Overhauser dynamic nuclear polarization and molecular dynamics simulations using pyrroline and piperidine ring nitroxide radicals

The efficiency of Overhauser dynamic nuclear polarization (DNP) depends on the local dynamics modulating the dipolar coupling between the two interacting spins. By attaching nitroxide based spin labels to molecules and by measuring the ¹H DNP response of solvent water, information about the local hydration dynamics near the spin label can be obtained. However, there are two commonly used types of nitroxide ring structures; a pyrroline based and a piperidine based molecule. It is important to know when comparing different experiments, whether changes in DNP enhancements are due to changes in local hydration dynamics or because of the different spin label structures. In this study we investigate the key parameters affecting DNP signal enhancements for 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-oxyl, a 5-membered ring nitroxide radical, and for 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy, a 6-membered ring nitroxide radical. Using X-Band DNP, field cycling relaxometry, and molecular dynamics simulations, we conclude that the key parameters affecting the DNP amplitude of the ¹H signal of water to be equal when using either nitroxide. Thus, experiments measuring hydration dynamics using either type of spin labels may be compared.     

In VivoLongitudinally Detected ESR Measurements at Microwave Regions of 300, 700, and 900 MHz in Rats Treated with a Nitroxide Radical

A signal detector of longitudinally detected ESR (LODESR) is independent of the resonant frequency. We developed anin vivoLODESR spectrometer operating in the regions of 300, 700, and 900 MHz. Using this apparatus, we estimated signal intensities at different operating frequencies obtained from non- or high-dielectric loss phantoms that contained nitroxide radical solutions and from live rats that had received a nitroxide radical. Our result, higher signal intensities in the high-dielectric loss samples (such as physiological saline solution and animals) at a lower frequency, shows that the influence of a decrease in dielectric loss dominates over the signal reduction caused by smaller Zeeman splitting. We believe that this finding strongly supports anin vivoESR resonant frequency that tends to be low.     

Localization of matters on the bent brane in bulk

We investigate the possibility of localizing various matter fields on a bent AdS₄ (dS₄) thick brane in AdS₅. For spin 0 scalar field, we find a massless zero mode and an excited state which can be localized on the bent brane. For spin 1 vector field, there is only a massless zero mode on the bent brane. For spin 1/2 fermion field, it is shown that, in the case of no Yukawa coupling of scalar-fermion, there is no existence of localized massless zero mode for both left and right chiral fermions. In order to localize massless fermions, some kind of Yukawa coupling must be included. We study two types of Yukawa couplings as examples. Localization property of chiral fermions is related to the parameters of the brane model, the Yukawa coupling constant and the cosmological constant of the 4-dimensional space–time.     

Saturation recovery EPR and ELDOR at W-band for spin labels

A reference arm W-band (94 GHz) microwave bridge with two sample-irradiation arms for saturation recovery (SR) EPR and ELDOR experiments is described. Frequencies in each arm are derived from 2 GHz synthesizers that have a common time-base and are translated to 94 GHz in steps of 33 and 59 GHz. Intended applications are to nitroxide radical spin labels and spin probes in the liquid phase. An enabling technology is the use of a W-band loop-gap resonator (LGR) [J.W. Sidabras, R.R. Mett, W. Froncisz, T.G. Camenisch, J.R. Anderson, J.S. Hyde, Multipurpose EPR loop-gap resonator and cylindrical TE₀₁₁ cavity for aqueous samples at 94 GHz, Rev. Sci. Instrum. 78 (2007) 034701]. The high efficiency parameter (8.2 GW^−1/2 with sample) permits the saturating pump pulse level to be just 5 mW or less. Applications of SR EPR and ELDOR to the hydrophilic spin labels 3-carbamoyl-2,2,5,5-tetra-methyl-3-pyrroline-1-yloxyl (CTPO) and 2,2,6,6,-tetramethyl-4-piperidone-1-oxyl (TEMPONE) are described in detail. In the SR ELDOR experiment, nitrogen nuclear relaxation as well as Heisenberg exchange transfer saturation from pumped to observed hyperfine transitions. SR ELDOR was found to be an essential method for measurements of saturation transfer rates for small molecules such as TEMPONE. Free induction decay (FID) signals for small nitroxides at W-band are also reported. Results are compared with multifrequency measurements of T_1e previously reported for these molecules in the range of 2–35 GHz [J.S. Hyde, J.-J. Yin, W.K. Subczynski, T.G. Camenisch, J.J. Ratke, W. Froncisz, Spin label EPR T₁ values using saturation recovery from 2 to 35 GHz. J. Phys. Chem. B 108 (2004) 9524–9529]. The values of T_1e decrease at 94 GHz relative to values at 35 GHz.     

