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Exploring the impact of opioids on serum chemistry: Insights from FT-Raman spectroscopy and biochemical analysis 探索阿片类药物对血清化学的影响:傅立叶变换拉曼光谱和生化分析的启示
IF 2.7 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-10 DOI: 10.1016/j.vibspec.2024.103742
Zeynep Ceylan , Devrim Sarıbal , Hasan Mırsal , Joanna Depciuch , Joseph Cebulski , Zozan Guleken
Opioids are drugs whose use has increased dramatically over the last two decades. Opioids are a family of drugs that includes the illegal drug heroin, synthetic opioids such as fentanyl, and painkillers that are legally available on prescription. Unfortunately, too long use of these drugs can lead to addiction, which might cause disturbed physiological and mental effects. Regular opioid usage might cause common mental disorders such as depression, anxiety, and panic disorder. However, there is still no rapid detection method to describe the chemical changes caused by the Opioid use disorder. For this reason, this study used conventional FT-Raman spectroscopic techniques with multivariate analysis to detect chemical changes in serum following opiate administration. In the FT-Raman spectrum collected from opioid-addicted patients, significant shifts of peaks at 892 cm−1, 966 cm−1, 1286 cm−1, 1459 cm−1 and 2940 cm−1 were visible in comparison with the spectrum of serum collected from the control group. Furthermore, changes in the ratio of amides and lipids were observed in the non-control group, suggesting that opioids could cause structural changes in the compounds. Synchronous spectra show auto peaks at 2914 cm−1, 3415 cm−1 while asynchronous negative cross area between 1005 cm−1 and 1800 cm−1 and around 3000 cm−1 indicate higher presence of polysaccharides and amides in comparison with other compounds in serum collected from non-control group. Finally, the PCA model, utilizing three components that explain 94.89 % of the data variation within the 300–3700 cm⁻¹ range, demonstrates excellent performance. The ensemble classification method achieves accuracies of 97.96 % and 95.00 % on the training and test datasets, respectively. Furthermore, the method achieves AUC-ROC scores of 1.00 and 0.99 for the training and test sets, effectively distinguishing between control and opioid-addicted individuals.
阿片类药物的使用在过去二十年中急剧增加。阿片类药物是一个药物家族,包括非法药物海洛因、合成阿片类药物(如芬太尼)和合法处方止痛药。不幸的是,长期使用这些药物会导致成瘾,并可能对生理和心理造成不良影响。经常使用阿片类药物可能会导致常见的精神障碍,如抑郁症、焦虑症和恐慌症。然而,目前仍没有快速检测方法来描述阿片类药物使用障碍所引起的化学变化。因此,本研究采用传统的傅立叶变换拉曼光谱技术和多元分析方法来检测服用阿片类药物后血清中的化学变化。在阿片类药物成瘾患者的傅立叶变换拉曼光谱中,与对照组血清光谱相比,892 厘米-1、966 厘米-1、1286 厘米-1、1459 厘米-1 和 2940 厘米-1 处的峰值发生了明显的移动。此外,在非对照组中观察到酰胺和脂质的比例发生了变化,这表明阿片类药物可能导致化合物的结构发生变化。同步光谱在 2914 厘米-1 和 3415 厘米-1 处显示自动峰,而 1005 厘米-1 和 1800 厘米-1 之间以及 3000 厘米-1 附近的非同步负交叉区表明,与其他化合物相比,非对照组血清中存在更多的多糖和酰胺。最后,PCA 模型利用三个成分解释了 300-3700 cm-¹ 范围内 94.89 % 的数据变化,表现出色。在训练数据集和测试数据集上,集合分类法的准确率分别达到 97.96 % 和 95.00 %。此外,该方法在训练集和测试集上的 AUC-ROC 分数分别为 1.00 和 0.99,能有效区分对照组和阿片类药物成瘾组。
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引用次数: 0
Application of Attenuated Total Reflectance Fourier-Transform Infrared Spectroscopy in Human Sera: Validate the method for contributing effective strategy for the storage and preservation 衰减全反射傅立叶变换红外光谱法在人类血清中的应用:验证方法,为储存和保存提供有效策略
IF 2.7 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-04 DOI: 10.1016/j.vibspec.2024.103741
Juthamas Jaimanee , Patutong Chatchawal , Molin Wongwattanakul , Supranee Phantanawiboon , Chanvit Leelayuwat , Amonrat Jumnainsong
The serum is one of the biological specimens that have been extensively studied as biomarkers and is recognized as an effective tool for screening and diagnosing a variety of diseases. Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR) is a practical technique utilized in investigating characteristic spectra in infectious diseases cancer, and metabolic status. However, the pre-analytical procedure as storage condition is a crucial phase that directly impacts the accuracy of the result. In this study, we intend to investigate the effects of serum stabilization under both identical and distinct storage conditions on the FTIR spectral patterns, intensity variations, and macromolecule composition. The ten serum samples were stored in 3 different conditions including 4 °C, −20°C, and −80°C for six different time intervals (7, 14, 21, 28, 56, and 84 days). The spectra were obtained by ATR-FTIR spectroscopy. The serum stabilization was studied in two investigations: one focusing on the stability of serum under identical conditions over six different time intervals, and the other examining the stability of serum stored under three distinct conditions. Principal Component Analysis (PCA) and Area Under the Peak (AUP) were used to investigate clusters in different sets of data across five spectral ranges. The macromolecule composition was identified in conjunction with the intensity measurements. The results showed that the same conditions remained stable across six different time intervals, as indicated by the consistent PCA results. In contrast, the stabilization of serum under different temperature condition showed different major intensities across the five selected positive bands, including 1781 cm−1, 1740 cm−1 1727 cm−1 corresponding to lipid region (1800–1700 cm−1), and Amide region (1700 −1500 cm−1) at 1646 cm−1, and 1632 cm−1, when the serum was stored over 28 days. This might involve lipid peroxidation-induced changes in the secondary structure of proteins. Our findings indicated that serum should be stored at −80°C to ensure stabilization and achieve the highest intensity. Additionally, preserving serum under consistent conditions was crucial to minimize variability and prevent external factors from affecting the results.
血清是作为生物标记物被广泛研究的生物标本之一,是筛查和诊断各种疾病的有效工具。衰减全反射-傅立叶变换红外光谱法(ATR-FTIR)是一种实用技术,可用于研究传染病、癌症和新陈代谢状况的特征光谱。然而,分析前的存储条件是直接影响结果准确性的关键阶段。在本研究中,我们打算研究在相同和不同储存条件下稳定血清对傅立叶变换红外光谱模式、强度变化和大分子组成的影响。十份血清样品分别在 4°C、-20°C 和 -80°C 三种不同条件下储存了六种不同的时间间隔(7 天、14 天、21 天、28 天、56 天和 84 天)。光谱由 ATR-FTIR 光谱仪获得。对血清稳定性的研究分为两项:一项侧重于在相同条件下六个不同时间间隔内血清的稳定性,另一项则考察了在三种不同条件下储存血清的稳定性。研究人员使用主成分分析法(PCA)和峰下面积法(AUP)研究了五种光谱范围内不同数据集群。结合强度测量结果确定了大分子的组成。结果表明,在六个不同的时间间隔内,相同的条件保持稳定,这一点从一致的 PCA 结果可以看出。相反,在不同温度条件下,血清的稳定性在五个选定的阳性条带上显示出不同的主要强度,包括 1781 cm-1、1740 cm-1 1727 cm-1(对应于脂质区(1800-1700 cm-1)),以及 1646 cm-1 和 1632 cm-1 的酰胺区(1700 -1500 cm-1)。这可能与脂质过氧化引起的蛋白质二级结构变化有关。我们的研究结果表明,血清应保存在 -80°C 温度下,以确保其稳定性并达到最高强度。此外,在一致的条件下保存血清对减少变异性和防止外部因素影响结果至关重要。
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引用次数: 0
Forensic significance of decay-related spectral changes in ante-mortem and post-mortem injuries using ATR-FTIR spectroscopy 利用 ATR-FTIR 分光仪分析死前和死后损伤中与衰变相关的光谱变化的法医学意义
IF 2.7 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-09-16 DOI: 10.1016/j.vibspec.2024.103740
Damascene Nteziryayo , Zhenhua Wang , Ran An , Hongyan Qian , Gao Baoyao , Min Liang , Zijun Liu , Xingyao Chen , Xinshe Liu , Tao Li

