Research on a deconvolution algorithm for laser-induced fluorescence diagnosis based on the maximum entropy principle

Laser-induced fluorescence(LIF)spectroscopy is employed for plasma diagnosis,necessitating the utilization of deconvolution algorithms to isolate the Doppler effect from the raw spectral signal.However,direct deconvolution becomes invalid in the presence of noise as it leads to infinite amplification of high-frequency noise components.To address this issue,we propose a deconvolution algorithm based on the maximum entropy principle.We validate the effectiveness of the proposed algorithm by utilizing simulated LIF spectra at various noise levels(signal-to-noise ratio,SNR=20–80 d B)and measured LIF spectra with Xe as the working fluid.In the typical measured spectrum(SNR=26.23 d B)experiment,compared with the Gaussian filter and the Richardson–Lucy(R-L)algorithm,the proposed algorithm demonstrates an increase in SNR of 1.39 d B and 4.66 d B,respectively,along with a reduction in the root-meansquare error(RMSE)of 35%and 64%,respectively.Additionally,there is a decrease in the spectral angle(SA)of 0.05 and 0.11,respectively.In the high-quality spectrum(SNR=43.96 d B)experiment,the results show that the running time of the proposed algorithm is reduced by about98%compared with the R-L iterative algorithm.Moreover,the maximum entropy algorithm avoids parameter optimization settings and is more suitable for automatic implementation.In conclusion,the proposed algorithm can accurately resolve Doppler spectrum details while effectively suppressing noise,thus highlighting its advantage in LIF spectral deconvolution applications.

FLUORESCENCE SPECTRUM ANALYSIS OF ETHER-WATER SOLUTION BASED ON GAUSSIAN DECOMPOSITION METHOD

The fluorescence spectrum of the ether-water solution excited by the ultraviolet light with the wavelength of 245 nm is experimentally detected. Based on the second derivative analysis, the fluorescence spectrum of the ether-water solution is used as Gaussian decomposition and seven Gaussian spectral lines are obtained. The center wavelength, the peak intensity and the half peak bandwidth of each Gaussian spectral line are measured, and the multi-peak fitting is made by using Gaussian primitive parameters. The highest and the lowest oscillation energy level differences in the ground state of each Gaussian spectrum are calculated. It is found that there are seven types of luminescent association molecules formed by ether and water molecules in different configurations existed in the solution. The location of each optimum absorption wavelength and the half peak bandwidth of the Gaussian spectral line is different. The energy level difference with the central wavelength of 304 nm attains the maximum value The result can contribute to the study of the molecular association in ether-water solution.

Spectrum Correction in Study of Solvation Dynamics by Fluorescence Non-collinear Optical Parametric Amplification Spectroscopy

Femtosecond time-resolved fluorescence non-collinear optical parametric amplification spec- troscopy can extract the curve of spectral gain from its parametric superfluorescence. This unique spectrum correction method enables fluorescence non-collinear optical parametric amplification spectroscopy acquiring the genuine transient fluorescence spectrum of the studied system. In this work we employ fluorescence non-collinear optical parametric amplification spectroscopy technique to study the solvation dynamics of DCM dye in ethanol solution, and confirm that genuine solvation correlation function and shift of peak frequency can be derived from transient fluorescence spectra after the spectral gain correction. It demonstrates that fluorescence non-collinear optical parametric amplification spectroscopy can benefit the research fields, which focuses on both fluorescence intensity dynamics and fluorescence spectral shape evolution.

Hydrothermal Synthesis,Crystal Structure and Fluorescence Spectrum Studies of a Supramolecular Compound {[2-(2-Pyridyl)benzimidazoleH_2]^(2+)·[SbCl_5]^(2-)}_2