Correlation inequalities for vector spin models

Correlation inequalities forn-vector spin models (n 2) are reviewed. A relatively simple and unified derivation of the inequalities is achieved, using duplicate variable methods, for spin dimensionalitiesn=2 (plane rotator model),n=3 (classical Heisenberg model), andn=4. Although correlation inequalities are lacking forn > 4, new proofs are presented for the comparison inequalities relating correlations for systems with arbitrary spin dimensionality to corresponding correlations for systems with low spin dimensionality (n = 1 or 2).Research supported by National Science Foundation under Grant DMR 76-23071.     

Contribution of superstring <Emphasis Type="Italic">Z</Emphasis>′ boson on the polarization effects in proton proton collisions

In this work we investigate the single- and the double-spin asymmetries at the collisions of polarized protons pp → (γ ^*, Z ⁰, Z′) + X within the scope of QCD, the electroweak interaction and superstring E ₆ theory. The helicity amplitude method is used. Analytical expressions for the single- and the double-spin asymmetries are obtained and their dependence on the transverse momentum of the lepton pair is investigated at the three different values of invariant masses of the lepton pair. The pure contribution coming from the superstring Z′ boson on the single- and double- spin asymmetries has been extracted. The results obtained allow investigation of the spin structure of the proton.     

The Temperature Dependence of Nitroxide Spin–Label Interaction Parameters: a High-Field EPR Study of Intramolecular Motional Contributions

High-field W-band electron paramagnetic resonance (EPR) spectroscopy was utilized to study the temperature dependence of the magnetic interaction parameters (g-, hyperfine-, quadrupole tensors) of two types of doublet-state nitroxide spin probes in glass-forming ortho-terphenyl solution: a five-membered ring system of pyrroline type (model for the commonly used methane thiosulfonate spin label) and a six-membered ring system of piperidine type (model for the commonly used TOAC spin label). The analysis of the g- and hyperfine tensors in terms of their isotropic and anisotropic parts reveals at least two mechanisms of motion that are responsible for the temperature dependence of the interaction parameters. The first mechanism is attributed to the overall small-angle motion of the nitroxide molecule in the glassy matrix; it leads to an averaging of the anisotropies of the EPR parameters. The second mechanism originates in an intramolecular out-of-plane motion of oxygen in the nitroxide group. This type of motion is evidenced by comparing the experimental findings for the spin-interaction parameters with the results of density functional theory calculations. The harmonic oxygen out-of-plane vibrations result in a variation of both the isotropic and anisotropic parts of the g- and hyperfine tensors. In contrast, the quadrupole tensor is not influenced by this vibration mechanism in the temperature range under study (90–240 K). Consequences of the applicability of such typical nitroxide radicals for probing details of their protein environment and for studying librational dynamics in frozen solutions are discussed.     

Derivation of the vacuum longitudinal fieldB (3) from the Dirac equation of the electron in the electromagnetic field

By solving the Diras equation for the motion of an electron (c) in the circularly polarized electromagnetic field it is shown that the intrinsic electron spin forms an interaction Hamiltonian with a time independent fieldB ⁽³⁾ of electromagnetic radiation in the vacuum. In the same way as intrinsic spin is a fundamental property of the electron,B ⁽³⁾ is therefore a fundamental and intrinsic property of the vacuum electromagnetic field.     