Every year, more than 5 million deaths are attributed to injuries worldwide. However, accurately identifying and distinguishing the types of injuries in decomposed corpses is a significant challenge in forensic identification. Determining the cause of death in cases involving decomposed cadavers is particularly difficult, because traditional methods often lack conclusive evidence. To address this gap, this study aimed to explore the potential of attenuated total reflection/Fourier-transform infrared (ATR-FTIR) spectroscopy in analyzing the molecular composition changes in tissue samples from putrefied corpses. To simulate different environmental conditions, 54 experimental mice were randomly divided into three groups: ante-mortem injury (AI), post-mortem injury (PI), and non-injury (NI) groups, and their bodies were monitored at different time points. Subsequently, we conducted comprehensive analyses of these tissue samples using ATR-FTIR. The results indicate that under winter conditions, PC1 explained 78.3 % of the variance, whereas PC2 explained 15.4 %. Similarly, under summer conditions, PC1 explained 75.3 % of the variance, whereas PC2 explained 16.1 %. The results under both conditions, the AUC values of the ROC curve exceeded 0.9, indicating the reliability and accuracy of this method in discriminating ante-mortem injuries from post-mortem injuries on decomposed bodies, highlighting its significance in forensic investigations. This demonstrates the capability of ATR-FTIR technology to identify distinct molecular changes linked to ante-mortem and post-mortem injuries in decomposed corpses. The findings of this study underscores the forensic significance of understanding the molecular composition changes in decomposed cadavers. Therefore, ATR-FTIR is a valuable tool for differentiating ante-mortem and post-mortem injuries while also considering environmental factors.

