula is derived which explicitly relates the M.C.P.E. of a vibronic emission line to its M.C.D. absorption counterpart.