Quadrupolar interaction study of various cations confined in porous charged polymer film of sPI ionomers

The structure of a sulfonated polyimide (sPI) ionomer membranes was investigated via the transport properties of various confined cations (7Li+, 23Na+, 87Rb+, 133Cs+). Their NMR spectra show large residual quadrupolar splitting depending on the orientation of the film in the static magnetic field B0. This behavior is the fingerprint of a macroscopic nematic ordering of charged interfaces. This is also confirmed by the anisotropy of the self-diffusion tensor measured by 1H and 7Li PGSE experiments on N(CH3)4+ and Li+ cations, respectively.     

Characterization of microporous aluminophosphate IST-1 using (1)H Lee-Goldburg techniques

The presence of two independent methylamine species in microporous aluminophosphate IST-1 (|(CH(3)NH(2))(4)(CH(3)NH(+)(3))(4)(OH(-))(4)|[Al(12)P(12)O(48)]) has been shown previously by synchrotron powder X-ray diffraction. One of these species, [N(1)-C(1)], links to a six-coordinated framework Al-atom [Al(1)], while the other methylamine [N(2)-C(2)] is protonated and hydrogen-bonded to three O-atoms [O(1), O(2) and O(12)]. We revisit the structure of IST-1 and report the complete assignment of the (1)H NMR spectra by combining X-ray data and high-resolution heteronuclear/homonuclear solid-state NMR techniques based on frequency-switched Lee-Goldburg homonuclear decoupling and (31)P-(31)P homonuclear recoupling. Careful analysis of the 2D (1)H-X homonuclear correlation (X=(1)H) and 2D heteronuclear correlation (X=(13)C, (31)P and (27)Al) spectra allowed the distinction of both methylamine species and the assignment of all (31)P and (13)C resonances. For the first time at a relatively high (9.4 T) magnetic field, symmetric doublet patterns have been observed in the (13)C spectra, caused by the influence of the (14)N second-order quadrupolar interaction.     

Evidence of simple intramolecular rearrangement at polymer end groups in secondary ion mass spectrometry

Polystyrenes with various end groups were analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS). These end groups were obtained by termination of the active anionic group by sulfonate or chlorosilane derivatives. Characteristic end group fragments for each sulfonate derivative were observed. On the one hand, for PS capped by methyl sulfonate, or -(CH(2))(4)-O-SO(2)-CH(3), almost complete end group fragment is observed at m/z 95 and a [O-SO(2)-CH(3)](-) molecular structure. On the other hand, when PS is terminated by silyl methyl sulfonate, or -Si(CH(3))(2)-(CH(2))(3)-O-SO(2)-CH(3), the most characteristic fragment in the fingerprint secondary ion mass spectrum is located at m/z 153 with [Si(CH(3))(2)-O-SO(2)-CH(3)](+) and the complete end group peak, [Si(CH(3))(2)-(CH(2))(3)-O-SO(2)-CH(3)](+), at m/z 201, is absent. According to the molecular structure, characteristic end group secondary ions can be emitted as complete or rearranged fragments. Various silylalkyl alcohol or sulfonate functionalities are analyzed and fragmentation pathways are discussed. To our knowledge, this is the first time that such rearrangement at silyl functions has been observed and demonstrated in fingerprint secondary ion mass spectra. Copyright 1999 John Wiley & Sons, Ltd.     

Mixed ion effects in Na/Ag-NaZr2(PO4)3

The ionic conductivity against the ionic ratio showed a shallow minimum in Na/Ag-NaZr₂(PO₄)₃ with a three-dimensional diffusion path. The ionic conductivity of the mixed ion system Na/Ag was calculated by means of the path probability method (PPM) using a two-dimensional honeycomb lattice model, resulting from the weak interaction between two different ions.²³Na MAS NMR spectra showed the second-order quadrupole interaction with the electric field gradient. It is concluded that the mixture of two ions in NaZr₂(PO₄)₃ with a three-dimensional diffusion path led to the conductivity minimum due to the ordered distribution of Ag and Na ions. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Ionic conductivity and anion diffusion in single crystals of lead chloride

The ionic conductivity and self-diffusion of chlorine ions in undoped single crystals of zone-refined lead chloride have been measured over the temperature range 625–370K. These measurements suggest that the conductivity and self-diffusion are due to simple vacancy migration as confirmed by the observed correlation factor. The activation energy of formation of vacancies is found to be 1.55 eV and that for migration of an anion is 0.38 eV. In the extrinsic region, the two measurements show marked discrepancies which are explained by assuming the presence of oxygen impurity ions in the lattice, and the mechanisms for their contribution to the observed excess conductivity are discussed.     