全世界每年有 500 多万人死于外伤。然而,准确识别和区分腐烂尸体的损伤类型是法医鉴定中的一项重大挑战。在涉及腐烂尸体的案件中,确定死因尤其困难,因为传统方法往往缺乏确凿证据。为弥补这一不足,本研究旨在探索衰减全反射/傅立叶变换红外光谱(ATR-FTIR)在分析腐败尸体组织样本分子组成变化方面的潜力。为了模拟不同的环境条件,我们将 54 只实验小鼠随机分为三组:死前损伤组(AI)、死后损伤组(PI)和非损伤组(NI),并在不同的时间点对它们的尸体进行监测。随后,我们利用 ATR-FTIR 对这些组织样本进行了全面分析。结果表明,在冬季条件下,PC1 解释了 78.3 % 的方差,而 PC2 解释了 15.4 % 的方差。同样,在夏季条件下,PC1 解释了 75.3 % 的方差,而 PC2 解释了 16.1 % 的方差。在这两种条件下,ROC 曲线的 AUC 值均超过 0.9,表明该方法在鉴别腐尸的生前损伤和死后损伤方面非常可靠和准确,在法医调查中具有重要意义。这表明 ATR-FTIR 技术有能力识别与腐烂尸体生前和死后损伤有关的不同分子变化。这项研究的结果强调了了解腐烂尸体分子成分变化的法医学意义。因此,ATR-傅立叶变换红外技术是区分死前和死后损伤的重要工具,同时也考虑了环境因素。
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引用次数: 0
Efficient identification and distinction of musgravite and taaffeite with the utilization of ATR-FTIR spectroscopy and Raman spectroscopy 利用 ATR-FTIR 光谱和拉曼光谱有效识别和区分麝香石和霞糠石
IF 2.7 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-09-06 DOI: 10.1016/j.vibspec.2024.103733
Pimthong Thongnopkun

Taaffeite (BeMg3Al8O16) and musgravite (Be(Mg,Fe,Zn)2Al6O12) are two of the rarest gem kinds worldwide, and their scarcity greatly enhances their extraordinary worth. Due to their nearly matched physical properties, discriminating between the two gems using basic gemological equipment will be exceedingly difficult, considering that they both belong to the same mineral family. Distinguishing between these two categories is crucial due to the substantial variation in their rarity levels, which greatly impacts on their market pricing. Nevertheless, there is a lack of published data in the scientific literature about the spectroscopic characterization of musgravite and taaffeite.

