阿达玛变换光谱和图象及其在分析化学中的应用

本文对阿达玛变换光谱和成象的原理进行了简单介绍，并对８０年代以来阿达玛变换技术在分析化学中的应用进行了评述。     

Multielement atomic absorption analysis using Hadamard transform spectroscopy with a new computation and superposition procedure

The application of Hadamard transform spectroscopy (HTS) to analytical atomic spectroscopy has been investigated. A theoretical examination of the signal to noise ratio indicates that HTS offers a slight multiplex advantage over single slit scanning of the spectrum for the measurement of intense lines, as in atomic absorption, but is disadvantageous for measuring small signals in atomic emission and fluorescence. Using a simple HT spectrometer Mg and Pb were determined simultaneously by flame atomic absorption spectrometry. Sensitivities similar to those of conventional systems were obtained but, owing to instrumental imperfections and a short data collection time, detection limits were worse. Optimum system performance was obtained when the mask interval width was equal to the width of the image of the spectrometer entrance slit. Greater spectral detail was revealed by superposition of a set of computed spectra in which the starting point of each spectrum was displaced from the others by a distance less than the interval width of the Hadamard mask. This approach gave improved spectra without increased instrumental complexity.     

Selective multiplex advantage with an electro-optic Hadamard transform spectrometer for multielemental atomic emission

A liquid-crystal spatial light-modulator Hadamard transform spectrometer is adapted for multielemental atomic spectrochemical analysis. The flame emissions of alkali metals are studied as a preliminary example. The multiplex disadvantage normally plaguing application of Hadamard and Fourier transform methods to atomic analysis is circumvented. Permanent electro-optic "closure" of certain Hadamard mask slits (corresponding to intense major element emissions) improves the signal-to-noise ratio (SNR) of the remaining trace element emissions. This approach to SNR enhancement of weaker spectral features by blocking known intense features is called the selective multiplex advantage. A problem with the contrast ratio (relative transmissions of the transparent and opaque states) of the liquid-crystal Hadamard mask has been identified in terms of "optical leakage". This produces an offset in the Hadamard encodegram, and leads to concentration-dependent baseline-offset effects in the transformed spectrum. A mathematical correction procedure was devised and evaluated experimentally.     

双编码阿达玛变换光谱法：原理,仪器及光谱分析研究

本文根据阿达玛变换的原理研制成一种双编码阿达玛变换光谱仪，与单编码及常规光谱仪相比，该仪器具有高信噪比、高输入和单检测器多通道同时检测的优点。试样分析表明：该仪器能用于荧光谱分析和原子线光谱分析。     

Detecting and Removing Data Artifacts in Hadamard Transform Ion Mobility-Mass Spectrometry Measurements

Applying Hadamard transform multiplexing to ion mobility separations (IMS) can significantly improve the signal-to-noise ratio and throughput for IMS coupled mass spectrometry (MS) measurements by increasing the ion utilization efficiency. However, it has been determined that fluctuations in ion intensity as well as spatial shifts in the multiplexed data lower the signal-to-noise ratios and appear as noise in downstream processing of the data. To address this problem, we have developed a novel algorithm that discovers and eliminates data artifacts. The algorithm employs an analytical approach to identify and remove artifacts from the data, decreasing the likelihood of false identifications in subsequent data processing. Following application of the algorithm, IMS-MS measurement sensitivity is greatly increased and artifacts that previously limited the utility of applying the Hadamard transform to IMS are avoided. Figure

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Theoretical multiplex gain in a UV/VIS Hadamard transform spectrometer utilizing a uniformly imperfect encoding mask

The effect of a uniformly imperfect (non-ideal) encoding mask on the signal-to-noise ratio improvement in a Hadamard transform spectrometer utilizing photon detection is theoretically studied. General equations are developed for the calculation of the multiplex gain (the Fellgett advantage) under conditions of limitation by shot noise and source-fluctuation noise. It is shown that for both cases, the multiplex gain depends on the transmission properties of the encoding mask, the UV/VIS spectrum impinging upon the mask, and the multiplex size, N. It is demonstrated that a uniformly imperfect encoding mask allows sufficient multiplex gain, and that photon-detection in Hadamard transform spectrometry can have advantages in some spectroscopic applications. In addition, comparisons are made between the multiplex gain advantages present in UV/VIS FTS and those present in UV/VIS HTS.     

