Effects of residual single-quantum coherences in intermolecular multiple-quantum coherence studies

Intermolecular multiple-quantum coherences (iMQCs) have been reported to offer a sensitivity to sample structure at a specific user-defined length scale down to the order of 10 microm. When assessing this novel contrast mechanism in controlled phantom experiments, we have observed three different mechanisms whereby residual single-quantum coherences (SQCs) arising from intense high spatial frequencies, stimulated echoes and strong spatially encoding gradients can produce significant changes in signal contrast at particular length scales. These changes which only appear when components arising from SQCs and iMQCs are both present in the detected signal, are similar to changes previously attributed to iMQCs alone. We demonstrate each mechanism by which these residual SQCs arise and describe methods for their suppression.     

Signal enhancement in CRAZED experiments

Many of the promising applications of the CRAZED (COSY Revamped with Asymmetric Z-gradient Echo Detection) experiments are in biomedical and clinical technologies. In tissue, however, signal from the typical CRAZED experiment is largely limited by transverse relaxation. When relaxation is included, the maximum achievable signal from a prototypical CRAZED sequence, in the linear regime, is proportional to T(2)/tau(d). This means that for samples with a short T(2), as encountered in vivo, signals from intermolecular multiple-quantum coherences (iMQCs) reach very diminished signal intensities. While relaxation is generally regarded as a fundamental constraint, we show here that when T(2) is short but T(1) is long, as in tissue, there are simple sequence modifications that can increase signal beyond the T(2) limit. To better utilize the available signal intensity from iMQCs we propose a method to substitute part of the transverse magnetization with the longitudinally modulated magnetization. In this paper we show, with both simulations and experimental results, that in the presence of strong transverse relaxation the standard CRAZED scheme is not the optimal method for observing iMQCs, and can be improved upon with simple modifications.     

分子间多量子相干横向弛豫时间(和自扩散系数)测量的参数优化和数据处理方法

针对测量横向弛豫时间T₂的CPMG脉冲序列和我们所设计的可同时测量高极化单组份单 峰核自旋体系n阶分子间多量子相干横向弛豫时间T_2,n和自扩散系数D_n的改进的CRAZED脉冲序列,分析了影响测量T₂、T_2,n（或D_n）的各种因素,并着重从技术方面讨论了准确测量T_2,n和D_n的实验参数优化和实验数据处理方法.     

Functional magnetic resonance imaging with intermolecular multiple-quantum coherences

For the first time, we demonstrate here functional magnetic resonance imaging (fMRI) using intermolecular multiple-quantum coherences (iMQCs). iMQCs are normally not observed in liquid-state NMR because dipolar interactions between spins average to zero. If the magnetic isotropy of the sample is broken through the use of magnetic field gradients, dipolar couplings can reappear, and hence iMQCs can be observed. Conventional (BOLD) fMRI measures susceptibility variations averaged over each voxel. In the experiment performed here, the sensitivity of iMQCs to frequency variations over mesoscopic and well-defined distances is exploited. We show that iMQC contrast is qualitatively and quantitatively different from BOLD contrast in a visual stimulation task. While the number of activated pixels is smaller in iMQC contrast, the intensity change in some pixels exceeds that of BOLD contrast severalfold.     

Magnetic resonance microscopic imaging based on high-order intermolecular multiple-quantum coherences

Most imaging studies using intermolecular multiple-quantum coherences (iMQCs) have focused on the two-spin dipolar interactions--zero and double quantum coherences. Here, we report the results of various experimental studies to assess the feasibility of magnetic resonance microscopy with high-order iMQCs in model systems at 7 and 14 T. Experimental results demonstrated that the iMQC microscopic images with high coherence orders are readily observable at high field and have unique contrast depending on the sample microstructure and coherence order.     

