A dynamic nuclear polarization strategy for multi-dimensional Earth's field NMR spectroscopy

Dynamic nuclear polarization (DNP) is introduced as a powerful tool for polarization enhancement in multi-dimensional Earth’s field NMR spectroscopy. Maximum polarization enhancements, relative to thermal equilibrium in the Earth’s magnetic field, are calculated theoretically and compared to the more traditional prepolarization approach for NMR sensitivity enhancement at ultra-low fields. Signal enhancement factors on the order of 3000 are demonstrated experimentally using DNP with a nitroxide free radical, TEMPO, which contains an unpaired electron which is strongly coupled to a neighboring ¹⁴N nucleus via the hyperfine interaction. A high-quality 2D ¹⁹F–¹H COSY spectrum acquired in the Earth’s magnetic field with DNP enhancement is presented and compared to simulation.     

~(129)Xe核自旋极化转移增强分子的核磁共振信号

激光极化的12 9Xe核具有极高的非平衡极化度和长的弛豫时间 ,这一特点使得它能够极化转移增强液体、固体或者固体表面分子中原子核自旋极化。因而 ,提高了它们的核磁共振探测灵敏度和扩展了在材料和表面科学研究中的应用。综述激光极化12 9Xe核与其它分子中原子核之间的极化转移研究与进展 ,介绍相关物理机制和参数的测量。     

NMR and IR investigations of biologically active peptides in solution

Summary Nuclear-magnetic-resonance and infra-red spectroscopic features in solution have been investigated for the delineation of conformation and dynamics of the chemotactic peptide formyl-L-methionyl-L-leucyl-L-phenylalanine. The main conformation is unfolded and characterized by a certain degree of weak intermolecular hydrogen bounding. The steric hindrance of neighbouring side chains limits the motional averaging of the several possible conformers by excluding some of the rotamers. Dipolar and scalar connectivities, as detected by 2D NMR spectroscopy, point to a cis configuration of the H−N−C−H_α moiety in the case of leucine and trans in the cases of methionine and phenylalanine.

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Riassunto Per il chiarimento della conformazione e della dinamica molecolare del peptide chemotattico formil-L-metionil-L-leucil-L-fenilalanina sono stati studiati i parametri spettroscopici di risonanza magnetica nucleare ed infrarosso in soluzione. La conformazione principale è distesa e caratterizzata da un certo grado di deboli legami a idrogeno intermolecolari. L’impedimento sterico di catene laterali vicine limita la possibilità che i vari conformeri possibili siano mediati dai moti molecolari, escludendo alcuni rotameri. Le connettività dipolari e scalari, messe in evidenza dalla spettroscopia 2D NMR, suggeriscono una configurazione cis del residuo H−N−C−H_α nel caso della leucina e trans nei casi della metionina e della fenila lanina.

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Реэюме Исследуются ядерный магнитный резонанс и инфра-красные спектроскопические характеристики в растворе с целью описания конформации и динамики хемотактичного пептида формия-Л-метионил-Л-лейцил-Л-фенилаланина. Основная конформация явлется раэвернутой и характериэуется определенной степенью слабой межмолекулярной водородной связй. Стерическое припятствие для соседних боковых цепей ограничивает динамическое усреднение для некоторых конформаций, исключая некоторые ротамеры. Дипольнье и скалярные связности, зарегистрированные с помощью 2D ЯМР-спектроскопии, указывают на цис-конфигурацию H−N−C−H_α в случае лейцина и на транс-конфигурацию в случаях метионина и фенилаланина.

     

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.     

毛细管电泳-核磁共振联用技术及其应用

毛细管电泳－核磁共振在线联用技术是新型的分离和生命大分子的有效手段之一。详细介绍了在ＣＥ－ＮＭＲ联用技术中最关键的ＮＭＲ对纳升数量级样品的检测技术和最新进展。     

Quantum phase transitions in antiferromagnets and superfluids

We present a general introduction to the non-zero temperature dynamic and transport properties of low-dimensional systems near a quantum phase transition. Basic results are reviewed in the context of experiments on the spin-ladder compounds, insulating two-dimensional antiferromagnets, and double-layer quantum Hall systems. Recent large N computations on an extended t–J model (Phys. Rev. Lett. 83 (1999) 3916) motivate a global scenario of the quantum phases and transitions in the high-temperature superconductors, and connections are made to numerous experiments.     