A new supramolecular compound, { [2-（2-pyridyl）benzimidazoleH2]2＋.[SBC15]2-}2, was synthesized by the hydrothermal reaction of o-diaminobenzene, 2-pyridinecarboxylie acid and SbCl3 in 1：1 HC1 solution, and characterized by chemical analysis, elemental analysis, IR spectra, thermogravimetfic analysis and fluorescence spectra. The crystal structure was deter- mined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P211c, with a = 16.0397（13）, b = 14.3189（12）, c = 15.6370（13） A, β = 105.8980（10）°, V = 3454.0（5） A3, Z = 4, C24H22Cl10N6Sb2, Mr = 992.48, Dc = 1.909 g/cm3,/z = 2.366 mm-1, S = 1.010, F（000） = 1920, R = 0.0254 and wR = 0.0555. The coordination anion, [SbCl5]2- which is a distorted tetragonal pyramid, is composed by coordinating action with Sb3＋ ion and five adjacent chloride ions. Every four coordination anions of [SbCl5]2- form a biquaternion ring structure through the secondary bonding of Sb...Cl. Moreover, the compound adopts a three-dimensional network supramolecular structure because of the hydrogen bonds and π-π stacking between the rings and the 2-（2-pyridyl）benzimidazole divalent cations. The title compound also shows good fluorescent behaviors.

Chemical Modification and Fluorescence Spectrum of Tryptophan Residues in Pullulanase

Tryptophan（Trp） residues in a pullulanase were modified by N-bromosuccinimide（NBS）. The results of the Spande method indicate that there are 18 Trp residues in the pullulanase and nine of them are located on the surface af the enzyme. Three of these Trp residues are nonessential residues which show the fastest reaction rate according to the Zou＇s plot. Two of the seven relative faster reacting residues are essential for the activity of the enzyme. The other eight are the slowest in the reaction rate or non-reactive residues for the reaction. The fluorescence and circular dichroism（CD） spectra of the pullulanase have been changed after the reaction with NBS. Potassium iodide（KI） and acrylamide also have remarkable influences on the fluorescence spectra of the pullulanase.

Fluorescence spectrum characteristic of ethanol-water excimer and mechanism of resonance energy transfer

The steady-state fluorescence spectrum characteristic of ethanol-water excimer has been studied in this paper. By analysing the features of the sharp emission spectrum with fine structures in a shortwave band and the characteristics of the broad and featureless fluorescence peaks in the longwave band, one can conclude that the excimers are formed between the new ethanol-water cluster molecules in the excited state and the ground state through the interaction among different chromophores. The excitation spectra in the two fluorescence bands have been studied, and their emission mechanisms have been ascertained based on the energy transfer theory. Furthermore, the critical distance of the resonance energy transfer has been calculated.

Highly sensitive detection of Rydberg atoms with fluorescence loss spectrum in cold atoms

Fluorescence loss spectrum for detecting cold Rydberg atoms with high sensitivity has been obtained based on lock-in detection of fluorescence of 6 P3/2 state when cooling lasers of the magneto-optical trap are modulated.The experiment results show that the signal to noise ratio has been improved by 32.64 dB when the modulation depth(converted to laser frequency)and frequency are optimized to 4 MHz and 6 kHz,respectively.This technique enables us to perform a highly sensitive non-destructive detection of Rydberg atoms.

Quantitative energy-dispersive X-ray fluorescence analysis for unknown samples using full-spectrum least-squares regression

The full-spectrum least-squares(FSLS) method is introduced to perform quantitative energy-dispersive X-ray fluorescence analysis for unknown solid samples.Based on the conventional least-squares principle, this spectrum evaluation method is able to obtain the background-corrected and interference-free net peaks, which is significant for quantization analyses. A variety of analytical parameters and functions to describe the features of the fluorescence spectra of pure elements are used and established, such as the mass absorption coefficient, the Gi factor, and fundamental fluorescence formulas. The FSLS iterative program was compiled in the C language. The content of each component should reach the convergence criterion at the end of the calculations. After a basic theory analysis and experimental preparation, 13 national standard soil samples were detected using a spectrometer to test the feasibility of using the algorithm. The results show that the calculated contents of Ti, Fe, Ni, Cu, and Zn have the same changing tendency as the corresponding standard content in the 13 reference samples. Accuracies of 0.35% and 14.03% are obtained, respectively, for Fe and Ti, whose standard concentrations are 8.82% and 0.578%, respectively. However, the calculated results of trace elements (only tens of lg/g) deviate from the standard values. This may be because of measurement accuracy and mutual effects between the elements.