Simultaneous acquisition of multiple orders of intermolecular multiple-quantum coherence images

Recent studies have demonstrated the ability to detect images based on intermolecular multiple-quantum coherences (iMQCs) that correspond to flipping of two or more separated spins simultaneously, as opposed to conventional magnetic resonance where only one spin is flipped at a time. Until now, iMQC imaging has only acquired one coherence signal per pulse sequence. Here we report a new sequence that successfully detects five orders of coherence (2, 1, 0, −1, and −2-quantum coherence images) in one pulse sequence, with each signal having its full intensity. The simultaneous acquisition highlights substantial contrast differences between conventional and iMQC images, and between the different types of iMQC images.     

Simultaneous acquisition of multiple orders of intermolecular multiple-quantum coherence images in vivo

Until recently, NMR imaging with intermolecular multiple-quantum coherences (iMQCs) has been based on the acquisition of a single echo. In vivo studies of iMQC image contrast would greatly benefit from a method that could acquire several orders of quantum coherence during the same acquisition. This would enable comparison of the image contrast for various orders and eliminate image coregistration problems between scans. It has previously been demonstrated that multiple orders of iMQC images can be simultaneously acquired of a simple phantom. Here, we examine the technique and its effect on biological tissue, both in vivo and in vitro. First, we establish the effectiveness of the iMQC sequence in vivo using earthworms as specimens. We then further show that the multi-CRAZED sequence enhances detection of next generation (nanoparticle) contrast agents on excised tumor tissue.     

Analysis of mechanism of carbon removal from GaAs(1 0 0) surface by atomic hydrogen

Etching of carbon contaminations from the GaAs(1 0 0) surface by irradiating with atomic hydrogen, which is one of the key reactions to promote high-quality thin films growth by molecular beam epitaxy (MBE), has been investigated by mass spectrometry (MS), Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). It is shown that during the cleaning process at room temperature a total reduction of the Auger carbon signal, accompanied by desorption of methane as major reaction product, can be observed. The reaction pathways as well as the processes responsible for the observed carbon removal are discussed in detail to give a support for etching and growth quality enhancement not only in thin films epitaxy but in all atomic hydrogen promoted gas-phase III-V semiconductor processes.     

A model of the multiple adsorption of hydrogen atoms on the surface of carbon nanotubes

A model of the multiple adsorption of atomic hydrogen on the surface of single-walled carbon nanotubes of the zigzag and arm-chair types was constructed. The adsorption model is based on the Anderson periodic model. An analytic equation for the band structure of carbon nanotubes with adsorbed hydrogen atoms was obtained, and the special features of this structure were studied. The dependence of the band structure of carbon nanotubes on the concentration of adsorbed hydrogen atoms was analyzed. The model constructed can be used to study adsorption of other univalent atoms on the surface of carbon particles.     

Adsorption kinetics and absolute coverages for C2H2 and C2H4 on a tantalum (110) surface held at 465 and 680 K

Auger spectroscopy has been used to measure the adsorption kinetics of acetylene and ethylene gases at 300 K on a clean tantalum (110) surface held at either 465 or 680 K, at gas pressures near 10^?6 Pa. Adsorption occurs irreversibly with identical initial sticking probabilities for both gases leading to the conclusion that its value is unity. This assumption permits a calculation of absolute coverage of approximately 2 carbon atoms for each tantalum atom in both cases. The fact that this value is the same for both gases suggests that ethylene may dehydrogenate to an acetylenic species as claimed for W(110). Heating a sample previously saturated at 465 K results in desorption of hydrogen accompanied by an increase in the carbon Auger signal. This is interpreted as evidence that at least some of the hydrogen atoms lie further from the surface than do the carbon.     

Fast high-resolution 2D correlation spectroscopy in inhomogeneous fields via Hadamard intermolecular multiple quantum coherences technique

Recently, a method based on intermolecular multiple quantum coherences (iMQCs) has been proposed to obtain high-resolution 2D COSY spectra in inhomogeneous fields via 3D acquisitions. However, the very long acquisition time prevents its practical application. To overcome this shortage, the Hadamard technique was applied for the iMQC method in this paper. For the new pulse sequence, the direct frequency-domain excitation is used in the first indirect detection dimension, so the 3D acquisition was replaced by an array of 2D acquisitions. The acquisition time can be reduced to 10 min. The resulting spectra retain useful structural information including chemical shifts and multiplet patterns of J coupling even when the inhomogeneous line broadening leads to overlap of neighboring diagonal resonances in the conventional COSY spectrum. The experimental results are consistent with the theoretical predictions and computer simulations. The new sequence may provide a time-efficient way for the studies of chemical solution in inhomogeneous fields.     

