The conductivity properties of protons in ice and mechanism of magnetization of liquid water

From a study of electrical conductivity of protons in the hydrogen-bonded chains in ice we confirm that the magnetization of liquid water is caused by proton transfer in closed hydrogen-bonded chains occurring as a first order phase transition, through which the ice becomes liquid water. We first study the conductive properties of proton transfer along molecular chains in ice crystals in our model. Ice is a typical hydrogen-bonded molecular system, in which the interaction of localized fluctuation of hydrogen ions (H⁺) with deformation of a structure of hydroxyl group (OH) results in soliton motion of the protons along the molecular chains via ionic and bonded defects. We explain further the quantum conductive properties of proton transfer and determine its mobility and conductivity under constant electric-field using a new theory of proton transfer, which agree with experimental values. From features of first order phase-transition for ice, and some experimental data of pure and magnetized water we confirm further that there are not only free water molecules, but also many linear and closed hydrogen-bonded chains consisting of many polarized water-molecules in the liquid water. Thus a ring proton-current, which resembles to a “molecular current” or a “small magnet” in solids, can occur in the closed hydrogen-bond chains under action of an externally applied magnetic field. Then the water molecules in the closed chains can be orderly arrayed due to the magnetic interaction among these ring proton currents and the externally applied magnetic field. This is just the magnetized effect of the water. In such a case the optical and electronic properties of the water, including the dielectric constant, magnetoconductivity, refraction index, Raman and Infrared absorption spectra, are changed. We determine experimentally the properties of the magnetized water which agree with the theoretical results of our model. However, the magnetized effect of water is, in general, very small, and vanishes at temperatures above 100 ^○C.     

Kinetics and mechanism of proton transport across membrane nanopores

We use computer simulations to study the kinetics and mechanism of proton passage through a narrow-pore carbon-nanotube membrane separating reservoirs of liquid water. Free energy and rate constant calculations show that protons move across the membrane diffusively along single-file chains of hydrogen-bonded water molecules. Proton passage through the membrane is opposed by a high barrier in the effective potential, reflecting the large electrostatic penalty for desolvation and reminiscent of charge exclusion in biological water channels. At neutral pH, we estimate a translocation rate of about 1 proton per hour and tube.     

NMR evidence for a "Generalized spin-peierls Transition" in the high-magnetic-field phase of the spin ladder Cu2(C5H12N2)2Cl4

The magnetic-field-induced 3D ordered phase of the two-leg spin ladder Cu2(C5H12N2)2Cl4 has been probed through measurements of 1H NMR spectra and 1/T1 in the temperature range 70 mK-1.2 K. The second order transition line T(c)(H) has been determined between H(c1) = 7.52 T and H(c2) = 13.5 T and varies as (H-H(c1))(2/3) close to H(c1). From the observation of anomalous shifts and a crossover in 1/T1 above T(c), the mechanism of the 3D transition is argued to be magnetoelastic as in spin-Peierls chains, here involving a displacement of the protons along the longitudinal exchange ( J( parallel)) path.     

3D HCCH(3)-TOCSY for resonance assignment of methyl-containing side chains in (13)C-labeled proteins

Two 3D experiments, (H)CCH(3)-TOCSY and H(C)CH(3)-TOCSY, are proposed for resonance assignment of methyl-containing amino acid side chains. After the initial proton-carbon INEPT step, during which either carbon or proton chemical shift labeling is achieved (t(1)), the magnetization is spread along the amino acid side chains by a carbon spin lock. The chemical shifts of methyl carbons are labeled (t(2)) during the following constant time interval. Finally the magnetization is transferred, in a reversed INEPT step, to methyl protons for detection (t(3)). The proposed experiments are characterized by high digital resolution in the methyl carbon dimension (t(2max) = 28.6 ms), optimum sensitivity due to the use of proton decoupling during the long constant time interval, and an optional removal of CH(2), or CH(2) and CH, resonances from the F(2)F(3) planes. The building blocks used in these experiments can be implemented in a range of heteronuclear experiments focusing on methyl resonances in proteins. The techniques are illustrated using a (15)N, (13)C-labeled E93D mutant of Schizosacharomyces pombe phosphoglycerate mutase (23.7 kDa).     