Nematic ordering of suspension of charged anisotropic colloids detected by multinuclear quadrupolar spectra and 1H PGSE-NMR measurements

The structure of aqueous dispersion of charged anisotropic nano-composites (synthetic Laponite clays) have been studied by NMR and numerical simulations based on a multi-scale statistical analysis have been used to interpret the mobility of the confined water molecule diffusing within dense Laponite aqueous dispersions (29-52% w/w) prepared by uniaxial compression. Firstly, the lineshape detected by NMR quadrupolar spectroscopy of the counterions ((23)Na or (7)Li) exhibits a large residual splitting Delta nu which is the fingerprint of the macroscopic nematic ordering of the anisotropic particles. Secondly, these results are also confirmed by the anisotropy of the self-diffusion tensor of the water molecule measured by (1)H Pulsed Gradient Spin Echo NMR. This self-diffusion anisotropy increases with the suspension density. Thirdly, the multi-scale statistical analysis of the water mobility bridges the gap between the time-scale (ps) accessible by Molecular Dynamics simulations and the time-scale (micros) accessible by Brownian Dynamics, leading to macroscopic behaviour comparable with PGSE-NMR data measurements.     

Mixed ion effects in Na/Cu-NaZr2(PO4)3

The mixed ion effect by which the conductivity minimum of a crystal with three dimensional diffusion path is observed is firstly reported for Na/Cu-NaZr₂(PO₄)₃. The phase diagram is also obtained by estimating the frequency dependence of ionic conductivity. The behavior is in agreement with the conductivity result. NMR spectra (²³Na MAS) showed the formation of an ordered distribution among different kinds of ions. The ionic conductivity of the mixed ion system Na/Cu was calculated for a two dimensional honeycomb lattice by means of the path probability method (PPM). It suggested that the mixture of two ions led to the conductivity minimum. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Entropy and enthalpy of formation and migration of lattice defects in Na(I)

The self-diffusion coefficients of Na⁺ and I^?, as well as the ionic conductivity, are measured in Na(I) single crystals, pure and doped with Ca²⁺ ions. The computer analysis of the whole set of data shows that the atom transport in Na(I) is ensured essentially by the free vacancies with a very small contribution (～4%) of the vacancy pairs. The thermodynamic parameters of vacancy formation and migration are derived by taking the long range interactions into account (activity coefficients on the concentrations and relaxation factors on the mobilities). The respective entropies of Schottky defect formation, cation migration and anion migration are equal to 7.64, 3.23 and 2.91 k while the corresponding enthalpies are equal to 2.00, 0.58 and 0.77 eV.     

低能氮离子注入固态羧酸钠的光谱分析

对２５ｋｅＶ Ｎ＾＋离子束辐照羧酸钠引起其分子结构的变化进行了研究,通过紫外光谱的分析,得到了离子注入后苯甲酸钠的残存剂量效应曲线,辐照后乙酸钠样品产生了新的具有紫外吸收的物质。傅里叶红外光谱分析证明,两种羧酸钠样品辐照后的产物中含有新的化学基团氰基。     

Competition between Na(+) and Li(+) for unsealed and cytoskeleton-depleted human red blood cell membrane: a (23)Na multiple quantum filtered and (7)Li NMR relaxation study.