Chemical Modification of Tryptophan Residues in Superoxide Dismutase from Camellia Pollen and Its Fluorescence Spectrum

The amino acid composition of the superoxide dismutase（SOD） from camellia pollen was measured and the tryptophan（Trp） residues were modified by using N-bromosuccinimide（NBS）. The results show that there are 21 Trp residues in an SOD molecule and seven of which are located on the surface of the enzyme. By researching the fluorescence spectra of the native SOD and the modified SOD, we have found that the emission wavelength of Trp is at 335 nm and the fluorescence intensity will decrease when the enzyme is modified. The results also show that potassium iodide（KI） can significantly quench the fluorescence of the native SOD, but it has a less pronounced effect on the modified enzyme. Glycerin as a surface activation reagent can stabilize the fluorescence of the modified enzyme.

Tryptophan Modification and Fluorescence Spectrum of Hyaluronidase

Tryptophan residues in hyaluronidase （HAase） were modified by N-bromosuccinimide （NBS）, the results indicated that there were eleven tryptophan residues in HAase, one of which was exposed and essential for the activity of the enzyme. The study on fluorescence quenching showed that KI could not quench all of the fluorescence from Trp residues in HAase, while acrylamide （Acr） could quench almost all of the fluorescence from Trp residues in HAase. The collisional quenching constants （KD） of HAase at different concentrations of Acr were calculated in terms of Stern-Volmer equation. The results implied that some of the Trp residues were buried in the interior of HAase and the Trp residue on the surface of HAase was not located in the hydrophobic pocket.

Laser-induced Fluorescence Excitation Spectrum of NiS in 15500-17200 cm^-1

The laser-induced fluorescence excitation spectrum of jet-cooled NiS molecule has been recorded in the energy range of 15500 17200 cm-1. Fifteen bands have been assigned as three transition progressions：[15.65]^3Ⅱ1（v′=0-4）-X^3∑0^-（v″=0）,[15.69]^3∑0^-（v′=0-4）-X^3∑0^-（v″=0）,and [15.81]^3Ⅱ1（v′=0-4）-X^3∑0^-（v″=0）.Spectroscopic constants for the three newly identified electronically excited states have been determined for the first time. In addition,the lifetimes for most observed vibronic bands have also been measured.

Study on the Regulation of Diorganogermanium Compounds on the Maillard Reaction of Histidine and Glycine by Fluorescence Spectrum

The suppression of diorganogermanium compounds on the Maillard reaction of histidine(His) and glycine (Gly) with glucose has been determined by fluorescence spectrum underphysiological conditions. The title compounds show inhibition for the fluorescence intensity (FI) ofglycosylated andno acids stronger than Ge-132.

Ultrasonic-Assisted Synthesis of Monodisperse Ag Nanoparticles and Their Applications in Surface Enhanced Raman Scattering and Fluorescence Enhancement

Monodisperse Ag nanoparticles with diameters of about 3.4 nm were synthesized by a facile ultrasonic synthetic route at room temperature with the reduction of borane-tert-butylamine in the presence of oleylamine （OAm） and oleic acid （OA）. The reaction parameters of time, the molar ratios of OAm to OA were studied, and it was found that these parameters played important roles in the morphology and size of the products. Meanwhile, surface enhanced Raman spectrum （SERS） property suggested the Ag nanoparticles exhibited high SERS effect on the model molecule Rhodamine 6G. And also, two-photon fluorescence images showed that the silver nanoparticles had high performances in fluorescence enhancement.

Synthesis, Characterization and Fluorescence of Phenylcarboxymethyl Sulfoxide Complexes with Lanthanide Nitrates

Phenylcarboxymethyl Sulfoxide, PhSOCH 2COOH(LH), complexes of six lanthanide nitrates: Ln 2L 2(NO 3) 4·2LH· n H 2O(where Ln=La, Ce, Pr, Nd, Sm, Eu) were synthesized. Elemental analyses, molar conductivities, IR, 1HNMR and TG DTA measurements were used to characterize the complexes. The results show that the ligand(L) is coordinated to metal ions through two oxygen atoms of the carboxyl group and one oxygen atom of the sulfoxide moieties. Neutral ligang (LH)is coordinated to two metal ions through two oxygen atoms of carboxyl group as an asymmetrical bridging bidentate. The fluorescence spectra of Eu 3+ complex indicates that there is no inversion symmetry at the site of Eu 3+ ion, but the emission intensity of fluorescence is quite good.The solubility of the complexes is very good in water.