Charge Separation at the Evaporation (Condensation) Front of Water and Ice. Charging of Spherical Droplets

Charge separation at evaporation (condensation) front of water and ice is analyzed. Relatively low distribution coefficient of protons and hydroxide ions between vapor and condensed phase that is less than the distribution coefficient of water molecules leads to accumulation of protons and hydroxide ions at the phase front upon evaporation and a decrease in the amount of such species upon condensation. Interphase charge separation is caused by the subsequent diffusion of nonequilibrium protons and hydroxide ions. The charge separation is also affected by the double electric layer generated by orientation defects at the water and ice surfaces. Dependences of electric field at a plane surface of water and ice on the rate of phase transformation are calculated. Electric charges of spherical water droplets are estimated at different field strengths and droplet radii.     

Anisotropic water chain growth on Cu(110) observed with scanning tunneling microscopy

We report a novel structure of water aggregate by means of scanning tunneling microscopy. Water molecules are self-assembled into one-dimensional chains on Cu(110) at 78 K. The chain exhibits a zigzag structure with a period of 7.2 A and grows to a length of approximately 1000 A. We propose that water hexamers are arranged alternately along the chain. Interchain repulsion due to dipole interaction facilitates the 1D chain growth. A two-dimensional overlayer develops only at high coverage.     

螺双杯[4]芳烃-冠-3醚在溶液中构象的研究

研究了螺双杯[4]芳烃-冠-3醚在溶液状态下的¹H、¹³C、¹H-¹³C HMQC、¹H-¹³C HMBC、¹H-¹H TOCSY等核磁共振谱,对其¹H、¹³C谱进行了归属,确定了室温该化合物在溶液状态下的稳定构象为锥式,并利用2D NOESY近似求出杯芳烃区的各种氢的距离,以此为约束进行了模拟淬火计算,证实了2D NOESY谱中多种羟基存在方式,并利用二维交换矩阵计算得出几种羟基的交换速率及其与溶剂中痕量水的交换速率.     

2D 1H-31P solid-state NMR studies of the dependence of inter-bilayer water dynamics on lipid headgroup structure and membrane peptides

The dynamics of hydration-water in several phospholipid membranes of different compositions is studied by 2D (1)H-(31)P heteronuclear correlation NMR under magic-angle spinning. By using a (1)H T(2) filter before and a (1)H mixing-time after the evolution period and (31)P detection, inter-bilayer water is selectively detected without resonance overlap from bulk water outside the multilamellar vesicles. Moreover the (1)H T(2) relaxation time of the inter-bilayer water is measured. Lipid membranes with labile protons either in the lipid headgroup or in sterols exhibit water-(31)P correlation peaks while membranes free of exchangeable protons do not, indicating that the mechanism for water-lipid correlation is chemical exchange followed by relayed magnetization transfer to (31)P. In the absence of membrane proteins, the inter-bilayer water (1)H T(2)'s are several tens of milliseconds. Incorporation of charged membrane peptides shortened this inter-bilayer water T(2) significantly. This T(2) reduction is attributed to the peptides' exchangeable protons, molecular motion and intermolecular hydrogen bonding, which affect the water dynamics and the chemically relayed magnetization transfer process.     

Fluorescence of Zinc Complex with N,N'-Bis(5-Bromosalicylidene)Ethylenediamine

Infrared (IR) spectra of a number of crystals with proton conductivity have been investigated. The width of the band gap is determined, and most lines of the IR absorption spectra are identified. A direct proof of the existence of protons, defects ОН–and Н₃О⁺, molecules of adsorbed and crystallization water in the crystals grown in ordinary and in heavy water is also carried out. The transparency of the rectangular potential barrier for protons is calculated, and the possibility of tunneling and translational diffusion of protons in wide-band-gap crystals is shown.     