In this article, ATR-FTIR spectroscopy successfully distinguished Tanzanian musgravite from taaffeite for the first time. In addition, Raman spectroscopy and EPMA are employed for the identification of musgravite and taaffeite specimens. The EPMA results confirm that the Tanzanian gems under investigation have similar elemental compositions to those of the same kinds of stones discovered from other sources. The peaks observed in the ATR and Raman spectra serve as indicators for distinguishing between musgravite and taaffeite gemstones, with the goal of simplifying the identification process. The ATR and Raman spectra of musgravite and taaffeite are comprehensively analyzed and found to be achievable. The main Raman bands used to identify Tanzanian musgravite are situated at 412 and 713 cm−1, whereas for taaffeite, the significant bands were detected at 416 and 761 cm−1. The distinct ATR bands observed at 773 cm−1, corresponding to the vibration of Al–O, can be efficiently utilized as indications to differentiate Tanzanian musgravite from taaffeite. The results prove that ATR-FTIR spectroscopy, like Raman spectroscopy, is a very effective non-invasive method for rapidly distinguishing these precious gemstones.

太妃石(BeMg3Al8O16)和麝香石(Be(Mg,Fe,Zn)2Al6O12)是世界上最稀有的两种宝石,它们的稀有性大大提升了它们的非凡价值。由于它们的物理特性几乎完全相同,考虑到它们同属一个矿物家族,使用基本的宝石学设备对这两种宝石进行鉴别是极其困难的。区分这两类宝石至关重要,因为它们的稀有程度有很大差异,这极大地影响了它们的市场定价。在本文中,ATR-傅立叶变换红外光谱首次成功地将坦桑尼亚的麝香石和塔夫石区分开来。此外,还采用拉曼光谱和 EPMA 对麝香石和太妃石标本进行了鉴定。EPMA 结果证实,所调查的坦桑尼亚宝石与其他来源发现的同类宝石具有相似的元素组成。在 ATR 和拉曼光谱中观察到的峰值可作为区分麝香石和太妃石宝石的指标,目的是简化鉴定过程。对麝香石和太妃石的 ATR 和拉曼光谱进行了全面分析,发现是可以实现的。用于鉴别坦桑尼亚麝香石的主要拉曼光谱带位于 412 和 713 cm-1,而taaffeite 的重要光谱带则位于 416 和 761 cm-1。在 773 cm-1 处观察到的明显的 ATR 波段与 Al-O 的振动相对应,可以有效地用作区分坦桑尼亚麝香石和塔菲特的指标。结果证明,ATR-傅立叶变换红外光谱与拉曼光谱一样,是快速区分这些珍贵宝石的一种非常有效的非侵入式方法。
{"title":"Efficient identification and distinction of musgravite and taaffeite with the utilization of ATR-FTIR spectroscopy and Raman spectroscopy","authors":"Pimthong Thongnopkun","doi":"10.1016/j.vibspec.2024.103733","DOIUrl":"10.1016/j.vibspec.2024.103733","url":null,"abstract":"<div><p>Taaffeite (BeMg<sub>3</sub>Al<sub>8</sub>O<sub>16</sub>) and musgravite (Be(Mg,Fe,Zn)<sub>2</sub>Al<sub>6</sub>O<sub>12</sub>) are two of the rarest gem kinds worldwide, and their scarcity greatly enhances their extraordinary worth. Due to their nearly matched physical properties, discriminating between the two gems using basic gemological equipment will be exceedingly difficult, considering that they both belong to the same mineral family. Distinguishing between these two categories is crucial due to the substantial variation in their rarity levels, which greatly impacts on their market pricing. Nevertheless, there is a lack of published data in the scientific literature about the spectroscopic characterization of musgravite and taaffeite.</p><p>In this article, ATR-FTIR spectroscopy successfully distinguished Tanzanian musgravite from taaffeite for the first time. In addition, Raman spectroscopy and EPMA are employed for the identification of musgravite and taaffeite specimens. The EPMA results confirm that the Tanzanian gems under investigation have similar elemental compositions to those of the same kinds of stones discovered from other sources. The peaks observed in the ATR and Raman spectra serve as indicators for distinguishing between musgravite and taaffeite gemstones, with the goal of simplifying the identification process. The ATR and Raman spectra of musgravite and taaffeite are comprehensively analyzed and found to be achievable. The main Raman bands used to identify Tanzanian musgravite are situated at 412 and 713 cm<sup>−1</sup>, whereas for taaffeite, the significant bands were detected at 416 and 761 cm<sup>−1</sup>. The distinct ATR bands observed at 773 cm<sup>−1</sup>, corresponding to the vibration of Al–O, can be efficiently utilized as indications to differentiate Tanzanian musgravite from taaffeite. The results prove that ATR-FTIR spectroscopy, like Raman spectroscopy, is a very effective non-invasive method for rapidly distinguishing these precious gemstones.</p></div>","PeriodicalId":23656,"journal":{"name":"Vibrational Spectroscopy","volume":"135 ","pages":"Article 103733"},"PeriodicalIF":2.7,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142167535","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Dual-channel Raman spectrometer device based on multi-field-of-view spectrometer for on-line detection 基于多视场光谱仪的双通道拉曼光谱仪装置,用于在线检测
IF 2.7 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-09-01 DOI: 10.1016/j.vibspec.2024.103732
Guo Xia , Qingfa Pan , Qin Pan , Yanduo Li , Defeng Yu , Jianfei Zhu

