Performance of cryogenic probes as a function of ionic strength and sample tube geometry

The pursuit for more sensitive NMR probes culminated with development of the cryogenic cooled NMR probe. A key factor for the sensitivity is the overall resistance of RF circuitry and sample. Lowering the coil temperature to approximately 25 K and the use of superconducting coil material has greatly reduced the resistance contribution of the hardware. However, the resistance of a salty sample remains the same and evolves as the major factor determining the signal-to-noise ratio. Several approaches have been proposed to reduce the resistance contribution of the sample. These range from encapsulating proteins in a water cavity formed by reverse micelles in low viscosity fluids to the optimal selection of low mobility, low conductivity buffer ions. Here we demonstrate that changing the sample diameter has a pronounced effect on the sample resistance and this results in dramatic improvements of the signal-to-noise ratio and shorter pi/2 pulses. We determined these parameters for common 5 mm NMR tubes under different experimental conditions and compared them to the 2, 3 and 4 mm tubes, in addition, 5mm Shigemi tubes were included since these are widely used. We demonstrate benefits and applicability of studying NMR samples with up to 4M salt concentrations in cryogenic probes. Under high salt conditions, best results in terms of short pi/2 pulses and high signal-to-noise ratios are obtained using 2 or 3mm NMR tubes, especially when limited sample is available. The 4 mm tube is preferred when sample amounts are abundant at intermediate salt conditions.     

Spectral unraveling by space-selective Hadamard spectroscopy

Spectral unraveling by space-selective Hadamard spectroscopy (SUSHY) enables recording of NMR spectra of multiple samples loaded in multiple sample tubes in a modified spinner turbine and a regular 5mm liquids NMR probe equipped with a tri-axis pulsed field gradient coil. The individual spectrum from each sample is extracted by adding and subtracting data that are simultaneously obtained from all the tubes based on the principles of spatially resolved Hadamard spectroscopy. The well-known Hadamard spectroscopy has been applied for spatial selection and the method utilizes standard configuration of NMR instrument hardware. The SUSHY method can be easily incorporated in multi-dimensional multi-tube NMR experiments. This method combines the excitation multiplexing, natural advantage of FTNMR, and sample multiplexing and offers high-throughput by reducing the total experimental time by up to a factor of four in a 4-tube mode.     

Reducing the NMR sample volume using a single organic liquid: Increased sensitivity for mass-limited samples with standard NMR probes

A simple inexpensive protocol for confining an aqueous sample to the active region of a standard NMR probe is examined for high-resolution NMR. The aqueous sample is sandwiched between an inert perfluorinated organic liquid that has been exploited in the design of micro-coil NMR probes. The procedure is demonstrated with 3 mm NMR tubes at ambient and elevated temperatures but should be equally applicable to smaller diameter tubes. It is shown that confinement has minimal effects on line shape and provides at least a two fold increase in sensitivity over a conventional sample, for the same mass of solute.     

Development of a dual cell, flow-injection sample holder, and NMR probe for comparative ligand-binding studies

NMR based ligand screening is becoming increasingly important for the very early stages of drug discovery. We have proposed a method that makes highly efficient use of a single sample of a scarce target, or one with poor or limited solubility, to screen an entire compound library. This comparative method is based on immobilizing the target for the screening procedure. In order to support the method, a dual cell, flow injection probe with a single receiver coil has been constructed. The flow injection probe has been mated to a single high performance pump and sample handling system to enable the automated analysis of large numbers of compound mixes for binding to the target. The probe, having an 8 mm 1H/2H dual tuned coil and triple axis gradients, is easily shimmed and yields NMR spectra of comparable quality to a standard 5 mm high-resolution probe. The lineshape in the presence of a solid support is identical to that in glass NMR tubes in a 5 mm probe. Control spectra of each cell are identical and well separated, while ligand binding in a complex mixture can be readily detected in 20-30 min, thus paving the way for use of the probe for actual drug discovery efforts.     