Field Experiments of Multi-Channel Oceanographic Fluorescence Lidar for Oil Spill and Chlorophyll-a Detection

A Multi-channel Oceanographic Fluorescence Lidar(MOFL), with a UV excitation at 355 nm and multiple receiving channels at typical wavelengths of fluorescence from oil spills and chlorophyll-a(Chl-a), has been developed using the Laser- induced Fluorescence(LIF) technique. The sketch of the MOFL system equipped with a compact multi-channel photomultiplier tube(MPMT) is introduced in the paper. The methods of differentiating the oil fluorescence from the background water fluorescence and evaluating the Chl-a concentration are described. Two field experiments were carried out to investigate the field performance of the system, i.e., an experiment in coastal areas for oil pollution detection and an experiment over the Yellow Sea for Chl-a monitoring. In the coastal experiment, several oil samples and other fluorescence substances were used to analyze the fluorescence spectral characteristics for oil identification, and to estimate the thickness of oil films at the water surface. The experiment shows that both the spectral shape of fluorescence induced from surface water and the intensity ratio of two channels(I495/I405) are essential to determine oil-spill occurrence. In the airborne experiment, MOFL was applied to measure relative Chl-a concentrations in the upper layer of the ocean. A comparison of relative Chl-a concentration measurements by MOFL and the Moderate Resolution Imaging Spectroradiometer(MODIS) indicates that the two datasets are in good agreement. The results show that the MOFL system is capable of monitoring oil spills and Chl-a in the upper layer of ocean water.

Three-dimensional fluorescence characteristics of dissolved organic matter produced by Prorocentrum donghaiense Lu

Filtration and cross-flow ultrafiltration techniques were used to separate culture media of Prorocentrurn donghaiense at the exponential growth, stationary and decline stages into 〈0.45 μm filtrate, 100 kDa-0.45 μm, 1%100 kDa and 1-10 kDa retentate and 〈1 kDa ultrafiltrate fractions. The fluorescence properties of different molecular weights of dissolved organic matter （DOM） were measured by excitation-emission matrix spectra. Protein-like and humic-like fluorophores were observed in the DOM produced by P. donghaiense. The central positions of protein-like fluorophores showed a red shift with prolonged growth duration, shifting from tyrosine-like properties at the exponential growth stage to tryptophan-like properties at the stationary and decline stages. The excitation wavelengths of protein-like fluorophores exhibited some change in the exponential growth and stationary stages with increased molecular size, but showed little change in the decline stage. However, the emission wavelengths in the decline stage exhibited a blue shift. Very distinct C type and A type peaks in humic-like fluorophores were observed. With a prolonged culture time, the intensities of both of the peaks became strong and the excitation wavelengths of peak A showed a red shift, while the A：C ratios fell. More than 94% of fluorescent DOM was in the lower than 1 kDa molecular weight fraction.

Research on the discrimination methods of algae based on the fluorescence excitation spectra

The excitation spectra of chlorophyll （Chl） fluorescence can be used to differentiate phytoplankton populations at phylum level in vivo and in situ within a few minutes.The investigated phytoplankton divisions （Dinophyta,Bacillariophyta,Chrysophyta,Cyanophyta,Cryptophyta,Chlorophyta） are each characterized by a specific composition of photosynthetic antenna pigments and,consequently,by a specific excitation spectrum of the Chl fluorescence.Norm excitation spectra （emission of 680 nm and excitation of 400–600 nm） of every division were obtained from several species per division by a F4500 fluorescence spectrophotometer.Fisher’s linear discriminant analysis of the norm spectra shows that the divisions could be discriminated.The discrimination method,established by multivariate linear regression and weighted least squares,was used to differentiate the phytoplankton samples cultured in the laboratory and samples collected from the Jiaozhao Bay at division level.The correctly discriminated samples were more than 94% for single algal species ones,more than 84% for simulatively mixed ones,more than 83% for real mixed ones and 100% for samples collected from the Jiaozhou Bay for the dominant species.The method for phytoplankton differentiation described here can be applied to routine checking by fluorescence spectrophotometer,and benefit the monitoring and supervision tasks related to phytoplankton populations in the marine environments.