使用一维机械模板的高分辨阿达玛变换显微图像探测技术研究

阿达玛变换（HT）是一种类似于傅里叶变换（FT）的光谱调制技术,具有多通道同时检测和多通道成像能力等优点,但两者的数学模型、对光信号的调制方法和调制手段都不一样。由于HT仅涉及四则运算,而FT涉及较为复杂的三角函数和复数运算,所以HT的解码速度快于FT。在成像技术方面,HT具有直接成像的能力,而FT只能对通过其它方式获取的图像进行加工处理。     

A comparison of signal-to-noise ratios for single channel methods (sequential and multiplex) vs multichannel methods in optical spectroscopy

Four major types of spectroscopic systems for quantitative analysis of one or more spectral components we compared, with regard to signal-to-noise ratio for constant analysis time. These four methods are based on sequential-linear scan, sequential-slew scan, multichannel, and multiplex approaches. The multiplex methods can generally be classified into two types, namely Fourier transform spectroscopy and Hadamard transform spectroscopy. It is shown that for the same spectral source, for the same resolving power luminosity product of the optical system, and the same detector, the multichannel approach is the best and the sequential slew scan system is nearly as good for relatively simple spectra in the u.v.- Visible region. Multiplex methods have little to offer in the u.v.- Visible region, where the detector noise limitation seldom applies and where background shot and/or fluctuation noise are dominant but could find considerable use in the u.v.- Visible region for atomic fluorescence or emission spectroscopy especially if the density of spectral lines in the measurement region is not too great and the background intensity is low.     

Hadamard transform fluorescence image microscopy using one-dimensional movable mask

With a 511-slit one-dimensional (1D) Hadamard mask and a highly sensitive linear charge-coupled device (CCD), spatial multiplexing is performed and a programmable Hadamard transform (HT) microscopic fluorescence imaging system was developed. The system can generate 511×512 pixel format images for small samples. Sensitivity, signal to noise ratio, imaging speed and spatial resolution of this system were discussed. The results show that the system can be applied for single-cell imaging sensitively in a short time. Spatial resolution up to 0.24 μm/pixel, which is close to the resolution limit of the conventional optical microscope, has been obtained under oil lens. The weak native fluorescence imaging for pollen cells can be realized within 1 min. The system has been applied for multi-parameter evaluation of tumor malignancy based on nuclear DNA ploidy measurements for one breast tumor specimen. The result indicates that the system has good application prospect in cell biology and medicine.     

高分辨阿达玛变换显微荧光图像分析(Ⅱ)单细胞DNA荧光图像生成、处理及自动定量分析研究

本研究把荧光显微镜，阿达玛变换多通道成像技术和计算机图象处理技术结合起来，建立了一种单细胞DNA荧光图像自动定量分析系统，对系统的成像原理、信号编码和解码方法及单细胞定量分析方法进行了讨论，分析结果表明，本系统提供的单细胞定量分析数据稳定可靠。     

Hadamard Transform Time‐of‐Flight Mass Spectrometry: More Signal,More of the Time

Hadamard transform time‐of‐flight mass spectrometry (HT‐TOF MS) is a type of mass analysis that was developed to couple continuous ion sources to the inherently pulsed nature of time‐of‐flight measurements. Unlike conventional TOF MS, the Hadamard transform method offers a duty cycle of 50 %, with the possibility of extending it to 100 %. Because it is a multiplexing technique, the attainable signal‐to‐noise ratio (SNR) is also significantly higher than that of conventional TOF MS. This review covers the basic principles behind HT‐TOF MS. We illustrate, through examples, the source of the high‐duty cycle and the increase in SNR. These features translate to a mass spectral storage rate that is the fastest among similar instruments, which enables its use as a detector for high‐speed separations.     

Multitechnique spectroscopic analysis of polymer surfaces

The analysis of polymeric materials by modern surface sensitive spectroscopic experiments has yielded results which can be useful in solving both fundamental structural questions and problems which arise with the use of working materials. This paper will review the developments in polymer surface analysis which utilize the techniques of X-ray photoelectron spectroscopy (XPS or ESCA), secondary ion mass spectrometry (SIMS), ion scattering spectrometry (ISS), and fourier transform IR (FT-IR) spectroscopy stressing the complementary nature of the information derived from these methods.     

Positive confirmation of identity of doping agents using gas chromatography-mass spectrometry with Fourier transform infrared spectrometry

During the past two decades, the use of retention times in gas chromatography has been augmented by mass spectrometric data. By providing both the retention indices and spectrometric data, this technique has greatly improved gas chromatographic identification analysis. However, although gas chromatography-mass spectrometry has become pre-eminent, several drawbacks still remain. The mass spectral library often gives erroneous identifications when concentrations near the detection limit are analysed, when gas chromatographically interfering substances are present, or when structural isomers or compounds exhibiting identical retention behaviour are analysed. Linked with gas chromatography-mass spectrometry, Fourier transform infrared spectroscopy can be a powerful complementary technique in peak identification analysis. Some spectral data to illustrate this point are presented.     