铁磁/半导体/铁磁结构的双量子环自旋输运的特性

研究了与铁磁/半导体/铁磁结构相关的双量子环自旋输运的规律,研究结果表明：总磁通为零条件下,铁磁电极磁化方向反平行时,双量子环与单量子环相比提高了自旋电子透射概率的平均值.铁磁电极磁化方向平行时,双量子环对提高自旋向下电子平均透射概率的效果更明显;双量子环受到Rashba自旋轨道耦合作用影响时,自旋电子的平均透射概率明显高于单量子环,即使再加上外加磁场的影响,透射概率较高这一特征依然存在;双量子环所含的δ势垒具有阻碍自旋电子输运的作用,随δ势垒强度Z的增大透射概率 关键词： 双量子环 Rashba自旋轨道耦合 透射概率 δ势垒')" href="#">δ势垒     

Structural and spectroscopic properties of small Pun （n= 2-5） molecules

The equilibrium structures and the electronic, spectroscopic and thermodynamic properties of small Pu_n (n=2-5) molecules are systematically investigated using the methods of general gradient approximation (GGA) of density functional theory (DFT). The results show that the bond length of the lowest-energy structure of Pu₂ is 2.578 AA. The ground state structure of Pu₃ is a triangle with D_3h symmetry, whereas for Pu₄, the ground state structure is a square (D_4h) and the spin polarization of 16 for molecule Pu₅ with square geometry (D_4h) is the most stable structure. For the ground state structures, the vibrational spectra as well as thermodynamic parameters are worked out. In addition, the values for the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) along with the energy gap of all the Pu_2-5 structures are presented. The relevant structural and chemical stabilities are predicted.     

Calculation of pulsed NMR signal in I=3/2 quadrupolar spin system

The rf pulse response of I=3/2 spin system experiencing first order quadrupolar splitting is studied using density matrix approach. A general expression is derived in terms of spin populations, quadrupole splitting and duration and amplitude of the rf pulse for calculating the NMR signal arising due to the centre line and satellite resonances for the situation where the impressed rf pulse excites the resonances selectively as well as non-selectively. The necessary 4×4 transformation matrix obtained analytically by diagonalyzing the Hamiltonian are used to get the expression for the centre line response. The satellite signals are obtained in the same way but by using the numerical values of the roots of the related quartics. The widths of the corresponding π/2-pulses are calculated for different initial spin populations. The variations of this pulse-width and the corresponding signal amplitude as a function of satellite splitting are studied.     

SU(N) supersymmetry onS 3 × R spacetime

As the whole physical community is celebrating 30 years of supersymmetry, the aim of the present paper is to analyse an 50(3,1) ×SU(N)— gauge invariant supersymmetric model on the Einstein’s universe. Thus, by exploiting the maximalS ³ symmetry, which allows the use of group theoretical techniques, we deal with a (1/2, 1, 3/2)—spin particle system on theS ³ ×R manifold. After we derive the Dirac-Rarita-Schwinger-Yang-Mills-type field equations, we focus on the additional terms that come into theory as a result of the compactness of space and spin coupling to gravity.     

Density-functional calculations of the nuclear magnetic shielding and indirect nuclear spin–spin coupling constants of three isomers of C20

The parameters of the nuclear magnetic resonance (NMR) spectrum – shielding constants and indirect spin–spin coupling constants – of three isomers of C₂₀ are studied using density-functional theory. The performance of different exchange–correlation functionals is analysed by optimising the geometry for the ring, bowl and cage isomers, followed by a computation of the NMR constants at the optimised structure. The results are analysed and rationalised by performing comparisons of the three isomers with one another and with related systems such as polyynes (for the ring), o-benzyne (for the bowl) and C₆₀ (for the cage). The shielding and spin–spin parameters calculated using the Perdew–Burke–Ernzerhof (PBE) exchange–correlation functional are sufficiently reliable to assist in future experimental NMR studies of C₂₀ and, in particular, the identification of its isomers.     