Evidence for competition between Li(+) and Na(+) for binding sites of human unsealed and cytoskeleton-depleted human red blood cell (csdRBC) membranes was obtained from the effect of added Li(+) upon the (23)Na double quantum filtered (DQF) and triple quantum filtered (TQF) NMR signals of Na(+)-containing red blood cell (RBC) membrane suspensions. We found that, at low ionic strength, the observed quenching effect of Li(+) on the (23)Na TQF and DQF signal intensity probed Li(+)/Na(+) competition for isotropic binding sites only. Membrane cytoskeleton depletion significantly decreased the isotropic signal intensity, strongly affecting the binding of Na(+) to isotropic membrane sites, but had no effect on Li(+)/Na(+) competition for those sites. Through the observed (23)Na DQF NMR spectra, which allow probing of both isotropic and anisotropic Na(+) motion, we found anisotropic membrane binding sites for Na(+) when the total ionic strength was higher than 40 mM. This is a consequence of ionic strength effects on the conformation of the cytoskeleton, in particular on the dimer-tetramer equilibrium of spectrin. The determinant involvement of the cytoskeleton in the anisotropy of Na(+) motion at the membrane surface was demonstrated by the isotropy of the DQF spectra of csdRBC membranes even at high ionic strength. Li(+) addition initially quenched the isotropic signal the most, indicating preferential Li(+)/Na(+) competition for the isotropic membrane sites. High ionic strength also increased the intensity of the anisotropic signal, due to its effect on the restructuring of the membrane cytoskeleton. Further Li(+) addition competed with Na(+) for those sites, quenching the anisotropic signal. (7)Li T(1) relaxation data for Li(+)-containing suspensions of unsealed and csdRBC membranes, in the absence and presence of Na(+) at low ionic strength, showed that cytoskeleton depletion does not affect the affinity of Na(+) for the RBC membrane, but increases the affinity of Li(+) by 50%. This clearly indicates that cytoskeleton depletion favors Li(+) relative to Na(+) binding, and thus Li(+)/Na(+) competition for its isotropic sites. Thus, this relaxation technique proves to be very sensitive to alkali metal binding to the membrane, detecting a more pronounced steric hindrance effect of the cytoskeleton network to binding of the larger hydrated Li(+) ion to the membrane phosphate groups.     

乙胺分子的多光子电离过程质谱研究

报道了乙胺分子在４４０～４７５ｎｍ波长范围内多光子电离（ＭＰＩ）质谱（ＭＳ）研究结果。碎片离子主要由母体离子碎裂模式产生。母体离子ＣＨ３ＣＨ２Ｎ＋·Ｈ２由经３ｓ里德堡态的（２＋２）共振多光子电离产生后，大部分发生β键断裂，形成ＣＨ２＝Ｎ＋Ｈ２离子，还有一部分再吸收一个光子，通过Ｃ－Ｈ（ＣＨ２）键的断裂产生了ＣＨ３ＣＨ＝Ｎ＋Ｈ２离子。ＣＨ３ＣＨ＝Ｎ＋Ｈ２和ＣＨ２＝Ｎ＋Ｈ２离子最容易发生的碎裂过程是脱去氢分子，分别产生Ｃ２Ｈ４Ｎ＋（分子式）离子和ＣＨ≡Ｎ＋Ｈ离子。     

Sodium diffusion in cryolite at elevated temperatures studied by quasielastic neutron scattering

Quasielastic neutron scattering (QENS) has been applied to study the sodium mobility on nanosecond time scales in the perovskite fluoride cryolite, Na₃AlF₆, at high temperatures. Up to T = 1153 K the diffusion of Na ions is well described by a diffusion process of jumps between six and eight-fold coordinated sites. Above this temperature, where a step-like increase in the electrical conductivity occurs, the jump length increases, which indicates additional jumps over larger distances. The electrical conductivity derived from the self-diffusion coefficient via the Nernst–Einstein relation and the corresponding activation energy are in excellent agreement with the previous conductivity measurements. We conclude that the jump diffusion of sodium ions is the dominant mechanism for the electrical conductivity in cryolite at high temperatures up to T = 1153 K.     

Doping of LiNbO<Subscript>3</Subscript> and (Na,Li)NbO<Subscript>3</Subscript>-based solid solutions

Doping of LiNbO₃ and (Na,Li)NbO₃ with ions of different valence above stoichiometry has been performed. The effect of modifiers on the grain structure and electrical properties of these compounds has been investigated. It is shown that the conductivity of ceramics can be controlled.     

