Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy最新文献_第6页

Human neuroglobin and H64A distal variant: How mutation and pH affect the heme pocket 人类神经红蛋白和H64A远端变异：突变和pH值如何影响血红素袋。

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-29 DOI: 10.1016/j.saa.2025.127401

Mirco Meglioli , Laura Cesati , Gianantonio Battistuzzi , Marco Borsari , Federico Sebastiani , Giulietta Smulevich

Neuroglobins (Ngbs) are low spin heme proteins, with His64 and His96 residues bound to the distal and proximal positions of the heme iron, respectively. His64 must be displaced to allow the ligation of exogenous molecules to the heme, thus regulating ligand binding. In fact, in the absence of the distal His, at physiological pH, the protein becomes high spin in both the ferric and ferrous states. However, the variant undergoes a pH-dependent coordination/spin state transition to a hexacoordinated low-spin species at alkaline pH, featuring Lys67 as the distal endogenous ligand. Here, we have investigated the effect of pH on the wild-type (WT) protein and the distal H64A variant of human Ngb in solution by a combination of UV–Vis electronic absorption, Magnetic Circular Dichroism and resonant Raman spectroscopies. In the WT protein, only a vinyl substituent conformational change is observed with increasing pH, due to the strong stability of the bis-histidyl heme coordination. Conversely, in the H64A variant alkaline pH induces a major structural rearrangement of the active site with the distal coordination of Lys67 to the heme, a change in the strength of the hydrogen bonds of the propionate groups and a conformational rearrangement of one vinyl substituent. We propose that these findings are due to the modifications in the E-helix as a consequence of Lys67 deprotonation in both the WT and the variant. These results provide further details at the molecular level on the fundamental role of distal residues for heme binding within the active site and protein stability.

神经球蛋白（Ngbs）是一种低自旋血红素蛋白，其His64和His96残基分别结合在血红素铁的远端和近端位置。His64必须移位，以允许外源分子连接到血红素，从而调节配体结合。事实上，在没有远端His的情况下，在生理pH值下，蛋白质在铁态和铁态都变得高自旋。然而，该变体在碱性pH下经历pH依赖的配位/自旋状态转变为六配位的低自旋物种，以Lys67为远端内源性配体。本文采用紫外可见电子吸收、磁圆二色性和共振拉曼光谱相结合的方法，研究了pH对溶液中野生型（WT）蛋白和人类Ngb远端H64A变体的影响。在WT蛋白中，随着pH值的增加，只观察到乙烯基取代基构象的变化，这是由于双组氨酸血红素配位的强稳定性。相反，在H64A变体中，碱性pH诱导活性位点的主要结构重排，Lys67与血红素的远端配位，丙酸基团的氢键强度的变化以及一个乙烯基取代基的构象重排。我们认为这些发现是由于在WT和变体中由于Lys67去质子化而导致的e -螺旋的修饰。这些结果在分子水平上为血红素结合活性位点和蛋白质稳定性的远端残基的基本作用提供了进一步的细节。

{"title":"Human neuroglobin and H64A distal variant: How mutation and pH affect the heme pocket","authors":"Mirco Meglioli , Laura Cesati , Gianantonio Battistuzzi , Marco Borsari , Federico Sebastiani , Giulietta Smulevich","doi":"10.1016/j.saa.2025.127401","DOIUrl":"10.1016/j.saa.2025.127401","url":null,"abstract":"<div><div>Neuroglobins (Ngbs) are low spin heme proteins, with His64 and His96 residues bound to the distal and proximal positions of the heme iron, respectively. His64 must be displaced to allow the ligation of exogenous molecules to the heme, thus regulating ligand binding. In fact, in the absence of the distal His, at physiological pH, the protein becomes high spin in both the ferric and ferrous states. However, the variant undergoes a pH-dependent coordination/spin state transition to a hexacoordinated low-spin species at alkaline pH, featuring Lys67 as the distal endogenous ligand. Here, we have investigated the effect of pH on the wild-type (WT) protein and the distal H64A variant of human Ngb in solution by a combination of UV–Vis electronic absorption, Magnetic Circular Dichroism and resonant Raman spectroscopies. In the WT protein, only a vinyl substituent conformational change is observed with increasing pH, due to the strong stability of the bis-histidyl heme coordination. Conversely, in the H64A variant alkaline pH induces a major structural rearrangement of the active site with the distal coordination of Lys67 to the heme, a change in the strength of the hydrogen bonds of the propionate groups and a conformational rearrangement of one vinyl substituent. We propose that these findings are due to the modifications in the <em>E</em>-helix as a consequence of Lys67 deprotonation in both the WT and the variant. These results provide further details at the molecular level on the fundamental role of distal residues for heme binding within the active site and protein stability.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127401"},"PeriodicalIF":4.6,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145936308","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Spectroscopic analysis reveals an opposite pattern between carnosic and rosmarinic acid concentrations in rosemary (Salvia rosmarinus) 光谱分析揭示了迷迭香（鼠尾草）中鼠尾草酸和迷迭香酸浓度的相反模式。

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-29 DOI: 10.1016/j.saa.2025.127392

A. Mishra , A. Krief , M.M. Sahoo , A. Schachter , I. Gonda , N. Dudai , T. Trigano , I. Herrmann

Carnosic acid (CA) and rosmarinic acid (RA) are the principal secondary metabolites (SMs) of rosemary (Salvia rosmarinus Spenn. – Lamiaceae). Previous studies have examined CA and RA separately. However, their opposing CA and RA concentration trends have not been examined. This study tested the hypothesis that CA (

C_{CA}

) and RA (

C_{RA}

) concentrations exhibit an opposite pattern that can be rapidly and non-destructively spectrally detected using visible-near infrared spectroscopy. Hyperspectral data were acquired using three methods: field-based canopy measurements with a bare-fiber spectrometer, unmanned aerial vehicle (UAV)-borne hyperspectral imagery of the canopy, and laboratory measurements of rosemary leaf powder using a spectrometer with bifurcated-fiber. The datasets were analyzed using one-band correlations and normalized difference spectral indices. Furthermore, to identify wavelengths contributing to the opposite pattern, partial least squares regression coefficients were examined exclusively in rosemary leaf powder, as water absorption bands masked the