Scanning tunneling microscopy of carbon nanotubes

This article reports on the application of scanning tunneling microscopy for the study of surface structures and electronic properties of carbon nanotubes. Geometric effects resulting from the cylindrical shape of the tubes as well as the particular band structure of the graphitic crystal lattice can lead to a variety of contrast patterns. On the atomic scale, it is sometimes possible to see the full honeycomb lattice structure but often different structures are observed. Besides distortions caused by tip–sample interactions, we find that a complex superstructure superimposed on the simple atomic contrast pattern arises from elastic scattering of the Fermi states at defects or impurities. From a careful analysis of high-resolution images it is possible to extract information about elastic strain of individual tubes. A new combination of scanning tunneling and scanning force microscopy enables near-atomic point resolution of the force signal the tubes can be identified without the need of a conducting substrate. This imaging mode is a crucial step for the characterization of electronic devices based on individual single-wall tubes. This mode can be further enhanced by the use of single-walled tubes as probe tips. Received: 17 May 1999 / Accepted: 18 May 1999 / Published online: 4 August 1999     

Intertube coupling in ropes of single-wall carbon nanotubes

We investigate the coupling between individual tubes in a rope of single-wall carbon nanotubes using four probe resistance measurements. By introducing defects through the controlled sputtering of the rope we generate a strong nonmonotonic temperature dependence of the four terminal resistance. This behavior reflects the interplay between localization in the intentionally damaged tubes and coupling to undamaged tubes in the same rope. Using a simple model we obtain the coherence length and the coupling resistance. The coupling mechanism is argued to involve direct tunneling between tubes.     

Electron Spin Resonance Imaging Probes and a Sample Holder for Thin and Long One-Dimensional Samples

Most electron spin resonance (ESR) experiments involve the use of samples that can be easily placed in millimeter-size tubes and measured efficiently in conventional resonators. However, in some cases, the samples must remain intact, due to which conventional commercial resonators may not be suitable to measure them. Here, we describe a set of three resonators, which can be combined and incorporated as part of a 1-D continuous wave ESR imaging probe to measure and image very thin (~50–500 μm) and very long (~10–30 mm) objects. The dielectric resonators we employ make it possible to greatly enhance spin sensitivity per unit of length––compared to the use of a rectangular ESR cavity, at ~9.3 GHz. In addition, a special sample holder was developed to facilitate the handling and measurement of such thin and long delicate objects, which in our case are the Arabidopsis roots. A detailed design of the resonators, imaging probe, and the sample holder is provided, along with experimental results for the resonator properties, its spin sensitivity, and imaging capability.     

Sandwich-ELISE NMR: reducing the sample volume of NMR samples

We present Sandwich-ELISE, a concatenated version of our previously proposed Experimental LIquid SEaling (ELISE) protocol, in which an aqueous sample is effectively sealed by the addition of a small layer of mineral oil, or, alternatively, a chloroform sample was sealed by a water layer. With Sandwich-ELISE, a triple layered geometry composed of deuterated chloroform/aqueous buffer/mineral oil can be used to limit the sample to the active coil volume, effectively replacing the popular Shigemi tubes. Importantly, this procedure is readily applicable to smaller diameter tubes, for which no Shigemi tubes are available. We further present spectra of a 1 microl protein sample sandwiched between the chloroform and Nujol phases in a 1mm tube, demonstrating thereby that the volume of the aqueous phase of interest can be reduced even further.     

内螺纹管管型结构对管内流动阻力特性的影响

对不同结构的内螺纹管内空气-水两相流动的阻力特性进行了实验研究,从实验方面得出了影响内螺纹管阻力特性的主要几何参数(螺纹高度,螺纹升角,螺纹宽度等)对内螺纹管阻力特性的影响规律。结合实验现象,引入了研究内螺纹管阻力特性的并联管路模型,最终得出适用于不同结构内螺纹管的阻力特性半理论经验公式。通过该公式可以较好地反映出各个几何参数对内螺纹管阻力特性的影响规律。     

Construction and performance of an NMR tube with a sample cavity formed within magnetic susceptibility-matched glass