Transport processes in heavy metal fluoride glasses

Na self-diffusion, Li self-diffusion, Na⁺–Li⁺ ion exchange, electrical conductivity, and mechanical relaxation have been studied below T_g on glasses of the system ZrF₄–BaF₂–LaF₃–AF (A=Na, Li), with A=10, 20, 30 mol%. Compared to the transport mechanism in alkali-containing silicate glasses, the mechanisms in these non-oxide glasses are anomalous. Thus the self-diffusion coefficient of Na decreases with increasing NaF content, whereas that of Li increases with increasing LiF content. Both the electrical conductivity and the Na⁺–Li⁺ ion exchange reach a minimum at ≈ 20 mol% LiF, and the mechanical relaxation shows one peak for the 20 and 30 mol% LiF-glasses and two peaks for the glass with 10 mol% LiF, evidencing both a contribution of F⁻ and Li⁺ ions to the transport. Moreover, the presence of the three partially interacting mobile species F⁻, Na⁺, Li⁺ obviously leads to an anionic–cationic mixed ion effect. Applying the Nernst–Einstein equation to the Li⁺ transport in LiF-containing glasses shows that its mechanism is dissimilar to that in oxide glasses. Calculated short jump distances possibly can be interpreted as an Li⁺ movement via energetically suitable sites near F⁻ ions. Likewise the Nernst–Planck model, successfully applied to the ionic transport in mixed alkali silicate glasses, obviously does also not hold for the present heavy metal fluoride glasses.     

三种不同的钒氧簇合物的合成和光谱研究

利用水热法合成了三种钒氧簇合物：[{Ni(phen)₂}₂V₄O₁₂]H₂O (Ⅰ),[N(CH₂CH₂)₃NH]Na(H₂O)₆{K₄(H₂O)₄ [V₁₀O₂₈]}(H₂O)₄ (Ⅱ)和[(CH₃)₄N]₆[V₁₅O₃₆Cl] (Ⅲ)。通过用FTIR, UV-Vis DRS和荧光光谱研究了它们的结构和性能的关系。FTIR研究表明,化合物的相关基团的特征振动吸收峰和其结构相关。化合物Ⅰ的固体紫外漫反射光谱在200, 230, 260和350 nm出现四个宽峰,分别对应O_t→V, O_μ→Ni,O_μ→V荷移和phen的π-π*跃迁。文章还对这三个钒氧簇合物的荧光光谱进行了研究。最后,应用Gaussian98的量子化学计算,说明化合物Ⅰ的结构特点。     

Single-molecule conductance determinations on HS(CH2)4O(CH2)4SH and HS(CH2)2O(CH2)2O(CH2)2SH, and comparison with alkanedithiols of the same length

The acetyl-protected, thiol-terminated ethers AcS(CH(2))(4)O(CH(2))(4)SAc and AcS(CH(2))(2)O(CH(2))(2)O(CH(2))(2)SAc have been synthesised, and a range of related scanning tunnelling microscopy (STM)-based methods have been employed to fabricate and electrically characterise gold | single molecule | gold junctions involving these molecules. The single-molecule conductance values obtained are consistently found to be substantially higher (by a factor of 2-3) than the conductances of analogous alkanedithiols of similar length (HS(CH(2))(9)SH and HS(CH(2))(8)SH, respectively). A rationalisation of these findings is suggested, namely that the lone pair electrons on the oxygen atoms are substantially closer in energy to the Fermi energy of the gold leads than are the occupied and unoccupied states of methylene chains, so that the ether oxygens behave in a manner analogous to 'wells' in a double-tunnelling-barrier system. In agreement with this suggestion, the current-voltage behaviour of the monoether can be fitted using the Simmons approach, and the barrier height is found to be significantly lower than for alkanedithiols of approximately the same length.     