C_{RA}

coefficients in the field-based canopy spectra. First derivatives of the standard CA and RA spectra demonstrated the opposite pattern at certain wavelengths that aligns with our spectral analysis. The opposite patterns between CA and RA are not only subjected to spectral analysis, but for nutrient–SM correlations as well, such as nitrogen correlating positively with

C_{CA}

but negatively with

C_{RA}

, and magnesium showing the reverse. Analyses of the hyperspectral data acquired from field grown plants, leaf powder and standard in the lab, together with nutrient–SM correlations,demonstrated the robustness of the opposite pattern. These opposite patterns demonstrated a reliable basis for non-destructive SM dynamics monitoring in rosemary.

鼠尾草酸（Carnosic acid， CA）和迷迭香酸（rosemary acid， RA）是迷迭香的主要次生代谢产物。-唇形科)。以前的研究分别检查了CA和RA。然而，它们的CA和RA浓度的相反趋势尚未得到检验。本研究验证了CA （CCA）和RA （CRA）浓度表现出相反模式的假设，可以使用可见-近红外光谱快速非破坏性地检测。采用三种方法获取高光谱数据：利用裸光纤光谱仪对冠层进行野外测量，利用无人机对冠层进行高光谱成像，利用分岔光纤光谱仪对迷迭香叶粉末进行实验室测量。利用单波段相关性和归一化差谱指数对数据集进行分析。此外，为了确定对相反模式有贡献的波长，我们对迷迭香叶粉的偏最小二乘回归系数进行了专门研究，因为在基于场的冠层光谱中，水分吸收波段掩盖了CRA系数。标准CA和RA光谱的一阶导数在某些波长显示相反的模式，与我们的光谱分析一致。在光谱分析中，CA和RA表现出相反的模式，营养物与sm的相关性也表现出相反的模式，如氮与CCA呈正相关，而与CRA负相关，镁则相反。从田间种植植物、叶粉和实验室标准品中获得的高光谱数据分析，以及营养- sm相关性，证明了相反模式的稳健性。这些相反的模式为迷迭香非破坏性SM动态监测提供了可靠的基础。

{"title":"Spectroscopic analysis reveals an opposite pattern between carnosic and rosmarinic acid concentrations in rosemary (Salvia rosmarinus)","authors":"A. Mishra , A. Krief , M.M. Sahoo , A. Schachter , I. Gonda , N. Dudai , T. Trigano , I. Herrmann","doi":"10.1016/j.saa.2025.127392","DOIUrl":"10.1016/j.saa.2025.127392","url":null,"abstract":"<div><div>Carnosic acid (CA) and rosmarinic acid (RA) are the principal secondary metabolites (SMs) of rosemary (<em>Salvia rosmarinus</em> Spenn. – Lamiaceae). Previous studies have examined CA and RA separately. However, their opposing CA and RA concentration trends have not been examined. This study tested the hypothesis that CA (<span><math><msub><mrow><mi>C</mi></mrow><mrow><mi>CA</mi></mrow></msub></math></span>) and RA (<span><math><msub><mrow><mi>C</mi></mrow><mrow><mi>RA</mi></mrow></msub></math></span>) concentrations exhibit an opposite pattern that can be rapidly and non-destructively spectrally detected using visible-near infrared spectroscopy. Hyperspectral data were acquired using three methods: field-based canopy measurements with a bare-fiber spectrometer, unmanned aerial vehicle (UAV)-borne hyperspectral imagery of the canopy, and laboratory measurements of rosemary leaf powder using a spectrometer with bifurcated-fiber. The datasets were analyzed using one-band correlations and normalized difference spectral indices. Furthermore, to identify wavelengths contributing to the opposite pattern, partial least squares regression coefficients were examined exclusively in rosemary leaf powder, as water absorption bands masked the <span><math><msub><mrow><mi>C</mi></mrow><mrow><mi>RA</mi></mrow></msub></math></span> coefficients in the field-based canopy spectra. First derivatives of the standard CA and RA spectra demonstrated the opposite pattern at certain wavelengths that aligns with our spectral analysis. The opposite patterns between CA and RA are not only subjected to spectral analysis, but for nutrient–SM correlations as well, such as nitrogen correlating positively with <span><math><msub><mrow><mi>C</mi></mrow><mrow><mi>CA</mi></mrow></msub></math></span> but negatively with <span><math><msub><mrow><mi>C</mi></mrow><mrow><mi>RA</mi></mrow></msub></math></span>, and magnesium showing the reverse. Analyses of the hyperspectral data acquired from field grown plants, leaf powder and standard in the lab, together with nutrient–SM correlations,demonstrated the robustness of the opposite pattern. These opposite patterns demonstrated a reliable basis for non-destructive SM dynamics monitoring in rosemary.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127392"},"PeriodicalIF":4.6,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882643","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Near-infrared spectroscopy combined with multi-source feature fusion and transformer for identifying the extent of sulfur fumigation in dried ginger 近红外光谱结合多源特征融合和变压器技术鉴定干姜中硫熏蒸程度。

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-29 DOI: 10.1016/j.saa.2025.127396

Chengwu Chen , Tianshu Wang , Guisheng Zhou , Zhiyi Wu , Jia Liu , Xichen Yang , Hui Yan , Jinao Duan

The widespread use of sulfur fumigation in dried ginger processing poses significant quality and safety concerns, creating a pressing need for rapid, non-destructive discrimination techniques. While Near-Infrared (NIR) spectroscopy holds promise, effectively extracting subtle, fumigation-induced spectral features remains a challenge. The primary contribution of this study is the development of a novel multi-branch, multi-scale feature extraction framework that synergistically combines 1D-Convolutional Neural Networks (1D-CNN) and a Transformer model. This architecture processes raw and preprocessed NIR spectra in parallel, employing a hybrid strategy that fuses statistically significant features (identified by t-test filtering) with automatically learned deep features (from 1D-CNN). The integrated feature set is then modeled by the Transformer to capture global dependencies for highly accurate classification. Our model achieved exceptional performance, with 95.24% identification accuracy and average precision, recall, and F1-scores all exceeding 95%, significantly outperforming conventional methods. This work not only provides a robust and efficient solution for quality control of dried ginger but also establishes a new, transferable paradigm for feature extraction from spectroscopic data, with broad potential applications in pharmaceuticals, food, and agriculture.