介质极化的瞬时相位与振幅

求解电子运动的二阶微分方程，在旋转波近似下，介质在外场突然变化时产生的瞬态感应极化与外场同频，但相位总是落后，最大落后为π/2；振幅大小与初态有关，随时间按指数规律衰减，衰减快慢由介质的阻尼系数决定。     

Numerical investigation of influence of ionic space charge and flexoelectric polarization on measurements of elastic constants in nematic liquid crystals

Deformations of nematic layers caused by magnetic field allow determination of the elastic constants of liquid crystal. In this paper, we simulated numerically the deformations of planar and homeotropic nematic layers. The flexoelectric properties of the nematic and presence of ions were taken into account. Our aim was to show the influence of flexoelectricity on the results of the real measurement of the elastic constants k₃₃ and k₁₁. In these simulations, we calculated the optical phase difference ΔΦ between the ordinary and extraordinary rays of light passing through the layer placed between crossed polarizers as a function of the magnetic field induction B. One of the elastic constants can be calculated from the magnetic field threshold for deformation. The ratio k₃₃/k₁₁ can be found by means of fitting theoretical ΔΦ(B) dependence to the experimental results. The calculations reveal that the flexoelectric properties influence the deformations induced by the external magnetic field. In the case of highly pure samples, this may lead to false results of measurement of the elastic constants ratio k₃₃/k₁₁. This influence can be reduced if the nematic material contains ions of sufficiently high concentration. These results show that the flexoelectric properties may play an important role, especially in well purified samples.     

Measurement and calculation of the Q‐branch spectrum of nitrogen using inverse Raman spectroscopy and cw Raman‐induced polarization spectroscopy

The techniques of inverse Raman spectroscopy, Raman‐induced polarization spectroscopy (RIPS), and optical heterodyne RIPS (OHD‐RIPS) are compared by probing the Q‐branch of the nitrogen molecule. The signal is measured employing either a photomultiplier tube (low background level–RIPS) or a photodetector (high background level–IRS and OHD‐RIPS). The measurements are performed using atmospheric mixtures of N₂ Ar with concentrations varying from 0 to 79% N₂. This strategy permits estimation of detection limits using the different techniques. Pump and probe energy levels are varied independently to study signal dependence on laser irradiance. A theoretical treatment is presented on the basis of the Raman susceptibility equations, which permits the calculation of spectra for all three techniques. Calculated Q‐branch spectra are compared with the measured spectra for the interactions of a linearly polarized probe beam with a linearly or circularly polarized pump beam. The polarizer angle in the detection path for OHD‐RIPS has a dramatic effect on the shape of the spectrum. The calculated and experimental OHD‐RIPS spectra are in good agreement over the entire range of investigated polarizer angles. Detection limits using these techniques are analyzed to suggest their applicability for measuring other species of importance in combustion and plasma systems. Copyright © 2007 John Wiley & Sons, Ltd.     

Double resonance experiments in low magnetic field: Dynamic polarization of protons by N and measurement of low NQR frequencies

The possibilities of dynamically polarizing proton spin system via the quadrupole ¹⁴N spin system in low magnetic field are analyzed. The increase of the proton magnetization is calculated. The polarization rate of the proton spin system is related to the transition probabilities per unit time between the ¹⁴N quadrupole energy levels and proton energy levels. The experiments performed in 1,3,5-triazine confirm the results of the theoretical analysis. A new double resonance technique is proposed for the measurement of nuclear quadrupole resonance frequencies ν_Q of the order of 100 kHz and lower. The technique is based on magnetic field cycling between a high and a low static magnetic field and observation of the proton NMR signal in the high magnetic field. In the low magnetic field the quadrupole nuclei and protons resonantly interact at the proton Larmor frequency ν_H = ν_Q/2. The quadrupole nuclei are simultaneously excited by a resonant rf magnetic field oriented along the direction of the low static magnetic field. The experimental procedure is described and the sensitivity of the new technique is estimated. Some examples of the measurement of low ¹⁴N and ²H nuclear quadrupole resonance frequencies are presented.     

XMCD studies of magnetic polarization at Mo atoms in CoMo alloy and magnetically coupled Co/Mo multilayers

Magnetic polarization of Mo atoms in Co₉₆Mo₄ alloy film and Co/Mo multilayered structures has been studied by X‐ray magnetic circular dichroism. Samples with Mo spacers of two different thicknesses (0.9 nm and 1.8 nm) were investigated. Mo atoms receive a magnetic moment of ?0.21μ_B in the alloy. In the multilayer with the thinner Mo spacer (d_Mo = 0.9 nm) the magnetic moment is much smaller (?0.03μ_B). In both cases the measured induced moment at the Mo site is oriented antiparallel to the moment at the Co atoms. The presence of the induced moment in the Mo spacer coincides with antiferromagnetic coupling between the Co component slabs. In contrast, neither measurable induced moment at the Mo site nor interlayer coupling between the Co layers has been found for the multilayer with the thicker Mo spacer. Possible mechanisms of the coupling associated with the induced moment are discussed in detail.     