We describe the construction and performance of an NMR tube with a magnetic susceptibility matched sample cavity that confines the solution within the detection zone in the axial direction and in a quasi-rectangular region in the radial direction. The slot-like sample cavity provides both good sample volume efficiency and tolerance to sensitivity loss in the sample space. The signal-to-noise ratio per unit volume of the constructed tube was 2.2 times higher than that of a cylindrical tube of 5mm outer diameter with a sample containing 300 mM NaCl at a static magnetic field of 14.1T. Even the overall signal-to-noise ratio of the slot tube was 35% higher than that of the conventional 5mm tube for a sample containing 300 mM NaCl. Similar improvements over existing sample tube geometries were obtained at 950 MHz. Moreover the temperature rise resulting from RF heating was found to be significantly lower for the slot tube even when compared to 3 and 4mm outer diameter cylindrical tubes as measured in a 5mm cryoprobe. A further advantage of this type of tube is that a sample cavity of any desired size and shape can be formed within a cylindrical tube for use in a single cryogenic probe.     

La2/3Ca1/3Mn1-xCuxO3(x=0.15)系统低温下的电阻极小值现象及其起因

实验研究了La_2/3Ca_1/3Mn_1-xCu_xO₃(x=0和0.15)样品在温度远低于居里温度时的电阻随温度的变化行为.发现未加磁场时,Cu掺杂样品在低温下表现出电阻极小值行为.这一极小值现象在外加磁场后消失.基于Kondo理论,对实验观察进行了讨论,并作了定量的理论与实验的比较. 关键词：     

A high-resolution NMR probe in which the coil and preamplifier are cooled with liquid helium. 1984

In a well designed NMR spectrometer, the noise originates predominantly from the resistance of the receiver coil. Significant improvements in sensitivity can be achieved by cooling the coil to cryogenic temperatures, provided that a preamplifier can be designed to match the coil’s performance. A probe is described in which the coil and preamplifier are cooled with liquid helium, but the sample is maintained at room temperature. Carbon-l3 spectra at 45 MHz demonstrate improved sensitivity over conventional probes at the same field.     

用四探针技术测量半导体薄层电阻的新方案

本文介绍用四探针技术测量半导体薄层电阻的新方案。其特点是,不论对无穷大薄层还是有限尺寸小样品,都不要求探针之间的距离相等,测量结果与探针间距无关,消除了针距不等引起的误差;同时,对于矩形或圆形小样品,不需要另加边界修正,因而也不必知道样品几何尺寸,只从电测量中即可求出电阻值。 关键词：     

Specification of the acoustical input to the ear at high frequencies

The sound fields that arise in the auditory canals of cats have been examined both experimentally and theoretically. Of particular interest was the spatial variation of sound pressure near the eardrum, where reference probes are typically located. Using a computer controlled data acquisition system, sound pressure was measured between 100 Hz and 33 kHz for constant driver input at 14 different locations in the ear canal of a cat, and the standing wave patterns formed. The shape of the patterns could be predicted quite well above 12 kHz using a theory that requires specification of only the geometry of the ear canal. This theory, an extension of the one-dimensional horn equation, applies to three-dimensional, rigid-walled tubes that have both variable cross section and curvature along their lengths. Large variations of sound pressure along the ear canal and over the surface of the eardrum are found above about 10 kHz. As a consequence it is not possible to define the acoustical input to the ear from sound pressure level measured at any single location. Even in comparative experiments, in which only the constancy of the acoustical input is important, any uncertainty in reference probe location would lead to an uncertainty in sound pressure level when different sets of measurements are compared. This error, calculated for various probe locations and frequencies, is especially large when the probe is near a minimum of the sound field. Spatial variations in pressure can also introduce anomalous features into the measured frequency response of other auditory quantities when eardrum sound pressure is used as a reference. This is illustrated with measurements of the round window cochlear microphonic.     