硫熏蒸在干姜加工中的广泛应用引起了重大的质量和安全问题，迫切需要快速、非破坏性的鉴别技术。虽然近红外（NIR）光谱学有希望，但有效提取微妙的、熏蒸引起的光谱特征仍然是一个挑战。本研究的主要贡献是开发了一种新的多分支、多尺度特征提取框架，该框架协同结合了1d -卷积神经网络（1D-CNN）和Transformer模型。该架构并行处理原始和预处理的近红外光谱，采用混合策略，融合统计显著特征（通过t检验滤波识别）和自动学习的深度特征（来自1D-CNN）。然后，Transformer对集成的特性集进行建模，以捕获全局依赖项，以便进行高度精确的分类。我们的模型取得了优异的性能，识别准确率为95.24%，平均准确率、召回率和f1得分均超过95%，显著优于传统方法。该研究不仅为干姜的质量控制提供了可靠、高效的解决方案，而且为光谱数据的特征提取建立了一种新的、可转移的范式，在制药、食品和农业等领域具有广泛的应用前景。

{"title":"Near-infrared spectroscopy combined with multi-source feature fusion and transformer for identifying the extent of sulfur fumigation in dried ginger","authors":"Chengwu Chen , Tianshu Wang , Guisheng Zhou , Zhiyi Wu , Jia Liu , Xichen Yang , Hui Yan , Jinao Duan","doi":"10.1016/j.saa.2025.127396","DOIUrl":"10.1016/j.saa.2025.127396","url":null,"abstract":"<div><div>The widespread use of sulfur fumigation in dried ginger processing poses significant quality and safety concerns, creating a pressing need for rapid, non-destructive discrimination techniques. While Near-Infrared (NIR) spectroscopy holds promise, effectively extracting subtle, fumigation-induced spectral features remains a challenge. The primary contribution of this study is the development of a novel multi-branch, multi-scale feature extraction framework that synergistically combines 1D-Convolutional Neural Networks (1D-CNN) and a Transformer model. This architecture processes raw and preprocessed NIR spectra in parallel, employing a hybrid strategy that fuses statistically significant features (identified by <em>t</em>-test filtering) with automatically learned deep features (from 1D-CNN). The integrated feature set is then modeled by the Transformer to capture global dependencies for highly accurate classification. Our model achieved exceptional performance, with 95.24% identification accuracy and average precision, recall, and F1-scores all exceeding 95%, significantly outperforming conventional methods. This work not only provides a robust and efficient solution for quality control of dried ginger but also establishes a new, transferable paradigm for feature extraction from spectroscopic data, with broad potential applications in pharmaceuticals, food, and agriculture.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127396"},"PeriodicalIF":4.6,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145879714","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Designing free-base phenylcorroles to absorb in the phototherapeutic window 设计游离基苯基苯酚在光疗窗口的吸收

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-29 DOI: 10.1016/j.saa.2025.127366

Vinícius N. da Rocha, Maurick G. Barcelos, Rafael O. Terra, Paulo C. Piquini

Molecules used as photosensitizers in photodynamic therapy are required to satisfy several criteria for optimal performance. Among these, intense light absorption in the phototherapeutic window (650–950 nm) is highly desirable. Density functional theory QM/MM calculations were used to study the absorption spectra of a sample of free-base phenylcorroles in methanol. The distinctive structural parameters of the subset of phenylcorrole molecules in the sample, with absorption peaks in the phototherapeutic window, were identified. One of these structural parameters was exploited by introducing suitable atomic substitutions into the phenylcorrole, which resulted in red shifts (and blue shifts) in the lowest energy absorption peaks, with some of them occurring within the phototherapeutic window. These red shifts are shown to be related to the degree of variation of the structural parameter and to the atomic substitutions. These results show a strategy to design free base corroles that absorb within the phototherapeutic window.

光动力治疗中用作光敏剂的分子需要满足几个最佳性能标准。其中，光疗窗口（650-950 nm）的强光吸收是非常理想的。采用密度泛函理论（QM/MM）计算方法研究了游离基苯基苯酚在甲醇中的吸收光谱。确定了样品中苯基咯分子亚群的独特结构参数，并在光疗窗口中具有吸收峰。其中一个结构参数是通过在苯基氯中引入适当的原子取代来利用的，这导致了最低能量吸收峰的红移（和蓝移），其中一些发生在光疗窗口内。这些红移与结构参数的变化程度和原子取代有关。这些结果显示了一种设计在光疗窗口内吸收游离碱的策略。

引用次数: 0

Multicolor anti-counterfeiting and naked-eye visual temperature sensing based on niobate double perovskites 基于铌酸盐双钙钛矿的多色防伪裸眼视温传感

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-29 DOI: 10.1016/j.saa.2025.127410

Mengzhen Jia , Xiaoqi Zhao , Jiahui Ren , Tingting Li , Zhaoxia Fan , Mengyu Du , Rui Zhu , Luzhu Ma , Hao Suo

