双色散二维阿达玛变换光谱仪

设计了一种双色散二维调制的阿达玛变换光谱仪,利用光栅在水平方向的谱级色散和棱镜在垂直方向的谱线色散进行二维分光。与传统的二维光谱CCD探测方法不同,该设计独辟蹊径,采用面阵数字微镜对二维光谱进行阿达玛调制,并利用单点式检测器进行光信号的检测。理论计算及光学仿真表明,与传统的二维光谱探测仪器相比,该光谱仪不仅具有高的分辨率,同时还具有很高的信噪比。     

基于变量分离分解法的极紫外光刻三维掩模快速仿真方法

提出了一种基于分离变量法的极紫外光刻三维掩模衍射谱快速仿真方法,在保证一定仿真精度的前提下提高了仿真速度。该方法将三维掩模分解为2个相互垂直的二维掩模,对2个二维掩模采用严格电磁场方法进行衍射谱仿真并将结果相乘以重构成三维衍射谱。以6°主入射角、45°线偏振光照明及22nm三维方形接触孔掩模为例,在入射光方位角0°~90°变化范围内,相同仿真参数下,该方法的仿真结果与商用光刻仿真软件Dr.LiTHO的严格仿真结果相比,图形特征尺寸误差小于0.21nm,仿真速度提高约65倍。在上述参数下,该方法与Dr.LiTHO的域分解方法及基于掩模结构分解法等快速方法相比,仿真精度和速度均提高1倍以上。该模型无需参数标定,适用于矩形图形的三维掩模快速仿真。     

超导磁梯度张量探头结构优化方法研究

针对传统超导磁梯度张量探头中多个磁梯度计间的噪声互扰会降低系统灵敏度的问题，本文提出了一种基于二维傅里叶变换的磁梯度张量探头结构优化方法。通过二维傅里叶变换及逆变换将磁场矢量Z分量沿着Z轴方向的二阶空间导数B_zzz转换为磁场矢量的3个分量以及一阶磁梯度张量的5个独立元素，把通常至少需要6个SQUID一阶平面磁梯度计的探头结构简化为只需要1个二阶SQUID磁梯度计的探头结构，消除了磁梯度计之间的噪声干扰，系统灵敏度提高了1个数量级。实验结果表明该探头具有良好的探测能力，证明了这种优化方法的可行性。     

激光拉曼光谱技术对氯代有机混合物的快速检测研究

为实现对有机物混合物的快速、无损检测,提出一种基于激光拉曼光谱技术的二维分析方法。研究结果表明,采用532 nm波长激光作为激发光源,观测到236.2,348.9,449.4,513.6 cm-1四条振动拉曼谱线,且这些谱线的强度比为6.4∶1.7∶9.4∶1.0,可确定四氯乙烯的存在。观测到707.5,1 087.9,1 175.8, 3 078.6 cm-1四条振动拉曼谱线,其强度比为9.6∶6.4∶1.0∶3.9,可确定氯苯的存在。即通过综合分析特征谱线及若干特征谱线的强度比,可快速判断有机混合溶液中某种物质的存在。在定量分析方面,采用多光谱分析结合最小二乘法拟合提高了测量的可靠性,所测样品浓度的准确率为98.4%。本研究为有机物混合物成分识别和浓度探测提供了一套可行的光谱测量方法,有着十分重要的应用前景。     

多维核磁共振数据在通用计算机上的处理与三维谱的观测

本文分析、讨论了利用外部通用计算机处理核磁共振数据的方法及程序,包括数据格式转换,一维、二维、三维谱的数据处理,谱图的显示及输出,并以VAX机为例实现了三维谱的观测。文中还详细讨论了编程的原理和一些技术细节。     

含吡啶氮杂缰绳醚的NMR研究

本文研究了九种新合成含吡啶氮杂缰绳醚¹H、¹³C NMR谱。用经验计算、DEPT及二维异核相关谱等方法进行谱线归属。在此基础上讨论了溶液中样品的结构、取代基对其结构、构象的影响和取代基的化学位移规律。发现含吡啶氮杂缰绳醚D位质子谱线分裂。     

氨基酸合成方法研究—(XI)N-取代亚氨酸酯与芳醛缩合产物—去氢氨基酸衍生物的构型及其NMR研究

通过~1H NMR、NOE差谱和门控去偶~(13)C NMR等的研究确定了新合成的五对α-去氢氨基酸衍生物的构型,并利用部分弛豫、APT~(13)C NMR二维碳氢相关谱及~(13)C-~(19)F偶合常数等对NMR谱线进行了归属.     