A 1D sensitivity-enhanced 1H spin diffusion experiment for determining membrane protein topology

A sensitivity-enhanced 1D (1)H spin diffusion experiment, CHH, for determining membrane protein topology is introduced. By transferring the magnetization of the labeled protein (13)C to lipid and water protons for detection, the CHH experiment reduces the time of the original 2D (13)C-detected experiment by two orders of magnitude. The sensitivity enhancement results from (1)H detection and the elimination of the (13)C dimension. Consideration of the spin statistics of the membrane sample indicates that the CHH sensitivity depends on the (13)C labeling level and the number of protein protons relative to the mobile protons. 5-35% of the theoretical sensitivity was achieved on two extensively (13)C labeled proteins. The experimental uncertainties arise from incomplete suppression of the equilibrium (1)H magnetization and the magnetization of lipid protons directly bonded to natural-abundance carbons. The technique, demonstrated on colicin Ia channel domain, confirms the presence of a transmembrane domain and the predominance of surface-bound helices.     

Effects of thermal denaturation on the longitudinal relaxation time (T1) of water protons in protein solutions: study of the factors determining the T1 of water protons

The factors determining the longitudinal relaxation time (T1) of water protons in protein solutions were investigated by analyzing the effects of thermal denaturation on the T1 of the water protons. We treated the water protons and the protein protons "on a protein surface" as a dipole-dipole coupled two-spin system where relative translational diffusion is the dominant mechanism, and measured the change in the time development of the nuclear Overhauser effect (NOE) factors of the water protons. The T1 of the water protons was shortened markedly when the proteins were thermally denatured. Our analysis indicates that this relaxation enhancement is due to an increase in the value of the translational correlation time as well as the fraction of hydration water molecules, though the influence of "proton exchange" between the water protons and the labile protein protons cannot be completely neglected.     

Nonexponential nuclear spin-lattice relaxation in the isotropic phase of thermotropic liquid crystals

In the isotropic phase of nematic and smectic liquid crystals T₁ of CH3 and chain protons is larger than that of ring and ring-neighboured protons being caused by fast CH₃ reorientation and internal motions in chains, respectively.     

Radiation effects of 50-MeV protons on PNP bipolar junction transistors

The effects of radiation on 3CG110 PNP bipolar junction transistors (BJTs) are characterized using 50-MeV protons, 40-MeV Si ions, and 1-MeV electrons. In this paper, electrical characteristics and deep level transient spectroscopy (DLTS) are utilized to analyze radiation defects induced by ionization and displacement damage. The experimental results show a degradation of the current gain and an increase in the types of radiation defect with increasing fluences of 50-MeV protons. Moreover, by comparing the types of damage caused by different radiation sources, the characteristics of the radiation defects induced by irradiation show that 50-MeV proton irradiation can produce both ionization and displacement defects in the 3CG110 PNP BJTs, in contrast to 40-MeV Si ions, which mainly generate displacement defects, and 1-MeV electrons, which mainly produce ionization defects. This work provides direct evidence of a synergistic effect between the ionization and displacement defects caused in PNP BJTs by 50-MeV protons.     

月球表面环境对Mo/Si多层膜光学特性的影响

研究了月球表面高温、强辐射的空间环境下Mo/Si多层膜的热稳定性和辐照稳定性。Mo/Si多层膜采用磁控溅射法镀制,将制备好的多层膜在100℃和200℃高温下加热,利用激光等离子体反射率计和X射线衍射仪(XRD)对加热前后的多层膜进行了测量。结果显示在200℃以内,多层膜反射率和中心波长没有显著变化,表现出良好的热稳定性。利用Monte Carlo方法模拟了质子在多层膜内造成的缺陷的分布和浓度分布。模拟显示,能量大的质子沉积在多层膜内部,造成的缺陷也集中在多层膜内部。用能量为60keV,剂量分别为3×1012 cm-2和3×1014 cm-2的质子对Mo/Si多层膜进行辐照实验。发现多层膜内部出现了烧蚀损伤缺陷及节瘤缺陷。结果表明能量相同时,辐照剂量越大对多层膜反射率影响越大。     