Dynamics of NaHSeO3 and NaHSeO4 single crystals by observation of 1H and 23Na spin-lattice relaxation

The 1H and 23Na spin-lattice relaxation times of NaHSeO3 and NaHSeO4 single crystals grown by the slow evaporation method were measured. The phase transitions of the two crystals were studied using differential scanning calorimetry (DSC), and the environments of the 1H and 23Na nuclei in these crystals were investigated by means of 1H and 23Na NMR spectroscopy. The DSC results show that NaHSeO3 crystals do not undergo phase transitions, whereas for NaHSeO4 crystals there is a small endothermic peak at 419 K. The dimers in NaHSeO3 stabilize its structure to the extent that there are no phase transitions even in the presence of disordered hydrogen bonds. In addition, the NMR results indicate that the temperature dependencies of T1 for the 1H and 23Na nuclei in the two hydrogen-bonded crystals-the NaHSeO3 crystal with 3-coordinated SeO3 and the NaHSeO4 crystal with 4-coordinated SeO4--are significantly different. The different trends in T1 for Na in the two crystals are accompanied by different shifts of the oxygen atoms from the 3-coordinated SeO3 and the 4-coordinated SeO4 species around the Na+ ions. Thus, although the two crystals have hydrogen-bonded structures, the differences between the hydrogen bonding of the 3-coordinated SeO3 in NaHSeO3 and the hydrogen bonding of the 4-coordinated SeO4 in NaHSeO4 result in different T1 temperature dependences and different phase transitions.     

Violation of the holographic viscosity bound in a strongly coupled anisotropic plasma

We study the conductivity and shear viscosity tensors of a strongly coupled N=4 super-Yang-Mills plasma which is kept anisotropic by a θ parameter that depends linearly on one of the spatial dimensions. Its holographic dual is given by an anisotropic axion-dilaton-gravity background and has recently been proposed by Mateos and Trancanelli as a model for the preequilibrium stage of quark-gluon plasma in heavy-ion collisions. By applying the membrane paradigm which we also check by numerical evaluation of Kubo formula and lowest lying quasinormal modes, we find that the shear viscosity purely transverse to the direction of anisotropy saturates the holographic viscosity bound, whereas longitudinal shear viscosities are smaller, providing the first such example not involving higher-derivative theories of gravity and, more importantly, with fully known gauge-gravity correspondence.     

Velocity and diffusion imaging in dynamic NMR microscopy

The imposition of resolution gradients in a pulsed-gradient spin-echo (PGSE) NMR sequence induces motionally dependent phase and amplitude modulation in the image, a technique which we have termed dynamic NMR microscopy. Fourier analysis of this modulation gives a dynamic displacement profile for each pixel which can then be analyzed to obtain velocity and diffusion maps. The application of this method at high spatial resolution is motivated by a desire to measure vascular flow in living plants and variations in molecular self-diffusion under the influence of velocity shear in narrow capillaries. The theory of dynamic NMR microscopy is presented and potential artifacts discussed, including the effect of slice selection gradients, PGSE gradient nonuniformity, and specific problems associated with the measurement of self-diffusion in the presence of velocity gradients. It is demonstrated that a double-echo PGSE pulse sequence can be used to restore coherent phase shifts associated with steady-state flow, and examples of self-diffusion maps and signed velocity maps from sequences of phase-encoded images obtained by projection reconstruction are given. This method has been applied at 20,um transverse resolution in laminar capillary flow.     

Analysis and Improvement of Reflection-type Transverse Modulation Optical Voltage Sensors

Reflection-type transverse modulation optical voltage sensors, which employ reflection retarders to replace quarter-wave plates, are convenient for practical use. In previous literatures, the measured voltage was all applied to Bi4Ge3O12 crystal along the (110) direction for transverse modulation optical voltage sensor, and crystals are used as sensing materials. In this paper, reflection-type transverse modulation optical voltage sensor has been analyzed theoretically and a novel configuration in which the measured voltage is applied to a Bi4C-e3O12 crystal along the (001) direction with light wave passing through the crystal in the (110) direction has been proposed. According to this theoretical analysis, a novel optical voltage sensor, which can be used in a 220 kV optical fiber voltage transformer, has been designed and assembled. Experimental results showed that the linearity and the stability of the sensor during 24 hours can reach 0.3％.