共路径光相干成像系统光纤探头的研究

本文提出了基于楔形光纤以及端面成角度光纤的共路径光相干成像系统探头,实现背向散射信号在其端部的共路径相位干涉,从而获得待测件断面成像信息.首先,建立了共路径光相干成像系统光路及探头相位干涉的理论模型,分析了各光纤探头尺寸与干涉信号强度、系统性能的关系.其次,分别设计出楔形光纤、端面成角光纤探头,开展了共路径光路干涉实验,搭建了工作波长为1 550 nm的共路径光路测试系统.然后,根据不同待测样品的散射率,设计并研制了不同角度的楔形光纤探头,分析了不同尺寸的光纤探头对系统性能的影响,针对不同样品开展了固定探头探测实验.实验结果表明,楔形光纤端部可直接对输出光聚焦,照射在被测样品上,且其端面成一定角度时,可调节输出分光比,实现对参考信号的调节,提高了系统信噪比.为进一步开展共路径光相干成像系统的研究奠定了基础.     

Influence of the diameter and wall thickness of a quartz pipe inserted in the EPR cavity on the signal intensity

Some dependences between the EPR signal intensity of point samples and the diameter and wall thickness of the quartz tubes with which a standard rectangular TE₁₀₂ EPR cavity is loaded are reported. It is found that the EPR signal intensity linearly depends on the wall thickness of the container and can be increased approximately twice when thick sample tubes are used. The microwave power in the location of the sample increases similarly whereas the normalized bell-shape distribution of the signal intensity along thez-axis of the cavity remains unchanged. The effective microwave power necessary to saturate the sample decreases and the cavity filling factor increases.     

一种快速测量共聚焦X射线分析装置探测微元尺寸方法

共聚焦X射线荧光技术是一种无损的三维光谱分析技术,在材料,生物,矿物样品分析,考古,证物溯源等领域具有广泛应用。共聚焦X射线荧光谱仪的核心部件为两个多毛细管X光透镜。一个为多毛细管X光会聚透镜（PFXRL）,其存在一后焦点,作用是把X光管所发出的发散X射线会聚成几十微米大小的高增益焦斑。另一透镜为多毛细管X光平行束透镜（PPXRL）,其存在一几十微米大小前焦点,置于X射线能量探测器前端,其作用是接收特定区域的X射线荧光信号。在共聚焦Ｘ射线荧光谱仪中,PFXRL的后焦点与PPXRL的前焦点重合,所形成的区域称作探测微元。只有置于探测微元区域的样品能够被谱仪检测到,使样品与探测微元相对移动,逐点扫描,便能够对样品进行三维无损的X射线分析。探测微元的尺寸决定共聚焦X射线荧光谱仪的空间分辨率,因此精确测量谱仪的探测微元的尺寸是非常重要的。如图1所示,谱仪探测微元可以近似为椭球体,其尺寸可以用水平方向分辨率X, Y,和深度分辨率Z表示。目前,常采用金属细丝或金属薄膜通过刀口扫描的方法测量谱仪探测微元尺寸。为了精确的从三个维度测量探测微元尺寸,金属细丝直径要小于探测微元尺寸。金属细丝和探测微元都是数十微米级别的尺寸大小,很难把金属靠近探测微元。为了得到探测微元在不同X射线能量下尺寸变化曲线,要采用多种金属细丝测量。采用单个金属细丝依次测量比较耗费时间。采用金属薄膜可以很方便地测量探测微元的深度分辨率Z,但是当测量水平分辨率X, Y时,难以准确测量。为了解决以上谱仪探测微元测量中存在的问题,本文提出采用多种金属丝平行粘贴在硬纸片上作为样品用于快速测量探测微元尺寸。附有金属细丝的硬纸片靠近谱仪探测微元,可以将探测微元置于硬纸片所在平面。由于硬纸片与金属细丝在同一水平面,在谱仪摄像头的协助下,可以把金属细丝迅速的靠近探测微元。靠近探测微元后,在全自动三维样品台的协助下,金属细丝沿两个方向对探测微元分别进行一次二维扫描。通过对二维扫描数据的处理便可以获得探测微元尺寸随入射X射线能量变化曲线。采用此方法对实验室所搭建的共聚焦X射线荧光谱仪的探测微元进行了测量。     