单光子探测三维点云与可见光图像融合处理算法研究

为了提升光电系统对于目标的探测识别能力,实现单光子探测三维点云数据和二维可见光图像的融合处理,提出了单光子探测成像系统的融合处理算法,采用直接线性变换方法并利用同名特征点的选取和间接平差算法解决了融合处理过程中的参数标定问题。通过实验数据进行融合处理算法验证,实现了分辨率1024×768像素单光子探测三维点云和二维可见光图像的像素级融合处理。实验结果表明,提出的融合处理算法能够有效实现三维、二维图像的融合。     

基于二维相关荧光谱定量分析水中的PAHs

针对水环境中多环芳烃(PAHs)污染现状,提出并建立一种基于二维相关荧光谱水体中PAHs的检测方法。以菲和荧蒽为研究对象,配置36个蒽荧蒽混合水溶液样品(蒽和荧蒽的浓度范围均为1×10-4~1×10~(-6) g·L~(-1)),采集了所有样品的三维荧光光谱。以激发波长为外扰,构建同步二维相关荧光谱。在此基础上建立了定量分析水溶液中蒽和荧蒽浓度的多维偏最小二乘(N-PLS)模型,对蒽和荧蒽的预测均方根误差(RMSEP)分别为5.48×10~(-6) g·L~(-1)和6.25×10~(-6) g·L~(-1)。为了比较,基于常用的三维荧光谱建立了NPLS模型,对蒽和荧蒽的RMSEP分别为5.92×10~(-6) g·L~(-1)和7.33×10~(-6) g·L~(-1)。研究结果表明:基于二维相关荧光谱检测环境中PAHs污染物是可行。     

棱镜-光栅组合色散型超光谱成像系统的优化设计

大视场、超光谱分辨率、高空间分辨是光谱成像仪的发展方向,谱线弯曲和色畸变的抑制则是二维谱图信息准确提取的前提。提出了一种棱镜-光栅光谱成像结构形式,并采用矢量方法构建了棱镜-光栅组合色散元件的数学模型,优化了分光模块的结构参数,基于此组合色散元件设计了一个具有近直视光路结构的超光谱成像仪光学系统。该系统光谱范围为400~800nm,入射狭缝长为14mm,F数为2.4,其光谱分辨率达0.5nm,调制传递函数(MTF)在探测器奈奎斯特频率68lp/mm处均大于0.7,谱线弯曲和色畸变均小于1μm,低于单个像素的13.5%。     

DEPT spectral editing in HCCONH-type experiments. Application to fast protein backbone and side chain assignment

2D DEPT-H(alpha,beta)C(alpha,beta)(CO)NH and 2D CT-DEPT-HC(CO)NH-TOCSY experiments are presented which allow fast resonance assignment of aliphatic protein side chains. In these 2D reduced-dimensionality experiments, two or three nuclei are frequency labeled in the indirect dimension. DEPT spectral editing reduces the number of correlation peaks detected in each 2D spectrum, and helps in amino-acid-type determination during sequential backbone resonance assignment. Applications are shown for a small 68-residue, and a highly deuterated 167-residue protein. The new experiments complement the set of 2D HNX correlation experiments, previously proposed for fast protein resonance assignment [J. Biomol. NMR, 27 (2003) 57].     

Effects of various types of molecular dynamics on 1D and 2D (2)H NMR studied by random walk simulations