Ca₂LuNbO₆:Mn⁴⁺/Dy³⁺ (CLNO:Mn/Dy) phosphor was successfully synthesized by high-temperature solid-state reaction, and exhibited a composite luminescent characteristic composed of f-f transition of Dy³⁺ and d-d transition of Mn⁴⁺. The wavelength-dependent multi-color luminescence regulation from yellow to red was achieved by utilizing the different photoexcitation pathways of Mn⁴⁺ and Dy³⁺. By taking advantage of the inherent excellent thermal stability of inorganic oxides and the different temperature-dependent variations in the luminescence intensities of Mn⁴⁺ and Dy³⁺, a wide-temperature-range visual temperature sensing from red to yellow-green light was achieved by the luminescence intensity ratio (LIR)-based optical thermometry. The luminescence mechanism study showed that the luminescence processes of Mn⁴⁺ and Dy³⁺ are independent of each other. The temperature sensing property was attributed to the different thermal quenching behaviors of Dy³⁺ and Mn⁴⁺. The temperature sensing absolute sensitivity (S_a) and relative sensitivity (S_r) of CLNO:0.2 %Mn⁴⁺/2 %Dy³⁺ sample reached 0.023 K⁻¹ at 493 K and 1.86 % K⁻¹ at 473 K, respectively. The research result was significant for the development of multi-color luminescent anti-counterfeiting materials and non-contact visual temperature sensing materials.

采用高温固相反应成功合成了Ca2LuNbO6:Mn4+/Dy3+ (CLNO:Mn/Dy)荧光粉，并表现出Dy3+的f-f跃迁和Mn4+的d-d跃迁的复合发光特性。利用Mn4+和Dy3+不同的光激发途径，实现了从黄色到红色的波长依赖的多色发光调节。利用无机氧化物固有的优异热稳定性和Mn4+和Dy3+发光强度随温度变化的特性，采用基于发光强度比（LIR）的光学测温技术实现了从红光到黄绿光的宽温度范围的视觉测温。发光机理研究表明，Mn4+和Dy3+的发光过程是相互独立的。Dy3+和Mn4+具有不同的热猝灭行为。CLNO: 0.2% Mn4+/ 2% Dy3+样品的感温绝对灵敏度Sa和相对灵敏度Sr分别在493 K和473 K下达到0.023 K−1和1.86% K−1。该研究成果对多色发光防伪材料和非接触式视觉感温材料的开发具有重要意义。

{"title":"Multicolor anti-counterfeiting and naked-eye visual temperature sensing based on niobate double perovskites","authors":"Mengzhen Jia , Xiaoqi Zhao , Jiahui Ren , Tingting Li , Zhaoxia Fan , Mengyu Du , Rui Zhu , Luzhu Ma , Hao Suo","doi":"10.1016/j.saa.2025.127410","DOIUrl":"10.1016/j.saa.2025.127410","url":null,"abstract":"<div><div>Ca<sub>2</sub>LuNbO<sub>6</sub>:Mn<sup>4+</sup>/Dy<sup>3+</sup> (CLNO:Mn/Dy) phosphor was successfully synthesized by high-temperature solid-state reaction, and exhibited a composite luminescent characteristic composed of <em>f-f</em> transition of Dy<sup>3+</sup> and <em>d-d</em> transition of Mn<sup>4+</sup>. The wavelength-dependent multi-color luminescence regulation from yellow to red was achieved by utilizing the different photoexcitation pathways of Mn<sup>4+</sup> and Dy<sup>3+</sup>. By taking advantage of the inherent excellent thermal stability of inorganic oxides and the different temperature-dependent variations in the luminescence intensities of Mn<sup>4+</sup> and Dy<sup>3+</sup>, a wide-temperature-range visual temperature sensing from red to yellow-green light was achieved by the luminescence intensity ratio (LIR)-based optical thermometry. The luminescence mechanism study showed that the luminescence processes of Mn<sup>4+</sup> and Dy<sup>3+</sup> are independent of each other. The temperature sensing property was attributed to the different thermal quenching behaviors of Dy<sup>3+</sup> and Mn<sup>4+</sup>. The temperature sensing absolute sensitivity (<em>S</em><sub>a</sub>) and relative sensitivity (<em>S</em><sub>r</sub>) of CLNO:0.2 %Mn<sup>4+</sup>/2 %Dy<sup>3+</sup> sample reached 0.023 K<sup>−1</sup> at 493 K and 1.86 % K<sup>−1</sup> at 473 K, respectively. The research result was significant for the development of multi-color luminescent anti-counterfeiting materials and non-contact visual temperature sensing materials.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127410"},"PeriodicalIF":4.6,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145847600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Induction of chirality in rose Bengal via interaction with bovine serum albumin: Spectroscopic method to differentiate low- and high-affinity binding sites 通过与牛血清白蛋白相互作用诱导孟加拉玫瑰的手性：区分低亲和力和高亲和力结合位点的光谱方法

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-29 DOI: 10.1016/j.saa.2025.127400

Maurício Ikeda Yoguim , Maiara Stefanini Borges Caires , Aguinaldo Robinson de Souza , Nelson Henrique Morgon , Valdecir Farias Ximenes

Rose Bengal (RB) is a xanthene dye used for decades as a photosensitizer to produce singlet oxygen. Serum albumin, the main protein dissolved in blood plasma, plays vital roles, including transporting poorly soluble drugs, with RB being one of these ligands. In this study, we investigated the interaction between bovine serum albumin (BSA) and RB and discovered that it induces axial chirality in RB. More importantly, two distinct induced circular dichroism (ICD) bands were observed, with their shapes and intensities varying depending on the binding site within BSA. This approach enabled us to differentiate ICD signals associated with high- and low-affinity binding sites. By monitoring the quenching of the ICD band, we identified the high-affinity RB binding site as drug site 1 (DS1) on BSA. Conversely, the ICD band linked to low-affinity sites was associated with fatty acid-binding sites. Another key finding was that human serum albumin (HSA) did not produce an ICD signal at the lower-affinity sites. Using this property, we tracked the displacement of RB from BSA to HSA by observing the time-dependent loss of the ICD signal. The experimental results were supported by molecular docking studies, which showed that RB binds to multiple sites, with DS1 being the most favorable binding site. The ICD spectra for the RB conformations obtained from molecular docking were simulated using Density Functional Theory (DFT), revealing a correlation. These findings introduce new and potentially valuable spectroscopic methods for investigating albumin-ligand interactions.