High-throughput on-line Raman detection has become commonplace in pharmaceutical and PAT. This has increased the demand for efficient, parallel spectral detection. In this work, a method of adjusting the optical structure parameters through multi-field theory is proposed to realize the detector accepting two spectral information from the light source at the same time. By combining two Raman probes and two customized Y-fibers, Raman spectra of two samples at the same laser power can be acquired simultaneously online. Compared with the multi-channel Raman spectroscopy detection system based on microscope device and multiple Raman spectroscopy coupling system, the measurement time and cost are greatly reduced. Thus, dual-channel Raman spectroscopy detection devices provide a cost and time-saving method for modern high-throughput on-line Raman detection.

高通量在线拉曼检测已成为制药和 PAT 领域的普遍现象。这就增加了对高效、并行光谱检测的需求。在这项工作中,提出了一种通过多场理论调整光学结构参数的方法,以实现探测器同时接受来自光源的两种光谱信息。通过将两个拉曼探针和两根定制的 Y 型光纤组合在一起,可以同时在线获取相同激光功率下两个样品的拉曼光谱。与基于显微镜设备和多拉曼光谱耦合系统的多通道拉曼光谱检测系统相比,测量时间和成本大大降低。因此,双通道拉曼光谱检测装置为现代高通量在线拉曼检测提供了一种节省成本和时间的方法。
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引用次数: 0
Real-time monitoring of CBDA decarboxylation in solid state and cannabis flowers using mid infrared spectroscopy coupled with multivariate analysis 利用中红外光谱和多元分析对固态和大麻花中的 CBDA 脱羧过程进行实时监测
IF 2.7 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-09-01 DOI: 10.1016/j.vibspec.2024.103728
Olga Gigopulu , Nikola Geskovski , Gjoshe Stefkov , Ana Poceva Panovska , Marjan Piponski , Irena Slaveska Spirevska , Petre Makreski