Multiple Excitation Wavelength Fluorescence Emission Spectra Technique for Discrimination of Phytoplankton

In vivo fluorescence methods are efficient tools for studying the distribution of phytoplankton in nature.Different algae species usually have different pigments with different ratios,which results in different fluorescence emission spectra.Based on multiple excitation wavelength fluorescence emission spectra,a discrimination technique is established in this study.The discrimination method,established by multivariate linear regression and weighted least-squares,was used to differentiate the samples cultured in the laboratory and collected from Jiaozhou Bay near Qingdao at the division level.The correctly discriminated samples were ≥ 86% for single algae samples,≥ 88% for simulatively mixed ones,≥ 91% for physically mixed ones and 100% for samples collected from Jiaozhou Bay.The result in this research is more definite for the physically mixed samples in the laboratory.The method described here can be employed to monitor the phytoplankton population in the marine environment.

海面乳化溢油水包油乳化液的LIF接收光功率饱和强度分析

海面溢油的水包油乳化液对海洋造成严重的危害,水包油乳化液的识别以及定量分析,对于海洋污染的处理以及海洋环境的恢复具有重要意义。近年来一些研究对较薄的乳化溢油进行了定量分析,然而对于油层较厚的乳化溢油却鲜有深入的研究。激光照射到海面的水包油乳化液产生的荧光,在一定条件下会开始出现饱和而不再变化,针对这一饱和临界点以及相关范围的水包油乳化液的光谱特征进行研究。根据LIF探测系统接收到的光功率与BRRDF数值的关系,使用BRRDF模型对荧光光谱进行仿真。分析的油品使用Romashkino油和Petrobaltic油,分别代表深色不透明的油和明亮透明的油。提出一种针对厚度较大的水包油乳化液的荧光强度计算方法,计算出两种油在不同浓度和乳化时间下的乳化液出现荧光饱和的厚度。对计算结果进行比较可以看出饱和厚度随着浓度的增加而降低,随着乳化时间的增加而降低。分析结果显示,对于海水中的深色不透明的油的水包油乳化液,LIF接收到的荧光强度通常会出现饱和,因此单独使用LIF系统无法判断出超过饱和厚度的乳化液层的厚度。设计了一个4层神经元的神经网络,对饱和临界点附近的荧光光谱对乳化液浓度的识别能力进行验证。验证结果显示,不同浓度的水包油乳化液,只要达到或超过饱和厚度,其荧光光谱就具有较好的鉴别能力,可以用来区分不同浓度的乳化液。对于那些距离饱和厚度比较远的样本,荧光光谱具有分辨乳化液是否达到饱和厚度的能力。这些实验和结论将对较厚的水包油乳化液的识别和定量分析研究提供参考。

基于KPCA与KLPP及Wilks统计量的留兰香三维荧光数据特征提取与鉴别分析

为实现留兰香产地的快速鉴别,该研究提出了一种核主成分分析(kernel principal component analysis,KPCA)与核局部保持投影(kernel locality preserving projections,KLPP)及WilksΛ统计量序贯融合的特征波长提取策略,在此基础上鉴别5个产地的留兰香。首先,在采集5个产地300个留兰香样本的三维荧光数据后,运用三角形内插值法去除原始光谱中的瑞利散射和拉曼散射,并运用SG(Savitzky-Golay)对数据进行平滑预处理。然后,对预处理后的荧光光谱数据分别利用KPCA、KPCA+KLPP、KPCA+WilksΛ统计量、 KPCA+KLPP+WilksΛ统计量4种方法提取特征激发波长和特征发射波长。接着,按特征激发波长从小到大顺序将其对应的特征发射波长光谱值首尾相连转换成行向量;4种方法从300个样本中各得到1个300行的特征波长光谱值矩阵。再者,运用Fisher判别分析(fisher discriminant analysis,FDA)对特征波长光谱值矩阵进行数据可分性融合,生成可分性FD(fisher discriminant)变量。选取前4个累计判别能力达到99%的FD变量作为鉴别模型的输入向量。最后,用支持向量机(support vector machine,SVM)算法分析4个FD变量,分别得到对应于4种特征提取波长方法的FDA+SVM鉴别结果,其正确率分别为92.00%、96.00%、94.67%、100%。结果表明,所提出的KPCA+KLPP+WilksΛ统计量序贯融合的特征波长提取策略能够有效减少三维荧光光谱数据的冗余,并能表征原始荧光数据的信息特征,实现了5种留兰香产地的正确鉴别。该研究可为后续利用三维荧光光谱开展留兰香重要组分量化分析提供一定的基础。