By carrying out random walk simulations we systematically study the effects of various types of complex molecular dynamics on (2)H NMR experiments in solids. More precisely, we calculate one-dimensional (1D) (2)H NMR spectra and the results of two dimensional (2D) (2)H NMR experiments in time domain, taking into account isotropic as well as highly restricted motions which involve rotational jumps about different finite angles. Although the dynamical models are chosen to mimic the primary and secondary relaxation in supercooled liquids and glasses, we do not intend to describe experimental results quantitatively but rather to show general effects appearing for complex reorientations. We carefully investigate whether 2D (2)H NMR in time domain, which was originally designed to measure correlation times of ultraslow motions (tau >/= 1 ms), can be used to obtain shorter tau, too. It is demonstrated that an extension of the time window to tau >/= 10 &mgr;s is possible when dealing with exponential relaxation, but that it will fail if there is a distribution of correlation times G(lgtau). Vice versa, we show that 1D (2)H NMR spectra, usually recorded to look at dynamics with tau in the microsecond regime, are also applicable for studying ultraslow motions provided that the loss of correlation is achieved step by step. Therefore, it is useful to carry out 1D and 2D NMR experiments simultaneously in order to reveal the mechanism of complex molecular motions. In addition, we demonstrate that highly restricted dynamics can be clearly observed in 1D spectra and in 2D NMR in time domain if long solid-echo delays and large evolution times are applied, respectively. Finally, unexpected observations are described which appear in the latter experiment when considering very broad distributions G(lgtau). Because of these effects, time scale and geometry of a considered motion cannot be extracted from a straightforward analysis of experimental results. Copyright 2000 Academic Press.     

A new sensitive isotropic-anisotropic separation experiment-SPEED MAS

A new sensitive 2D isotropic-anisotropic separation experiment that utilizes stroboscopic phase encoding in the evolution dimension (SPEED) under magic angle sample spinning is presented. This 2D experiment consists of a train of 2N - 1 pi pulses that are applied over 2N rotor periods. The pi pulse train effectively reduces the apparent spinning speed in the evolution dimension by a factor of 1 / (2N) from the mechanical spinning speed. Thus, problems commonly associated with magic angle turning such as stable slow spinning, different matching and TPPM proton decoupling conditions are avoided. Data replication similar to the five pi replicated magic angle turning (FIREMAT) and pseudo 2D sideband suppression (P2DSS) experiments transfers resolution from the acquisition dimension to the evolution dimension. Hence, large spectral windows with good digital resolution are obtained with a few evolution increments. Here, slow spinning sideband patterns are extracted from the replicated 2D dataset with TIGER processing. Nevertheless, 2D Fourier transformation is also applicable. The extracted sideband patterns are identical to magic angle turning sideband pattern allowing for easy extraction of principal shift components. Accurate (13)C principal shift components are obtained for 3-methylglutaric acid using SPEED and FIREMAT experiments to validate the method. Furthermore, SPEED spectra for calcium acetate and alpha santonin are reported to show the wide applicability of this new experiment.     

Rapid solid-state NMR of deuterated proteins by interleaved cross-polarization from ¹H and ²H nuclei

We present a novel sampling strategy, interleaving acquisition of multiple NMR spectra by exploiting initial polarization subsequently from (1)H and (2)H spins, taking advantage of their different T(1) relaxation times. Different (1)H- and (2)H-polarization based spectra are in this way simultaneously recorded improving either information content or sensitivity by adding spectra. The so-called Relaxation-optimized Acquisition of Proton Interleaved with Deuterium (RAPID) (1)H→(13)C/(2)H→(13)C CP/MAS multiple-acquisition method is demonstrated by 1D and 2D experiments using a uniformly (2)H, (15)N,(13)C-labeled α-spectrin SH3 domain sample with all or 30% back-exchanged labile (2)H to (1)H. It is demonstrated how 1D (13)C CP/MAS or 2D (13)C-(13)C correlation spectra initialized with polarization from either (1)H or (2)H may be recorded simultaneously with flexibility to be added or used individually for spectral editing. It is also shown how 2D (13)C-(13)C correlation spectra may be recorded interleaved with (2)H-(13)C correlation spectra to obtain (13)C-(13)C correlations along with information about dynamics from (2)H sideband patterns.     

Improved Resolution from Double Constant-Time Evolution of 3D and 4D Triple-Resonance Experiments

Triple-resonance NMR experiments are nearly essential for performing backbone assignments of proteins larger than 15 kDa. Our work extends the double constant-time (2CT) evolution scheme to triple-resonance 3D and 4D experiments. The modifications needed to accomplish 2CT evolution in triple resonance experiments are straight forward, are completely general, and consequently, will yield increased resolution for all out-and-back experiments. We expect that the increased resolution of experiments presented here will be useful in the study of larger proteins (>30 kDa) and in the study of highly helical proteins where¹HN,¹⁵N, and¹³C dimensions are poorly dispersed.     

Fractal dimension of 40 MHz intravascular ultrasound radio frequency signals

Objective

Fully automatic tissue characterization in intravascular ultrasound systems is still a challenge for the researchers. The present work aims to evaluate the feasibility of using the Higuchi fractal dimension of intravascular ultrasound radio frequency signals as a feature for tissue characterization.