高斯涡旋光束在自由空间传输中电场和磁场的偏振奇点

利用矢量菲涅尔衍射积分公式, 以高斯涡旋光束为例, 推导出傍轴高斯涡旋光束在自由空间传输过程中电场分量和磁场分量的解析表达式, 详细研究了自由空间中电场和磁场的偏振奇点变化规律. 结果表明, 高斯涡旋光束在自由空间传输中, 存在二维和三维电场和磁场的偏振奇点, 其位置一般不重合. 改变光束束腰宽度比、 振幅比以及传输距离, 偏振奇点出现移动. 在二维电场和磁场中, 当满足一定条件时, 会有V点产生.     

聚焦高斯涡旋光束焦区电场和磁场的偏振奇点

以高斯涡旋光束为例,研究了聚焦场中电场和磁场的偏振奇点变化规律.结果表明,高斯涡旋光束经透镜聚焦后,在焦区存在二维和三维电场和磁场的偏振奇点,其位置一般不重合.适当改变与焦面的距离以及光阑截断参数等出现圆偏振奇点的移动、产生和湮没.不同二维和三维电场和磁场圆偏振奇点湮没所对应的各参数临界值不同.在二维电场中,几何焦面上会有V点的产生.     

Influence of polarization direction, incidence angle, and geometry on near-field enhancement in two-layered gold nanowires

The influences of polarization direction, incidence angle, and geometry on near-field enhancements in two-layered gold nanowires (TGNWs) have been investigated by using the vector wave function method. When the polarization direction is perpendicular to the incidence plane, the local field factor (LFF) in TGNW decreases first and then increases with the increase in the incidence angle. The minimum LFF is observed at an incidence angle of 41°. It is found that the increase in the dielectric constant of the inner core leads to a decrease in the LFF. With the increase in the inner core radius, the LFF in TGNW increases first and then decreases, and the maximum LFF is observed at an inner core radius of 27 nm. On the other hand, when the polarization direction is parallel to the incidence plane, the collective motions of the induced electrons are enhanced gradually with the decrease in the incidence angle, and hence the near-field enhancement is increased.     

Comparison of analyzing power and polarization in the reaction 3H(p,n)3He: (II). New polarization results below 4 MeV

The polarization P^y for the ³H(p, n)³He reaction was measured for energies between 2 and 4 MeV. Special care was given to minimizing the effects of background and to interpreting the experimental spectra. The new values for P^y are significantly higher than previous values, and comparison to the available data for the analyzing power A_y for the same reaction now shows that in this energy range P^y and A_y are equal within experimental uncertainties. This equality negates earlier conclusions that sizeable differences existed between these observables. In particular, our new results demonstrate that in this reaction the effects of charge symmetry breaking on differences between these observables must be small.     

核磁共振技术在物质表面性质表征领域的新应用

核磁共振(nuclear magnetic resonance)技术具有快速、精确、分辨率高等优点,并已不断成熟成为土壤分析、物质结构鉴定、食品分析和医学成像等领域重要的研究分析手段。本文通过介绍利用NMR技术研究液相环境中高分子聚合物在颗粒表面(主要为SiO₂颗粒)的吸附、解吸及扩散等行为和利用NMR技术研究受污染土壤中水的摄取过程及土壤润湿性两大方面,综述了NMR技术在物质表面性质表征领域的重要应用,展现了NMR技术在高分子材料和环境领域中独特的重要作用。重点介绍基于NMR技术的Acorn比表面分析仪能够直接测定液相环境中物质的弛豫时间,反映物质的表面性质和结构特征,为解释污染物环境行为提供数据支持从而在环境领域发挥重要作用,展现出Acorn比表面分析仪相比于传统BET法在测量环境和测量时间等方面的优越性,尤其是Acorn比表面分析仪可以反映液相环境中物质的表面性质和结构特征的重要特性,解决了传统BET法无法直接获得液相环境中物质的比表面积信息的难题,是液相环境中NMR技术在物质表面性质表征领域的新突破。对Acorn比表面分析仪在制药、化妆品材料和电子产品等方面的应用进行了分析,并在土壤有机质、药物和天然产物检测等方面对NMR技术的应用进行了展望。     

Molecular dynamics and phase transitions in paramagnetic [Mn(H2O)6][SiF6] investigated by H NMR