玫瑰孟加拉（RB）是一种用于产生单线态氧的光敏剂几十年的杂蒽染料。血清白蛋白是溶解在血浆中的主要蛋白，它起着至关重要的作用，包括运输难溶性药物，RB就是其中一种配体。在本研究中，我们研究了牛血清白蛋白（BSA）与RB的相互作用，发现它诱导RB的轴向手性。更重要的是，观察到两个不同的诱导圆二色性（ICD）带，其形状和强度随BSA内结合位点的不同而变化。这种方法使我们能够区分与高亲和力和低亲和力结合位点相关的ICD信号。通过监测ICD波段的猝灭，我们确定了高亲和力RB结合位点为BSA上的药物位点1 （DS1）。相反，连接到低亲和力位点的ICD带与脂肪酸结合位点相关。另一个重要发现是人血清白蛋白（HSA）在低亲和力位点不产生ICD信号。利用这一特性，我们通过观察ICD信号的时变损失来跟踪RB从BSA到HSA的位移。分子对接研究支持了实验结果，RB与多个位点结合，其中DS1是最有利的结合位点。利用密度泛函理论（DFT）对分子对接得到的RB构象的ICD谱进行了模拟，揭示了两者之间的相关性。这些发现为研究白蛋白配体相互作用引入了新的和潜在有价值的光谱方法。

{"title":"Induction of chirality in rose Bengal via interaction with bovine serum albumin: Spectroscopic method to differentiate low- and high-affinity binding sites","authors":"Maurício Ikeda Yoguim , Maiara Stefanini Borges Caires , Aguinaldo Robinson de Souza , Nelson Henrique Morgon , Valdecir Farias Ximenes","doi":"10.1016/j.saa.2025.127400","DOIUrl":"10.1016/j.saa.2025.127400","url":null,"abstract":"<div><div>Rose Bengal (RB) is a xanthene dye used for decades as a photosensitizer to produce singlet oxygen. Serum albumin, the main protein dissolved in blood plasma, plays vital roles, including transporting poorly soluble drugs, with RB being one of these ligands. In this study, we investigated the interaction between bovine serum albumin (BSA) and RB and discovered that it induces axial chirality in RB. More importantly, two distinct induced circular dichroism (ICD) bands were observed, with their shapes and intensities varying depending on the binding site within BSA. This approach enabled us to differentiate ICD signals associated with high- and low-affinity binding sites. By monitoring the quenching of the ICD band, we identified the high-affinity RB binding site as drug site 1 (DS1) on BSA. Conversely, the ICD band linked to low-affinity sites was associated with fatty acid-binding sites. Another key finding was that human serum albumin (HSA) did not produce an ICD signal at the lower-affinity sites. Using this property, we tracked the displacement of RB from BSA to HSA by observing the time-dependent loss of the ICD signal. The experimental results were supported by molecular docking studies, which showed that RB binds to multiple sites, with DS1 being the most favorable binding site. The ICD spectra for the RB conformations obtained from molecular docking were simulated using Density Functional Theory (DFT), revealing a correlation. These findings introduce new and potentially valuable spectroscopic methods for investigating albumin-ligand interactions.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127400"},"PeriodicalIF":4.6,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145847599","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Multiphoton imaging coupled with steady-state and time-resolved fluorescence spectroscopy reveals protein-bound FAD in femtosecond-laser–injured regenerating muscle 多光子成像结合稳态和时间分辨荧光光谱揭示了飞秒激光损伤再生肌肉中蛋白结合的FAD

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-29 DOI: 10.1016/j.saa.2025.127403

Zih-Wun Wang , Hui-Jen Lin , Amir Fathi , Ian Liau

Regeneration of skeletal muscle involves tightly coupled structural and redox processes that remain difficult to characterize in vivo or in situ with molecular specificity. Here, we introduce a label-free spectroscopic imaging framework that integrates multiphoton imaging—including second-harmonic generation (SHG) and two-photon-excited fluorescence (TPEF)—with steady-state and time-resolved fluorescence spectroscopy to visualize sarcomere remodeling and redox dynamics in living zebrafish muscle. SHG imaging revealed a transient disruption and gradual restoration of sarcomeric order, indicating an asynchronous, sequential reassembly of myofibrillar structures following localized femtosecond laser ablation. In parallel, TPEF imaging detected a pronounced and spatially confined increase in intrinsic emission at the injury site. Single-photon fluorescence spectroscopy and lifetime analysis identified this emission as protein-bound, oxidized flavin adenine dinucleotide (FAD), matching the photophysical signature of mitochondrial flavoproteins and revealing localized redox activation during the early phase of repair. Complementary reactive‑oxygen-species (ROS) imaging confirmed localized oxidative stress associated with elevated electron-transport activity, linking mitochondrial metabolism to structural recovery. Together, these multimodal observations establish a quantitative, label-free framework for correlating mitochondrial FAD-mediated redox activity with sarcomeric remodeling, establishing a versatile optical platform for investigating flavin photophysics, oxidative metabolism, and regenerative physiology in living muscle tissues.

骨骼肌再生涉及紧密耦合的结构和氧化还原过程，这些过程仍然难以在体内或原位用分子特异性表征。在这里，我们介绍了一种无标记光谱成像框架，该框架将多光子成像（包括二次谐波产生（SHG）和双光子激发荧光（TPEF））与稳态和时间分辨荧光光谱相结合，以可视化活斑马鱼肌肉的肌节重塑和氧化还原动力学。SHG成像显示肌原纤维秩序的短暂破坏和逐渐恢复，表明局部飞秒激光消融后肌原纤维结构的非同步、顺序重组。同时，TPEF成像检测到损伤部位明显且空间受限的内征辐射增加。单光子荧光光谱和寿命分析鉴定出这种发射是蛋白质结合的氧化黄素腺嘌呤二核苷酸（FAD），与线粒体黄素蛋白的光物理特征相匹配，揭示了修复早期局部氧化还原激活。互补活性氧（ROS）成像证实了局部氧化应激与电子传递活性升高相关，将线粒体代谢与结构恢复联系起来。总之，这些多模式观察建立了一个定量的、无标记的框架，将线粒体fad介导的氧化还原活性与肌肉重构联系起来，建立了一个多功能光学平台，用于研究活肌肉组织中的黄素光物理、氧化代谢和再生生理学。