Methods

Fractal dimension images are generated based on the radio frequency signals obtained using mechanically rotating 40 MHz intravascular ultrasound catheter (Atlantis SR Plus, Boston Scientific, USA) and compared with the corresponding correlation images.

Conclusion

An inverse relation between the fractal dimension images and the correlation images was revealed indicating that the hard or slow moving tissues in the correlation image usually have low fractal dimension and vice-versa. Thus, the present study suggests that fractal dimension images may be used as a feature for intravascular ultrasound tissue characterization and present better resolution then the correlation images.     

Heteronuclear X-Y double quantum MAS NMR in crystalline inorganic solids. Applications for indirect detection and spectral editing of rare-spin resonances.

Heteronuclear double quantum MAS NMR experiments in the solid state, involving pairs of highly abundant 31P spins and the rare spins 113Cd, 77Se, and 29Si, are described for the three crystalline compounds CdSiP2, CdGeP2, and Ag7PSe6. These experiments offer the opportunity of indirectly detecting the rare-spin resonance via chemical shift evolution of heteronuclear double quantum coherence. For suitable cases, this method results in significantly enhanced detection sensitivities. Criteria for favorable indirect detection experiments are established. Besides offering high sensitivity, the pulse sequence also acts as a heteronuclear double quantum filter, hence providing heteronuclear correlation and useful spectral editing for peak assignments.     

Triple resonance solid state NMR experiments with reduced dimensionality evolution periods

Two solid state NMR triple resonance experiments which utilize the simultaneous incrementation of two chemical shift evolution periods to obtain a spectrum with reduced dimensionality are described. The CO N CA experiment establishes the correlation of (13)C(i-1) to (13)C alpha(i) and (15)N(i) by simultaneously encoding the (13)CO(i-1) and (15)N(i) chemical shifts. The CA N COCA experiment establishes the correlation (13)Ca(i) and (15)CO(i) to (13)C alpha(i-1) and (15)N(i-1) within a single experiment by simultaneous encoding of the (13)C alpha(i) and (15)N(i) chemical shifts. This experiment establishes sequential amino acid correlations in close analogy to the solution state HNCA experiment. Reduced dimensionality 2D experiments are a practical alternative to recording multiple 3D data sets for the purpose of obtaining sequence-specific resonance assignments of peptides and proteins in the solid state.     

3D NMR spectroscopy for resonance assignment and structure elucidation of proteins under MAS: novel pulse schemes and sensitivity considerations

Two types of 3D MAS NMR experiments are introduced, which combine standard (NC,CC) transfer schemes with (1H,1H) mixing to simultaneously detect connectivities and structural constraints of uniformly 15N,13C-labeled proteins with high spectral resolution. The homonuclear CCHHC and CCC experiments are recorded with one double-quantum evolution dimension in order to avoid a cubic diagonal in the spectrum. Depending on the second transfer step, spin systems or proton-proton contacts can be determined with reduced spectral overlap. The heteronuclear NHHCC experiment encodes NH-HC proton-proton interactions, which are indicative for the backbone conformation of the protein. The third dimension facilitates the identification of the amino acid spin system. Experimental results on U-[15N,13C]valine and U-[15N,13C]ubiquitin demonstrate their usefulness for resonance assignments and for the determination of structural constraints. Furthermore, we give a detailed analysis of alternative multidimensional sampling schemes and their effect on sensitivity and resolution.     

Fast multi-dimensional NMR by minimal sampling

A new scheme is proposed for very fast acquisition of three-dimensional NMR spectra based on minimal sampling, instead of the customary step-wise exploration of all of evolution space. The method relies on prior experiments to determine accurate values for the evolving frequencies and intensities from the two-dimensional 'first planes' recorded by setting t1=0 or t2=0. With this prior knowledge, the entire three-dimensional spectrum can be reconstructed by an additional measurement of the response at a single location (t1( *),t2( *)) where t1( *) and t2( *) are fixed values of the evolution times. A key feature is the ability to resolve problems of overlap in the acquisition dimension. Applied to a small protein, agitoxin, the three-dimensional HNCO spectrum is obtained 35 times faster than systematic Cartesian sampling of the evolution domain. The extension to multi-dimensional spectroscopy is outlined.