牙本质龋的太赫兹成像研究

牙本质龋与牙髓感染状态及活力密切相关,龋损深度则决定临床治疗方案,但目前牙本质龋的检测及诊断方法如：视诊、探诊容易受到主观因素影响;X线辅助检查对龋病灵敏度低等,都有一定缺陷,可靠性及有效性仍有待提高。太赫兹时域光谱可以利用不同的物理参数成像,在牙本质龋在体、无损检测方面有较大应用潜力。为探索牙本质龋损的太赫兹光谱图像开展本研究。实验通过搭建透射、反射式扫描太赫兹平台,对15枚含牙本质龋离体牙磨片扫描,通过数据二维重构,获得了不同参数的太赫兹透射和反射图像,再将太赫兹图像与实验室研究龋病的光镜图像与X线图像对比、拟合并进行光镜下、太赫兹图像下龋损面积评价。结果表明：太赫兹图像与光镜图像相符,较X线图像灵敏度更高。反射模式下由于太赫兹反射信号较弱,使得样品厚度,表面粗糙程度以及系统噪声对实验结果影响较大,图像仅能辨识样本轮廓,不能用于区分牙釉质、牙本质及牙本质龋。透射模式下的频域1.4 THz相位差成像、时域信号最小值对应的时间成像都能区分牙釉质,牙本质和牙本质龋,可以用来鉴别三者,其中最小值对应的时间成像效果最佳。对光镜下测得牙本质龋损面积与太赫兹透射模式下的时域信号最小值对应的时间图像测得的牙本质龋损面积进行配对样本Wilcoxon符号秩和检验,结果（p＞0.05）尚不能认为两种方法测得的牙本质龋损面积有差别,两种方法测量的差值源于系统误差。故可以认为通过太赫兹透射模式下的时域信号最小值对应的时间图像获得牙本质龋损范围、大小等诊断信息。研究表明太赫兹成像技术可以为牙本质龋的早期诊断提供更为精确有效且无电离辐射的诊断方法,为临床数字化、微创去龋提供一定形态学依据。     

Design, construction, and validation of a 1-mm triple-resonance high-temperature-superconducting probe for NMR

We report a 600-MHz 1-mm triple-resonance high-temperature-superconducting (HTS) probe for nuclear magnetic resonance spectroscopy. The probe has a real sample volume of about 7.5 microl, an active volume of 6.3 microl, and appears to have the highest mass sensitivity at any field strength. The probe is constructed with four sets of HTS coils that are tuned to 1H, 2H, 13C, and 15N, and there is a z-axis gradient. The coils are cooled with a conventional Bruker CryoPlatform to about 20 K, and the sample chamber can be regulated above or below room temperature over a moderate range using a Bruker variable temperature unit. The absolute S/N for 0.1% ethylbenzene is approximately 1/3 that of a conventional 5mm probe with just 1/70 of the sample volume. We demonstrate the utility of this probe for small molecules and proteins with 2D spectra of just 1.7 microg of ibuprofen and 400 microM 15N-labeled ubiquitin.     

Some problems in understanding the electronic transport properties of carbon nanotube ropes

The resistance of single-wall carbon nanotube (SWCN) ropes or mats, and some individual tubes, typically shows a crossover from non-metallic to metallic temperature dependence as temperature increases. This systematic pattern is consistent with a series heterogeneous model involving metallic resistance and tunnelling through barriers such as defects and inter-rope contacts. The metallic resistivity term increases linearly with temperature for the ropes or mats, but faster for the individual nanotubes. In contrast to the almost vanishing thermoelectric power expected from electronic band structure calculations, the measured values for mats or films (including recent measurements in a vacuum) are even larger than for typical metals. The thermopower increases with temperature as for metals, but has a characteristic non-linear shape. This temperature dependence can be modelled, for example, with parallel conduction in metallic and semiconducting tubes, but the size of the metallic thermopower required is anomalously large.