{"title":"Multiphoton imaging coupled with steady-state and time-resolved fluorescence spectroscopy reveals protein-bound FAD in femtosecond-laser–injured regenerating muscle","authors":"Zih-Wun Wang , Hui-Jen Lin , Amir Fathi , Ian Liau","doi":"10.1016/j.saa.2025.127403","DOIUrl":"10.1016/j.saa.2025.127403","url":null,"abstract":"<div><div>Regeneration of skeletal muscle involves tightly coupled structural and redox processes that remain difficult to characterize <em>in vivo</em> or <em>in situ</em> with molecular specificity. Here, we introduce a label-free spectroscopic imaging framework that integrates multiphoton imaging—including second-harmonic generation (SHG) and two-photon-excited fluorescence (TPEF)—with steady-state and time-resolved fluorescence spectroscopy to visualize sarcomere remodeling and redox dynamics in living zebrafish muscle. SHG imaging revealed a transient disruption and gradual restoration of sarcomeric order, indicating an asynchronous, sequential reassembly of myofibrillar structures following localized femtosecond laser ablation. In parallel, TPEF imaging detected a pronounced and spatially confined increase in intrinsic emission at the injury site. Single-photon fluorescence spectroscopy and lifetime analysis identified this emission as protein-bound, oxidized flavin adenine dinucleotide (FAD), matching the photophysical signature of mitochondrial flavoproteins and revealing localized redox activation during the early phase of repair. Complementary reactive‑oxygen-species (ROS) imaging confirmed localized oxidative stress associated with elevated electron-transport activity, linking mitochondrial metabolism to structural recovery. Together, these multimodal observations establish a quantitative, label-free framework for correlating mitochondrial FAD-mediated redox activity with sarcomeric remodeling, establishing a versatile optical platform for investigating flavin photophysics, oxidative metabolism, and regenerative physiology in living muscle tissues.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127403"},"PeriodicalIF":4.6,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145883236","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

High-throughput identification of geographical origins of rubies using hyperspectral visible and fluorescence spectroscopy 利用高光谱可见和荧光光谱技术高通量鉴定红宝石的地理产地。

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-29 DOI: 10.1016/j.saa.2025.127405

Jiwoo Cho , Mieun Kim , Sanghoon Cho , Sang-Ho Nam , Yonghoon Lee , Hoeil Chung

This study explored hyperspectral (HS) visible and fluorescence spectroscopy as a high-throughput analytical tool for discrimination of rubies originating from Myanmar (MM), Mozambique (MZ), and Thailand (TH). Rubies are a variety of the mineral corundum (Al₂O₃), and their color is mainly related to Cr and Fe. In this study, multiple rubies were loaded onto a carbon-coated plate and measured under a HS camera for high-throughput analysis. The absorption peaks around 420 nm and 558 nm were apparent in the visible spectra. Interestingly, a Raman peak at 692 nm also appeared due to excitation by ultraviolet radiation emitted from a visible lamp. However, due to various factors such as surface reflection, inclusions, and impurities, baseline fluctuations among the visible spectra were large. In contrast, the fluorescence spectra were more reproducible, and the emission peaks of rubies were better discernible. Therefore, support vector machine (SVM)-based discrimination accuracy using the fluorescence spectra was 97.8 % based on 100 repetitions of 5-fold cross-validation, higher than 95.8 % employing the visible spectra, and slightly higher or comparable to that (96.6 %) based on the elemental analysis using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Therefore, the demonstrated HS fluorescence scheme, which enables high-throughput analysis of multiple rubies, could be a versatile alternative in the field of gemstone evaluation where individual sample-by-sample measurement has been a common practice.

本研究探讨了高光谱（HS）可见光谱和荧光光谱作为鉴别原产缅甸（MM）、莫桑比克（MZ）和泰国（TH）红宝石的高通量分析工具。红宝石是矿物刚玉（Al2O3）的变种，其颜色主要与Cr、Fe有关。在本研究中，将多个红宝石加载到碳涂层板上，并在HS相机下进行高通量分析。可见光谱中有420 nm和558 nm左右的吸收峰。有趣的是，由于可见光发出的紫外线辐射激发，也出现了692 nm的拉曼峰。然而，由于表面反射、夹杂物和杂质等多种因素的影响，可见光谱的基线波动较大。相比之下，荧光光谱的再现性更强，红宝石的发射峰可更好地识别。因此，基于支持向量机（SVM）的荧光光谱识别准确率为97.8%，经过100次5倍交叉验证，高于可见光光谱的95.8%，略高于或与基于激光烧蚀电感耦合等离子质谱（LA-ICP-MS）元素分析的准确率（96.6%）相当。因此，所演示的HS荧光方案能够对多种红宝石进行高通量分析，可能是宝石评估领域的一种通用替代方案，其中单个样品对样品的测量已经是一种常见的做法。