ESR and X-ray diffraction studies of the CVD diamond films

Thin polycrystalline, diamond films were prepared by thermal decomposition of hydrocarbon and hydrogen in the presence of a hot tungsten filament (HF CVD technique). Electron Spin Resonance (ESR) spectroscopy investigations were carried out and correlated to diamond microcrystal size estimated on the basis of X-ray diffraction (XRD) measurements. It was shown that both ESR signal and average crystal size of the thin CVD diamond films depend strongly on the ratio of hydrocarbon/hydrogen concentrations in the CVD reactor. XRD spectra indicate the presence of fullerence and, graphitic polytypes in most studied samples, independent of growth conditions. Observed reciprocal proportionality of the ESR signal intensity versus diamond grain size suggests that the above mentioned carbon phases are mainly dispersed at the grain boundaries.     

Advances in high-resolution nuclear magnetic resonance methods in inhomogeneous magnetic fields using intermolecular multiple quantum coherences

Strong and extremely homogeneous static magnetic field is usually required for high-resolution nu-clear magnetic resonance (NMR). However, in the cases of in vivo and so on, the magnetic field inho-mogeneity owing to magnetic susceptibility variation in samples is unavoidable and hard to eliminate by conventional methods such as shimming. Recently, intermolecular multiple quantum coherences (iMQCs) have been employed to eliminate inhomogeneous broadening and obtain high-resolution NMR spectra, especially for in vivo samples. Compared to other high-resolution NMR methods, iMQC method exhibits its unique feature and advantage. It simultaneously holds information of chemical shifts, multiplet structures, coupling constants, and relative peak areas. All the information is often used to analyze and characterize molecular structures in conventional one-dimensional NMR spec-troscopy. In this work, recent technical developments including our results in this field are summarized; the high-resolution mechanism is analyzed and comparison with other methods based on interactions between spins is made; comments on the current situation and outlook on the research directions are also made.     

The structure and dynamics of water inside armchair carbon nanotube

In this paper we present some simulation results about the behaviour of water molecules inside a single wall carbon nanotube (SWNT). We find that the confinement of water in an SWNT can induce a wave-like pattern distribution along the channel axis, similar phenomena are also observed in biological water channels. Carbon nanotubes(CNTs) can serve as simple nonpolar water channels. Molecular transport through narrow CNTs is highly collective because of tight hydrogen bonds in the protective environment of the pore. The hydrogen bond net is important for proton and other signal transports. The average dipoles of water molecules inside CNTs (7,7), (8,8) and (9,9) are discussed in detail. Simulation results indicate that the states of dipole are affected by the diameter of SWNT. The number of hydrogen bonds, the water--water interaction and water--CNT interaction are also studied in this paper.     

Evaluation of hydrogen chemisorption in nanostructured carbon films by near edge X-ray absorption spectroscopy

We have developed a method for the quantitative evaluation of the chemisorbed fraction of hydrogen in nanostructured carbon films using Near Edge X-ray Absorption Spectroscopy (NEXAFS). In the carbon K-edge spectrum the peak related to carbon bonded to hydrogen is assumed to be correlated with the amount of hydrogen bonded to carbon. This assumption is supported by a comparative analysis of gas-phase hydrocarbons obtained via Electron Energy Loss Spectroscopy (EELS). We applied the method to nanostructured carbon (ns-C) films synthesized by supersonic cluster beam deposition. The evaluated quantity of chemisorbed hydrogen in different samples exposed to molecular hydrogen (pressure of 0.12 MPa, for 3 hours at room temperature) is ∼1.5 wt.%.     