阿达玛变换光谱和成像技术的应用和研究进展

阿达玛变换(HT)作为一种多通道光谱调制技术，具有多通道同时检测能力、多通道成像能力以及适用于数据处理等优点。综述了近十年来HT光谱和成像技术在分析科学中的应用和研究进展。主要从HT模板编码技术和HT激发序列应用技术等方面讨论了其最新发展和存在的问题，并展望了其发展前景。     

阿达玛变换显微图象分析(Ⅱ)──荧光衰减对图象和定量分析数据的影响

采用计算机模拟的方法,系统地考察了试样的荧光衰减对阿达玛变换图象和定量分析数据的影响,并把阿达玛变换显微图象分析仪用于细胞内DNA的定量分析,得到了满意的结果。     

Instrument for Hadamard transform three-dimensional fluorescence microscope image analysis

An instrument combining fluorescence microscopy with Hadamard transform multiplexed imaging was designed by which a three-dimensional Hadamard transform fluorescence microscopic cell image was obtained. The image can provide useful information including, simultaneously, the apparent dimensions and the shape of the analytical sample, the content and the distribution of some species in it.     

Enhancement of the Nuclear Spin Noise Signal Using Wavelet Transform

Spin noise spectroscopy has attracted considerable attention recently owing partly to intrinsic interest in the phenomenon and partly to its significant application potential. Here, we address the inherent problem of low sensitivity of nuclear spin noise and examine the utility of wavelet transform to mitigate this problem by distinguishing real peaks from the noise contaminated data. Suppression of the random circuit noise and the consequent enhancement of the correlated nuclear spin noise signal have been demonstrated with discrete wavelet transform. Spectra of both ¹H and ¹³C nuclear spins have been considered and significant signal enhancements in both the cases have been observed. A detailed analysis of several possible wavelet, thresholding and decomposition solutions have been made to obtain the optimum condition for signal enhancement. It is observed that the application of wavelet transform leaves the spin noise signal line shape essentially unchanged, which is an advantage for several applications involving spin noise spectra.     

Fast 2D NMR ligand screening using Hadamard spectroscopy

Fast 2D NMR-based screening can be achieved using Hadamard encoded spectroscopy to focus on the signals of interest (e.g., enzyme active or ligand recognition sites). By recording a set of Hadamard spectra (a "Hadamard constellation") with relative offsets comparable to the excitation bandwidth, quantitative ligand-induced shifts can be obtained from peak intensities.     

PM3, AM1, MINDO3 semi-empirical IR spectra simulations for some nitriles of interest for Titan's chemistry

A set of the semi-empirical methods (PM3, AM1, MNDO and MINDO3) has been tested to find the best auxiliary tool for the identification of nitriles by gas chromatography/Fourier transform IR spectroscopy/mass spectrometry, considering five nitriles of interest for Titan's chemistry as test compounds: acetonitrile, acrylonitrile, cyanoacetylene, 2-butynenitrile and dicyanoacetylene. Of the four semi-empirical methods, MNDO can be considered as the most advantageous auxiliary tool for the gas chromatography/Fourier transform IR spectroscopy/mass spectrometry (GC/FTIR/MS) identification of nitriles of interest for Titan's atmospheric chemistry, since (1) the simulated IR spectra best match the experimental (in some cases AM1 gives comparable results); (2) it provides the best linearity between the calculated and experimental frequencies (correlation coefficient of 0.990); a scaling factor of 0.90 can be applied to afford better correspondence between the calculated and experimental wavenumbers. At the same time, none of the methods is able to predict infrared intensities and a spectral intensity pattern.     

石油组分高分辨质谱分析进展与展望

石油是一种复杂体系,研究石油分子组成是分析化学领域的经典难题.近年来,傅里叶变换离子回旋共振质谱技术(Fourier transform ion cyclotron resonance mass spectrometry,FT-ICR MS)的发展,为从分子水平认识石油组成提供了机会,引起了石油化学界的高度关注,并被期待能在石油、石化领域的相关研究中实现重大突破.本文从质谱分辨率和电离技术方面介绍了石油样品的分析需求,总结了近几年基于FT-ICR MS技术对石油分子组成的研究进展,分析了其在应用中存在的关键技术问题及下一步研究方向,并对FT-ICR MS的发展前景给予展望.