{"title":"High-throughput identification of geographical origins of rubies using hyperspectral visible and fluorescence spectroscopy","authors":"Jiwoo Cho , Mieun Kim , Sanghoon Cho , Sang-Ho Nam , Yonghoon Lee , Hoeil Chung","doi":"10.1016/j.saa.2025.127405","DOIUrl":"10.1016/j.saa.2025.127405","url":null,"abstract":"<div><div>This study explored hyperspectral (HS) visible and fluorescence spectroscopy as a high-throughput analytical tool for discrimination of rubies originating from Myanmar (MM), Mozambique (MZ), and Thailand (TH). Rubies are a variety of the mineral corundum (Al<sub>2</sub>O<sub>3</sub>), and their color is mainly related to Cr and Fe. In this study, multiple rubies were loaded onto a carbon-coated plate and measured under a HS camera for high-throughput analysis. The absorption peaks around 420 nm and 558 nm were apparent in the visible spectra. Interestingly, a Raman peak at 692 nm also appeared due to excitation by ultraviolet radiation emitted from a visible lamp. However, due to various factors such as surface reflection, inclusions, and impurities, baseline fluctuations among the visible spectra were large. In contrast, the fluorescence spectra were more reproducible, and the emission peaks of rubies were better discernible. Therefore, support vector machine (SVM)-based discrimination accuracy using the fluorescence spectra was 97.8 % based on 100 repetitions of 5-fold cross-validation, higher than 95.8 % employing the visible spectra, and slightly higher or comparable to that (96.6 %) based on the elemental analysis using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Therefore, the demonstrated HS fluorescence scheme, which enables high-throughput analysis of multiple rubies, could be a versatile alternative in the field of gemstone evaluation where individual sample-by-sample measurement has been a common practice.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127405"},"PeriodicalIF":4.6,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145914439","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Qualitative and quantitative analysis of Paris polyphylla var. yunnanensis from different origin using multi-dimensions FT-MIR and NIR spectroscopy, data fusion combined with machine learning 利用FT-MIR、NIR光谱、数据融合与机器学习相结合的方法，对不同产地云南多叶桦进行定性和定量分析。

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-29 DOI: 10.1016/j.saa.2025.127414

Yuangui Yang , Yuanzhong Wang

Geographical traceability is crucial to ensuring consistent quality of Paris polyphylla var. yunnanensis (PPY) from different regions. In this study, a multi-dimension FT-MIR and NIR spectroscopy, data fusion combined with machine learning were used for identifying PPY qualitatively and quantitatively. A multi-dimensional spectrum includes 1D, 2DCOS, 3DCOS (synchronous, asynchronous and integrative) were generated. FT-MIR, NIR and data fusion coupled to traditional machine learning includes principal component analysis (PCA), t-distributed Stochastic Neighbor Embedding (t-SNE) partial least squares discriminant analysis (PLS-DA), orthogonal partial least squares discriminant analysis (OPLS-DA) were used to identify PPY from different regions. Meanwhile, deep learning model ResNet based on multi-dimensional spectral images were established for different maps. FT-MIR, NIR and data fusion were applied to determine total saponins. The results shows that PCA and t-SNE can reveal the relationship of the general chemical information of PPY. PLS-DA and OPLS-DA based on data fusion had the best performance with greater R²X, R²Y and Q², and smaller RMSEE, RMSECV and RMSEP, and higher accuracy of training and test set. Multi-dimensional spectroscopy with no processing had good performance in classification. Both synchronous 2DCOS and 3DCOS images for FT-MIR and NIR could effectively classify samples. PLSR based on data fusion coupled to the combination of pretreatment spectral multiple scattering correction and first derivative had the better predictive results than others, achieving an RPD of 1.98, with Rc² and Rp² of 0.92 and 0.78, respectively. This study provides a rapid and robust strategy for quality control of Traditional Chinese medicine.

地理可追溯性是保证不同产地云南林分质量一致性的关键。本研究采用多维FT-MIR和近红外光谱，数据融合结合机器学习对PPY进行定性和定量识别。生成了一维、二dcos、三维cos（同步、异步和一体化）的多维光谱。利用FT-MIR、NIR和数据融合与传统机器学习相结合的主成分分析（PCA）、t分布随机邻居嵌入（t-SNE）偏最小二乘判别分析（PLS-DA）、正交偏最小二乘判别分析（OPLS-DA）对不同地区的PPY进行识别。同时，针对不同的地图建立了基于多维光谱图像的深度学习模型ResNet。采用FT-MIR、近红外光谱和数据融合法测定总皂苷。结果表明，主成分分析和t-SNE分析可以揭示聚吡啶的一般化学信息之间的关系。基于数据融合的PLS-DA和OPLS-DA具有较高的R2X、R2Y和Q2，较小的RMSEE、RMSECV和RMSEP，训练集和测试集精度较高的性能。未经处理的多维光谱在分类中具有良好的性能。FT-MIR和NIR的同步2DCOS和3DCOS图像都能有效地对样品进行分类。基于数据融合耦合预处理光谱多次散射校正和一阶导数相结合的PLSR预测效果较好，RPD为1.98，Rc2和Rp2分别为0.92和0.78。本研究为中药质量控制提供了一种快速有效的策略。

{"title":"Qualitative and quantitative analysis of Paris polyphylla var. yunnanensis from different origin using multi-dimensions FT-MIR and NIR spectroscopy, data fusion combined with machine learning","authors":"Yuangui Yang , Yuanzhong Wang","doi":"10.1016/j.saa.2025.127414","DOIUrl":"10.1016/j.saa.2025.127414","url":null,"abstract":"<div><div>Geographical traceability is crucial to ensuring consistent quality of <em>Paris polyphylla</em> var. <em>yunnanensis</em> (PPY) from different regions. In this study, a multi-dimension FT-MIR and NIR spectroscopy, data fusion combined with machine learning were used for identifying PPY qualitatively and quantitatively. A multi-dimensional spectrum includes 1D, 2DCOS, 3DCOS (synchronous, asynchronous and integrative) were generated. FT-MIR, NIR and data fusion coupled to traditional machine learning includes principal component analysis (PCA), t-distributed Stochastic Neighbor Embedding (t-SNE) partial least squares discriminant analysis (PLS-DA), orthogonal partial least squares discriminant analysis (OPLS-DA) were used to identify PPY from different regions. Meanwhile, deep learning model ResNet based on multi-dimensional spectral images were established for different maps. FT-MIR, NIR and data fusion were applied to determine total saponins. The results shows that PCA and t-SNE can reveal the relationship of the general chemical information of PPY. PLS-DA and OPLS-DA based on data fusion had the best performance with greater R<sup>2</sup>X, R<sup>2</sup>Y and Q<sup>2</sup>, and smaller RMSEE, RMSECV and RMSEP, and higher accuracy of training and test set. Multi-dimensional spectroscopy with no processing had good performance in classification. Both synchronous 2DCOS and 3DCOS images for FT-MIR and NIR could effectively classify samples. PLSR based on data fusion coupled to the combination of pretreatment spectral multiple scattering correction and first derivative had the better predictive results than others, achieving an RPD of 1.98, with Rc<sup>2</sup> and Rp<sup>2</sup> of 0.92 and 0.78, respectively. This study provides a rapid and robust strategy for quality control of Traditional Chinese medicine.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127414"},"PeriodicalIF":4.6,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145902165","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Rapid characterization of heavy metals in soil using a novel integrated strategy for near-infrared spectroscopy models 基于近红外光谱模型的新型集成策略快速表征土壤重金属