High-resolution absorptive intermolecular multiple-quantum coherence NMR spectroscopy under inhomogeneous fields

Intermolecular multiple-quantum coherence (iMQC) is capable of improving NMR spectral resolution using a 2D shearing manipulation method. A pulse sequence termed CT-iDH, which combines intermolecular double-quantum filter (iDQF) with a modified constant-time (CT) scheme, is designed to achieve fast acquisition of high-resolution intermolecular zero-quantum coherences (iZQCs) and intermolecular double-quantum coherences (iDQCs) spectra without strong coupling artifacts. Furthermore, double-absorption lineshapes are first realized in 2D intermolecular multi-quantum coherences (iMQCs) spectra under inhomogeneous fields through a combination of iZQC and iDQC signals to double the resolution without loss of sensitivity. Theoretically the spectral linewidth can be further reduced by half compared to original iMQC high-resolution spectra. Several experiments were performed to test the feasibility of the new method and the improvements are evaluated quantitatively. The study suggests potential applications for in vivo spectroscopy.     

Molecular dynamics simulations of hydrogen adsorption/desorption by palladium decorated single-walled carbon nanotube bundle

Utilising molecular dynamics simulations, the hydrogen molecules adsorption isotherms of the (8,?0) palladium decorated single-walled carbon nanotube (SWNT) were obtained. The hydrogen adsorption was studied on the external, interstial and internal surfaces of the SWNT bundle at several temperatures ranging from 77 to 400?K. The results were compared with the bare single-walled carbon nanotube bundle under the same conditions. The decorated carbon nanotube bundle hydrogen adsorption was significantly higher than that of the bare one. The hydrogen desorption and readsorption were studied using temperature as the readsorption/desorption variable. The rate constants were calculated for the hydrogen desorption at different temperatures. The calculated decorated SWNT bundle hydrogen desorption activation energy was higher than that for the bare SWNT bundle. The calculated activation energies for the hydrogen desorption in both nanotube bundles specified the temperature dependency of hydrogen desorption.     

等离子体诱导碳纳米管到纳米金刚石的相变

采用氢等离子体，实现了碳纳米管向金刚石的结构相变，并实现了金刚石的高密度成核，有效成核密度可达10\+\{11\}／cm\+2以上，处于目前金刚石成核密度的最高行列，为制备优质的金刚石薄膜提供了保证.高分辨透射电镜、x射线衍射和拉曼光谱都证实了金刚石的形成.同时，对纳米金刚石晶粒的生成机理进行了初步探讨. 关键词： 等离子体 碳纳米管 纳米金刚石 结构相变     

多壁碳纳米管储氢的物理吸附特性

采用巨正则蒙特卡罗方法 ,模拟常温、1 0MPa下氢在扶手椅型多壁壁碳纳米管中的物理吸附过程 .氢分子之间、氢分子与碳原子之间的相互作用采用Lennard Jones势能模型 .研究了双壁碳纳米管外 (内 )径固定而内 (外 )径改变时的物理吸附储氢情况 ,发现氢分子主要储存在双壁碳纳米管的管壁附近 ,当双壁碳纳米管的内外管壁间距由 0 .34nm增大到 0 .6 1或 0 .88nm时可有效增加物理吸附储氢量 ,并给出了相应的理论解释 .在此基础上 ,计算了管壁间距为 0 .34、0 .6 1和 0 .88nm时的三壁碳纳米管的物理吸附储氢量 ,并与相同条件下单壁和双壁碳纳米管的物理吸附储氢量作了比较 ,发现多壁碳纳米管的物理吸附储氢量随碳管层数的增加而减小 .     

Thermal desorption from metal surfaces: A review

In this review an attempt is made to draw correlations between thermal desorption and structural studies of chemisorption on metal surfaces. Alternative models are discussed for the appearance of multiple peaks and for lineshape analysis in desorption, the first involving multiple binding states and the second lateral interactions within a homogeneous chemisorbed layer. Criteria are discussed for distinguishing between the various possibilities for a particular system, in particular with relation to the adsorption of hydrogen and carbon monoxide on tungsten.