Cannabidiolic acid (CBDA) is found in cannabis as genuine phytocompound of the well-known non-psychoactive cannabinoid - cannabidiol (CBD), notable for its various therapeutic purposes. Decarboxylation of CBDA to CBD is commonly used in the production of finished cannabis products, thus increasing its bioavailability, and making it more effective for various therapeutic purposes. Optimization of decarboxylation time and the possibility of monitoring this process in real-time is quite a challenge for the cannabis producers' R&D divisions, since incomplete decarboxylation is associated with quality and efficiency concerns, whereas prolonged reaction time can lead to potentially lower production efficacy. The purpose of this study is to emphasize the use of mid-infrared (MIR) spectroscopy for in-situ real-time monitoring and understanding of the CBDA decarboxylation process. For the first time, the TG/DTG curves of CBDA provided insights into the solid-solid decarboxylation dynamics, process endpoint, and maximal conversion rate temperature, which were used for designing the subsequent infrared experiments. In addition, the DSC curve illustrated the melting point of the pure CBDA. Temperature-controlled infrared spectroscopy studies were performed on CBDA standard and cannabis flowers followed by precise band assignment and spectra-structure correlations based on the idea of functional group vibrations. In order to investigate the spectral regions of major relevance for the CBDA to CBD interconversion process, a principal component analysis (PCA) was used. In the obtained models, PC1 was capable to describe 81.3 %, 77.8 % and 77 % of the total spectral fluctuations in the CBDA standard and two plant samples, respectively. The PC1 score plot of the CBDA standard (as a function of temperature) showed a perfect complementarity to the TG/DTG curve, indicating that PC1 of the MIR spectrum model may quantitatively describe the CBDA decarboxylation dynamics, which allowed for the derivation of decarboxylation rate constants for the CBDA standard and the plant material at prechosen temperatures. The temperature-controlled experiments revealed significantly higher kinetics constants of CBDA decarboxylation in the plant material compared to the CBDA standard and supported the assumption that the complex matrix in cannabis plants accelerates the conversion of CBDA to CBD. In this way, progress in the development and optimization of an efficient and fast approach for monitoring and elucidation of the phytocannabinoid decarboxylation process was made, launching the possibility for further employment in the medical cannabis industry.

大麻二酚酸(CBDA)作为众所周知的非精神活性大麻素--大麻二酚(CBD)的真正植物化合物存在于大麻中,因其各种治疗用途而闻名。将 CBDA 脱羧成 CBD 通常用于生产大麻成品,从而提高其生物利用率,使其更有效地用于各种治疗目的。对于大麻生产商的研发部门来说,优化脱羧时间和实时监控这一过程的可能性是一个相当大的挑战,因为不完全脱羧会带来质量和效率问题,而反应时间过长则可能导致生产效率降低。本研究旨在强调使用中红外(MIR)光谱对 CBDA 的脱羧过程进行原位实时监测和了解。CBDA 的 TG/DTG 曲线首次揭示了固-固脱羧动态、过程终点和最大转化率温度,并用于设计后续的红外实验。此外,DSC 曲线还显示了纯 CBDA 的熔点。对 CBDA 标准品和大麻花进行了温控红外光谱研究,然后根据官能团振动的思想进行了精确的波段分配和光谱-结构相关性分析。为了研究 CBDA 与 CBD 相互转化过程中的主要相关光谱区域,采用了主成分分析法(PCA)。在获得的模型中,PC1 能够描述的光谱波动分别占 CBDA 标准样品和两种植物样品光谱波动总量的 81.3%、77.8% 和 77%。CBDA 标准物质的 PC1 分值图(与温度的函数关系)与 TG/DTG 曲线显示出完美的互补性,表明近红外光谱模型的 PC1 可以定量描述 CBDA 的脱羧动态,从而推导出 CBDA 标准物质和植物材料在预选温度下的脱羧速率常数。温控实验显示,与 CBDA 标准物质相比,植物材料中 CBDA 的脱羧动力学常数明显更高,这也支持了大麻植物中的复杂基质会加速 CBDA 向 CBD 转化的假设。因此,在开发和优化用于监测和阐明植物大麻素脱羧过程的高效快速方法方面取得了进展,为进一步应用于医用大麻行业提供了可能。
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引用次数: 0
Pedotransfer functions development for modeling FC and PWP using Vis-NIR spectra combined with PLSR and regression models 利用可见光-近红外光谱与 PLSR 和回归模型相结合,开发用于模拟 FC 和 PWP 的 Pedotransfer 函数
IF 2.7 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-28 DOI: 10.1016/j.vibspec.2024.103731
Xizhen Zhu , Piaoyun Gu , Gang Wu

