HREELS signal processing via wavelets

In spectroscopy, the recorded spectra can often be modelled as the noisy convolution product of an instrumental function with the ‘true’ signal to be estimated. Such models have often been used for high‐resolution electron energy‐loss spectroscopy (HREELS). In this article, a new method is suggested to estimate the ‘true’ HREELS signal, i.e. the original electronic diffusion function with ‘true’ peak intensities. Our method relies upon the use of wavelets that, because they exhibit simultaneous time and frequency localization, are well‐suited for signal analysis. Firstly, a wavelet shrinkage algorithm is used to filter the noise. This is achieved by decomposing the noisy signal into an appropriate wavelet basis and then thresholding the wavelet coefficients that contain noise. This algorithm has a particular threshold related to frequency and time. Secondly, the broadening due to the instrumental response is eliminated through a deconvolution process. This step mainly rests on the existing relation between the Lipschitz regularity of the signal and the decay with scale of its wavelet coefficients and on least squares. The efficiency of this technique is highlighted by comparing the results obtained with those provided by other published methods. This work is the second in a series of three papers in this issue. The first one presents background knowledge on the wavelets required to understand the estimation methods. The third paper explores the application of wavelet filtering and deconvolution techniques to x‐ray photoelectron spectroscopy. Copyright © 2004 John Wiley & Sons, Ltd.     

Deconvolving compactly supported densities

This paper addresses the statistical problem of density deconvolution under the condition that the density to be estimated has compact support. We introduce a new estimation procedure, which establishes faster rates of convergence for smooth densities as compared to the optimal rates for smooth densities with unbounded support. This framework also allows us to relax the usual condition of known error density with non-vanishing Fourier transform, so that a nonparametric class of densities is valid; therefore, even the shape of the noise density need not be assumed. These results can also be generalized for fast decaying densities with unbounded support. We prove optimality of the rates in the underlying experiment and study the practical performance of our estimator by numerical simulations.      

Efficiency of four different techniques in coupled HPLC-UV/VIS to quantify overlapping peaks with known spectral features

Summary Four different techniques to quantify unresolved chromatographic peaks with known spectral features combined with photodiode array detection, are investigated as regards their efficiency for the accurate and precise determination of drugs in the low g-range. The comparison includes peak suppression utilising difference chromatograms, first-order derivative chromatograms, selective chromatograms, generated by the calculation of orthogonal polynomial shares, and the powerful least-squares multicomponent analysis approach. Each of these methods uses UV-spectra taken throughout, the peak. The results presented and conclusions reached should enable the chromatographer to come to a decision about the reasonable use of these options now provided by multichannel detection in HPLC.     

FTIR-spectroscopy as a highly sensitive technique to study adsorption and desorption on ionic film and single crystal surfaces

Sample/spectrum relationships are investigated using both a low resolution rapid-scanning NIR monochromator and a Fourier transform instrument capable of high resolution and are evaluated in terms of whether or not the resolution of the instrument is sufficient for measuring the natural bandwidths corresponding to the sample. Based on the sample/spectrum relationship a criterion is developed which must be followed in order to apply either derivative spectroscopy or deconvolution to enhance the resolution of overlapped bands without generating spectral artifacts.     

A mathematical and physical Study of multiscale deconvolution models of turbulence

This work presents a rigorous analysis of mathematical and physical properties for solutions of multiscale deconvolution turbulence models. We show that solutions of these models exactly conserve model quantities for the integral invariants of fundamental physical importance: kinetic energy, helicity, and (in two dimensions) enstrophy. The kinetic energy conservation is the key that allows us to next apply the phenomenology of homogeneous, isotropic turbulence to establish the existence of a model energy cascade and, in particular, that the cascade exhibits enhanced energy dissipation in a secondary accelerated cascade, which ends at the model's microscale (which we establish is larger than the Kolmogorov microscale). We also prove that the model dissipates energy at the same rate as true turbulent flow, ～ O(U³ ∕ L), independent of Reynolds number. Lastly, we prove the existence of global attractors for the model solutions; the proof of which also shows that solutions are actually one degree of regularity higher than previously known. Copyright © 2012 John Wiley & Sons, Ltd.     

Experimental shift allowance in the deconvolution of SIMS depth profiles

We study the deconvolution of the secondary ion mass spectrometry (SIMS) depth profiles of silicon and gallium arsenide structures with doped thin layers. Special attention is paid to allowance for the instrumental shift of experimental SIMS depth profiles. This effect is taken into account by using Hofmann's mixing‐roughness‐information depth model to determine the depth resolution function. The ill‐posed inverse problem is solved in the Fourier space using the Tikhonov regularization method. The proposed deconvolution algorithm has been tested on various simulated and real structures. It is shown that the algorithm can improve the SIMS depth profiling relevancy and depth resolution. The implemented shift allowance method avoids significant systematic errors of determination of the near‐surface delta‐doped layer position. Copyright © 2013 John Wiley & Sons, Ltd.     