In vivo magnetic resonance study of the histochemistry of coconut (Cocos nucifera)

Magnetic resonance imaging (MRI) and localized proton MR spectroscopy (MRS) techniques have been applied for studying different maturation processes in the histochemistry of coconut (Cocos nucifera). Images of the tender and mature coconut are characterized by protons of the aqueous solution present in the cavity and from the surrounding pulp, whereas the image of the dry coconut is from the protons of the fat present in the pulp. Localized proton MR spectra of the water present in the cavity from the tender and the mature coconut show several resonances due to different chemical constituents of coconut water, whereas typical spectra of the pulp from dry coconut reveal a profile of the hydrogens present in the saturated and unsaturated fatty acid chains. In addition, images obtained from a rancid coconut show the extent of internal damage and degradation due to fungal growth; the corresponding localized MR spectra of the coconut water reveal that several proton resonances are absent.     

季铵盐型双子表面活性剂16-4-16聚集状态的NMR研究

核磁共振弛豫，自扩散以及2D NOESY谱研究结果表明：双子表面活性剂16-4-16溶液在形成胶束的过程中，联结基团及其邻近的碳氢链质子形成胶束的壳层，而距离离子头较远的疏水质子位于胶束的内部. 与对应的单链的表面活性剂CTAB相比，其分子运动更受限制. 2D NOESY谱显示联接基团及临近的碳氢链的质子间有较强的交叉峰，表明形成胶束时，分子在联结基团附近堆积的较为紧密. 由2D NOESY谱计算得到的质子间距与HYPERCHEM模拟值有偏差，表明这些强交叉峰是分子间相互作用的结果，并且对应质子对在双子表面活性剂16-4-16分子中位于邻近的区域. 因此我们推测，双子表面活性剂16-4-16分子在球形胶束中形成特殊的排列方式.     

Quantum confinement in monatomic Cu chains on Cu(111)

The existence of one-dimensional (1D) electronic states in Cu/Cu(111) chains assembled by atomic manipulation is revealed by low-temperature scanning tunneling spectroscopy and density functional theory (DFT) calculations. Our experimental analysis of the chain-localized electron dynamics shows that the dispersion is fully described within a 1D tight-binding approach. DFT calculations confirm the confinement of unoccupied states to the chain in the relevant energy range, along with a significant extension of these states into the vacuum region.     

Hairpin rubber elasticity

We model the elastic properties of main chain liquid crystalline elastomers, formed by cross linking chains in a strongly nematic state, when they have hairpin defects. We study the response of the elastomer to imposed uniaxial extension along the nematic direction, and employ a microscopic model of how the deformation is distributed non-affinely amongst the hairpin and straight chain populations. The rubber shows a plateau in the stress as a function of the elongation imposed along the director. It is a consequence of the depletion of the actively stretching population of hairpin chains and should not be confused with soft elasticity effects associated with director rotation.     

Direct writing of microtunnels using proton beam micromachining

The production of high aspect ratio microstructures is a potential growth area. The combination of deep X-ray lithography with electroforming and micromolding (i.e. LIGA) is one of the main techniques used to produce 3D microstructures. The new technique of proton micromachining employs focused MeV protons in a direct write process which is complementary to LIGA. During ion exposure of positive photoresist like PMMA, scission of molecular chains occurs. These degraded polymer chains are removed by the developer. The aim of this paper is to investigate the capabilities of proton micromachining as a lithographic technique. We show the realization of sub-surface channels, or microtunnels, which have been fabricated in only one exposure and without cutting or resurfacing the material. Using our Van-de-Graaff accelerator, the resist (PMMA) has been exposed with high-energy protons (2.5 MeV). The range of charged particles in matter is well-defined and depends on the energy. Therefore, it is possible to obtain a dose which is sufficient to develop the bottom part of the ion paths but not the top part. Thus, by selecting the energy and the exposure time, a big variety of microtunnels can be realized.