The temperature dependences of ²H NMR spectra and spin-lattice relaxation time T₁ have been measured for paramagnetic [Mn(H₂O)₆][SiF₆]. The obtained ²H NMR spectra were simulated by considering the quadrupole interaction and paramagnetic shift. The variation of the spectra measured in phase III was explained by the 180° flip of water molecules. The activation energy E_a and the jumping rate at infinite temperature k₀ for the 180° flip of H₂O were obtained as 35 kJ mol⁻¹ and 4×10¹⁴ s⁻¹, respectively. The spectral change in phases I and II was ascribed to the reorientation of [Mn(H₂O)₆]²⁺ around the C₃ axis where the E_a and k₀ values were estimated as 45 kJ mol⁻¹ and 1×10¹³ s⁻¹, respectively. From the almost temperature independent and short T₁ value, the correlation time for electron-spin flip-flops, τ_e, and the exchange coupling constant J were obtained as 3.0×10⁻¹⁰ s and 2.9×10⁻³ cm⁻¹, respectively. The II-III phase transition can be caused by the onset of the jumping motion of [Mn(H₂O)₆]²⁺ around the C₃ axis.     

One-step synthesis of hydrophobic mesoporous silica and its application in nonylphenol adsorption

Highly CH₃-functionalized mesoporous silica with nearly spherical morphology was synthesized under acidic conditions by co-condensation of two different silica precursors polymethylhydrosiloxane (PMHS) and tetraethoxysilane (TEOS) in the presence of triblock copolymer P123 as template. XRD, N₂ adsorption–desorption, HRTEM, SEM and ²⁹Si MAS NMR were used to identify its highly-ordered mesopore array structure, nearly spherical particle morphology and CH₃ functionalization of the as-synthesized material. The resulting hydrophobic mesoporous silica possessed regular mesochannel arrays, indicating that the introduction of PMHS had little impact on the formation of an ordered mesostructure. Also, PMHS played an important role in morphology control and organic functionalization, ensuring nearly spherical particle morphology and high CH₃ functionalization degree of the obtained mesoporous silica material. As compared with pristine mesoporous silica SBA-15, the hydrophobic mesoporous silica showed the higher adsorption performance when they were used as adsorbents to remove organic pollutant nonylphenol at a very low concentration from aqueous solution.     

Study of the ferroelectric–paraelectric phase transition of NaH3(SeO3)2 single crystals by H and Na NMR

The ¹H and ²³Na spin–lattice and spin–spin relaxation times of NaH₃(SeO₃)₂ single crystals grown using the slow-evaporation method were measured as functions of temperature and frequency in the ferroelectric and paraelectric phases. The changes in the symmetry of the (SeO₃)²⁻ dimers as a result of the ferroelectric–paraelectric phase transition are associated with large changes in the spin–lattice and spin–spin relaxation times, and in the number of resonance lines. The large changes in the relaxation times at 195 K indicate that the H and Na ions are significantly affected by this transition. The change in the number of resonance lines for the ¹H and ²³Na nuclei means that the orientations of the (SeO₃)²⁻ dimers and the environments of the Na ions change at T_C. Therefore, the orientations of the (SeO₃)²⁻ dimers and the environments of the Na ions play important roles in the phase transitions. In conclusion, the ferroelectric–paraelectric phase transition of NaH₃(SeO₃)₂ is accompanied by changes in hydrogen-bond structure and distortions of the (SeO₃)²⁻ and Na⁺ ion lattices, which form a slightly distorted octahedron.     

FTIR, XRD, SEM and solid state NMR investigations of carbonate-containing hydroxyapatite nano-particles synthesized by hydroxide-gel technique

Nano-crystalline hydroxyapatite (HA), Ca₁₀(PO₄)₆(OH)₂ has been synthesized by a precipitate conversion technique using hydroxide gel at lower temperatures, e.g. 80 °C. HA crystallizes in hexagonal structure (space group: P6₃/m) having lattice parameters: and and around 17 nm in crystallite-size for the 80 °C-heated sample. SEM micrographs show hexagonal crystallites of average particle dimensions approximately 50×20 nm for 80 °C heated sample. The structure analysis by XRD, FTIR, ¹H and ³¹P MAS NMR show the existence of structural disorder at the particle surface that either does not form hydrogen bonding due to lack of adequate bonding parameters or forms a very weak dipolar bonding. The structural disorder has been explained as a result of chemical interactions between the phosphate groups either with the surface adsorbed water or the hydroxyl groups at the surface of the nano-particles.