水声通信中基于信道辨识的盲turbo均衡方法

水声信道多途效应明显,造成接收信号存在严重的码间干扰(ISI,Intersymbol interference)。基于最小均方误差(MMSE,Minimum mean square error)准则的turbo均衡器级联了均衡和信道译码,能够有效去除ISI,并获得优良的性能。由于水声信道的时变性,传统MMSE-turbo均衡需要周期性的训练序列,以实现连续可靠的通信。训练序列虽然提高了通信的可靠性,但降低了信息的有效传输速率。因此,为提高通信效率,本文提出了一种盲turbo均衡方法,该方法通过引入新的盲信道辨识器来同时获得信道估计响应和已去除部分ISI的初步均衡输出信号,并为turbo均衡提供初始的响应参数和比特软信息。与水声通信中应用较多的盲判决反馈均衡器(DFE,Decision feedback equalizer)相比,海上实验结果证明本文提出的盲turbo均衡方法抗信道多途衰落的能力较强,并且与传统MMSE-turbo均衡相比无需训练序列,因此提高了信息的有效传输速率。     

Spectral analysis of Sr 3d XPS spectrum in Sr-containing hydroxyapatite

The Sr 3d X-ray photoelectron spectroscopy (XPS) spectrum of Sr-containing hydroxyapatite (SHAp) overlaps completely with the P 2p spectrum. Thus, the chemical state identification of Sr in SHAp is a challenging task. In this work, the Sr 3d spectrum was isolated from the overlapping spectra for analyzing the chemical state of Sr using a generic peak-fitting method. The SHAp layers containing various Sr concentrations were produced on a Ti substrate using a chemical treatment process with a calcium phosphate slurry that included Sr (NO₃)₂. The distribution of the constituent elements changed according to the Sr concentration, implying that the chemical state of Sr varied with concentration. The isolation of the Sr 3d XPS spectrum was conducted via spectral deconvolution using the P 2p spectrum corresponding to HAp. The isolated Sr 3d spectrum revealed that the chemical state of Sr was in SrO and Sr-substituted HAp states, and their ratio varied with the Sr concentration in the layer. The SrO to Sr-substituted HAp ratios affected the Sr ion releasing behavior from the SHAp layer, supporting the validity of the obtained analytical results.     

Site mapping and small molecule blind docking reveal a possible target site on the SARS-CoV-2 main protease dimer interface

The SARS-CoV-2 virus is causing COVID-19 resulting in an ongoing pandemic with serious health, social, and economic implications. Much research is focused in repurposing or identifying new small molecules which may interact with viral or host-cell molecular targets. An important SARS-CoV-2 target is the main protease (M^pro), and the peptidomimetic α-ketoamides represent prototypical experimental inhibitors. The protease is characterised by the dimerization of two monomers each which contains the catalytic dyad defined by Cys¹⁴⁵ and His⁴¹ residues (active site). Dimerization yields the functional homodimer. Here, our aim was to investigate small molecules, including lopinavir and ritonavir, α-ketoamide 13b, and ebselen, for their ability to interact with the M^pro. The sirtuin 1 agonist SRT1720 was also used in our analyses. Blind docking to each monomer individually indicated preferential binding of the ligands in the active site. Site-mapping of the dimeric protease indicated a highly reactive pocket in the dimerization region at the domain III apex. Blind docking consistently indicated a strong preference of ligand binding in domain III, away from the active site. Molecular dynamics simulations indicated that ligands docked both to the active site and in the dimerization region at the apex, formed relatively stable interactions. Overall, our findings do not obviate the superior potency with respect to inhibition of protease activity of covalently-linked inhibitors such as α-ketoamide 13b in the M^pro active site. Nevertheless, along with those from others, our findings highlight the importance of further characterisation of the M^pro active site and any potential allosteric sites.     

盲目反卷积光谱图超分辨复原算法

反卷积是实现光谱图超分辨复原的重要手段,与常规反卷积相比,盲目反卷积具有不需要预先准确获取卷积核函数的优势。着眼于充分利用光谱信号的特点和已有的光谱图反卷积成果,详细讨论了空域迭代盲目反卷积方法用于光谱图反卷积时的算法实现问题,并在分析光谱图卷积退化过程的基础上,针对光谱图反卷积算法特点,提出了光谱图卷积退化简化计算模型和最小二乘高斯拟合模型,以解决算法中相应的计算问题。基于Matlab平台的仿真表明,对于所用的高斯型谱线和点扩散函数,空域迭代盲目反卷积算法效果良好,在信噪比为50 dB时,分辨率提高约30％。