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-29 DOI: 10.1016/j.saa.2025.127404

Hairong Guo , Mingdian Guo , Yujia Liu

As one of the critical natural resources sustaining human survival and sustainable development, soil quality directly underpins ecological security and the sustainability of agricultural production. Given the escalating severity of soil pollution, particularly heavy metals (HMs) contamination, the development of a standardized, efficient, and high-precision technology for acquiring soil HMs information has become an urgent necessity. Traditional research approaches have typically focused on using diverse models to independently predict and analyze different physical and chemical properties of soil. The research focus has largely centered on comparing the performance of various models, while overlooking the fundamental challenges of single models, such as limitations in universality and insufficient reproducibility. In this study, linear and nonlinear modeling approaches were employed, combined with multi-step spectral data processing procedures, to construct near-infrared spectral prediction models for HMs (taking Pb, Cd, and Cr in soil as examples). Furthermore, the inversion methods of soil HM contents and model selection were analyzed. On this basis, by integrating the model averaging strategy and weighted fusion strategy respectively, the limitations and instability of single-model estimation were addressed by leveraging the operational characteristics of six sub-models. The results indicated that the complex architecture and parameter settings of nonlinear algorithms exhibit greater potential for inverting soil biochemical properties. Assigning different weights based on the predictive performance of sub-models can correct outliers occurring in single-model estimation. After applying the weighted fusion strategy, the average prediction errors for Pb, Cd, and Cr in soil were reduced to 2.12 %, 5.35 %, and 3.51 %, respectively. Compared with single-model prediction, the residual prediction deviations of the test set were improved by 0.43, 0.15, and 0.20, respectively. The integration strategy elevates the reference-level single models to a practically applicable level, thereby providing new insights for the subsequent development and optimization of soil regression models.

土壤质量是维持人类生存和可持续发展的重要自然资源之一，直接关系到生态安全和农业生产的可持续性。随着土壤污染特别是重金属污染的日益严重，开发一种标准化、高效、高精度的土壤重金属信息获取技术已成为迫切需要。传统的研究方法通常侧重于使用不同的模型来独立预测和分析土壤的不同物理和化学性质。研究重点主要集中在比较各种模型的性能，而忽略了单一模型的基本挑战，如通用性的限制和可重复性不足。本研究采用线性和非线性建模方法，结合多步光谱数据处理，构建土壤中重金属（以土壤中Pb、Cd和Cr为例）近红外光谱预测模型。分析了土壤HM含量的反演方法和模型选择。在此基础上，通过分别集成模型平均策略和加权融合策略，利用6个子模型的运行特点，解决了单模型估计的局限性和不稳定性。结果表明，复杂的非线性算法结构和参数设置在反演土壤生化特性方面具有更大的潜力。根据子模型的预测性能分配不同的权重，可以纠正单模型估计中出现的异常值。采用加权融合策略后，土壤中Pb、Cd和Cr的平均预测误差分别降至2.12%、5.35%和3.51%。与单模型预测相比，测试集的残差预测偏差分别提高了0.43、0.15和0.20。整合策略将参考水平的单一模型提升到实际适用水平，从而为后续土壤回归模型的开发和优化提供新的见解。

{"title":"Rapid characterization of heavy metals in soil using a novel integrated strategy for near-infrared spectroscopy models","authors":"Hairong Guo , Mingdian Guo , Yujia Liu","doi":"10.1016/j.saa.2025.127404","DOIUrl":"10.1016/j.saa.2025.127404","url":null,"abstract":"<div><div>As one of the critical natural resources sustaining human survival and sustainable development, soil quality directly underpins ecological security and the sustainability of agricultural production. Given the escalating severity of soil pollution, particularly heavy metals (HMs) contamination, the development of a standardized, efficient, and high-precision technology for acquiring soil HMs information has become an urgent necessity. Traditional research approaches have typically focused on using diverse models to independently predict and analyze different physical and chemical properties of soil. The research focus has largely centered on comparing the performance of various models, while overlooking the fundamental challenges of single models, such as limitations in universality and insufficient reproducibility. In this study, linear and nonlinear modeling approaches were employed, combined with multi-step spectral data processing procedures, to construct near-infrared spectral prediction models for HMs (taking Pb, Cd, and Cr in soil as examples). Furthermore, the inversion methods of soil HM contents and model selection were analyzed. On this basis, by integrating the model averaging strategy and weighted fusion strategy respectively, the limitations and instability of single-model estimation were addressed by leveraging the operational characteristics of six sub-models. The results indicated that the complex architecture and parameter settings of nonlinear algorithms exhibit greater potential for inverting soil biochemical properties. Assigning different weights based on the predictive performance of sub-models can correct outliers occurring in single-model estimation. After applying the weighted fusion strategy, the average prediction errors for Pb, Cd, and Cr in soil were reduced to 2.12 %, 5.35 %, and 3.51 %, respectively. Compared with single-model prediction, the residual prediction deviations of the test set were improved by 0.43, 0.15, and 0.20, respectively. The integration strategy elevates the reference-level single models to a practically applicable level, thereby providing new insights for the subsequent development and optimization of soil regression models.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"350 ","pages":"Article 127404"},"PeriodicalIF":4.6,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882642","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0