NiMgn(n=1—12)团簇的第一性原理研究

采用基于密度泛函理论(DFT)中的广义梯度近似 (GGA),在考虑自旋多重度的情况下,对NiMg_n(n=1—12)团簇进行了构型优化,频率分析和电子性质计算.结果表明：n=1,2时,体系的基态为自旋三重态,n≥3时,为单重态;Ni原子掺杂使主团簇结构发生了明显变化. n≤8时,三角双锥,四角双锥结构主导着NiMg_n基态团簇的生长行为; n在9—12之间时,主团簇Mg_n+1(n=1—12)的基于三棱柱构型的基态演化行为发生了一定程度的改变;n≥6时,Ni原子陷入了主团簇内部;掺杂使体系的平均结合能增大,能隙减小;n=4,6,10是团簇的幻数;不同尺寸团簇的s, p, d轨道杂化中,Ni原子3d, 4p成分所起作用不同; NiMg₆基态结构具有很高的对称性(O_h),很好的稳定性和化学活性,能隙仅为0.25eV. 关键词： n团簇')" href="#">NiMg_n团簇 几何结构 稳定性 化学活性     

内掺过渡金属非典型富勒烯M@C22(M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni) 几何结构、电子结构、稳定性和磁性的密度泛函研究

采用密度泛函理论中广义梯度近似对非典型富勒烯C₂₂和过渡金属内掺衍生物M@C₂₂(M=Sc,Ti,V,Cr,Mn,Fe,Co和Ni)的几何结构和电子结构进行计算研究.发现非典型富勒烯C₂₂的基态结构是含有一个四碳环的单重态笼状结构.过渡金属原子的掺入明显提高了体系的稳定性. C-M键既有一定共价性又有一定离子性.磁性、能级图、轨道分布和态密度图分析表明: M原子的3d轨道和碳笼的C原子的原子轨道之间存在较强的轨道杂化. Ti, Cr, Fe和Ni内掺的结构出现磁性完全猝灭现象. Sc和碳笼间是弱反铁磁作用, V,Mn和Co与碳笼间是弱铁磁作用.     

Structure of odd–odd La at high spin

The high spin states in the N=79 odd–odd ¹³⁶La nucleus have been investigated by in-beam γ-spectroscopic techniques following the ¹³⁰Te(¹¹B, 5n)¹³⁶La reaction at E=52 MeV using an array, consisting of eight Compton-suppressed clover germanium detectors. Thirty nine new γ rays have been assigned to ¹³⁶La on the basis of γ ray singles and γγ-coincidence data. The level scheme of ¹³⁶La has been extended above the known 115 ms isomer upto an excitation energy of 4.6 MeV and spin 18. Thirty one new levels have been proposed and spin-parity assignments for most of the newly proposed levels have been made on the basis of the deduced asymmetry ratios and polarisation information for the de-exciting transitions. The observed positive parity yrast band has been compared with the theoretical calculation, done within the framework of particle rotor coupling model (PRM) where the two odd quasi-particles are coupled to an axially symmetric core. The level structure has been discussed in the light of the known systematics of the neighbouring N=79 isotonic nuclei.     

A band-mixing Hartree-Fock model for62Zn

Energy levels and electromagnetic transitions in⁶²Zn have been calculated using band-mixing formalism in the framework of deformed Hartree-Fock theory. Matrix elements of Adjusted-Surface Delta Interaction (ASDI) and of Tabakin interaction have been used. Detailed structure of various nuclear states in terms of bands has been discussed. Although the calculated spectra for both the interactions are somewhat compressed as compared to the observed spectra, the ASDI results are in substantially better agreement with experiments. Several additional states of high spin (J>4) have been predicted.B(E2) transitions between inter-band as well as some of the intraband states are calculated to stimulate further experiments.     

Rotational co-existence in selenium isotopes

High spin states of ^72,73,74Se nuclei are discussed using calculations from the cranked Nilsson Strutinsky method with tuning to fixed spins. The low spin anomaly in the yrast bands of these nuclei is interpreted in a rotational co-existence picture. High K rotational isomers are proposed for I ^π =4⁺ in ⁷²Se and 6⁺ in ⁷⁴Se.