The utilization of the soil pedotransfer functions (PTFs) developed based on the basic soil propertied is an alternative, fast, cost-effective and applicable approach for the prediction of field capacity (FC) and permanent wilting point (PWP). In addition, the Visible–Near-Infrared (Vis-NIR) spectra in soil science has gained prominence due to its practicality and relevance. In this paper, we used the data of the soil PWP and FC of 135 soil samples, easily measurable soil properties and Vis-NIR spectroscopy. The multiple linear regression (MLR) model was utilized to formulate PTFs model and Vis-NIR spectroscopy combined with MLR and partial least-squares (PLSR) was used to develop Spectrotransfer Function (STF). Results showed that among the easily measurable soil properties, particle-size diameter (dg) with Beta of −0.72 and −0.63 the most influential parameters for predicting FC and PWP, respectively, followed by the clay content. Developed PTFs for both FC and PWP with a R2 of 0.71 and 0.68, respectively, had a better performance than other previous developed PTFs. Results also revealed that the PLSR with a higher R2 (0.81) and lower RMSE (4 %) significantly performed better in comparison to STF for both FC and PWP prediction.

利用基于基本土壤特性开发的土壤传粉函数 (PTF),是预测田间容重 (FC) 和永久枯萎点 (PWP) 的另一种快速、经济、适用的方法。此外,可见光-近红外(Vis-NIR)光谱因其实用性和相关性在土壤科学中的地位日益突出。本文利用 135 个土壤样本的土壤脉动温升(PWP)和耐旱性(FC)数据、易于测量的土壤特性和可见-近红外光谱。利用多元线性回归(MLR)模型建立了 PTFs 模型,并利用可见近红外光谱仪结合 MLR 和偏最小二乘法(PLSR)建立了光谱转移函数(STF)。结果表明,在易于测量的土壤特性中,粒径(dg)是对预测 FC 和 PWP 影响最大的参数,其 Beta 值分别为-0.72 和-0.63,其次是粘土含量。针对 FC 和 PWP 开发的 PTF 的 R2 分别为 0.71 和 0.68,其性能优于之前开发的其他 PTF。结果还显示,与 STF 相比,R2(0.81)更高、RMSE(4%)更低的 PLSR 在 FC 和 PWP 预测方面的性能明显更好。
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引用次数: 0
Correlative morphological, elemental and chemical phase analyses at the micrometric scale of powdered materials: Application to nuclear forensics 对粉末状材料进行微米尺度的形态、元素和化学相位关联分析:核鉴识应用
IF 2.7 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-24 DOI: 10.1016/j.vibspec.2024.103729
Fabien Pointurier, Faustine Berthy, Olivier Marie

To characterize a mixture of powders using several analytical techniques, it is necessary that successive analyses be carried out on well-identified and localized particles, so that each characterization corresponds to a given powder. In this publication, powdered nuclear materials are characterized at the morphological and elemental levels with a scanning electron microscope (SEM) equipped with an energy dispersive X-ray spectrometer (EDS) and at the chemical level with a micro-Raman spectrometer (MRS). However, to avoid a time-consuming and insufficiently accurate microparticle relocation process between SEM/EDS and MRS, micro-Raman analyses are carried out inside the SEM using a coupling device. In this way, all three pieces of information are obtained for exactly the same micrometric spot, without moving the sample or relocating the microparticles analyzed. The information can therefore be combined to characterize each component of the mixture. In this article, we describe in detail the methodology we have developed and optimized for morphological, elemental and chemical analysis of microparticles using a combined SEM/EDS and SRM. This methodology has been applied to powdered nuclear materials in two international nuclear forensics exercises. In the first exercise, named CMX-6, the combined use of the two instruments identified the presence of PuO2 microparticles and several uranium compounds (UO2, U3O8, UO2F2) in both materials. In the second exercise, called CMX-7, the methodology developed enabled us to distinguish two chemical phases of uranium, a uranyl oxy-hydroxide and a uranyl nitrate, each characterized by specific morphologies and the detection or non-detection of a minor elemental constituent (calcium).

要使用多种分析技术对粉末混合物进行表征,就必须对明确识别和定位的颗粒进行连续分析,以便每次表征都与特定粉末相对应。在本出版物中,使用配备了能量色散 X 射线光谱仪(EDS)的扫描电子显微镜(SEM)和微拉曼光谱仪(MRS)对粉末状核材料进行了形态和元素层面的表征。不过,为了避免在 SEM/EDS 和 MRS 之间进行耗时且不够精确的微粒子重新定位过程,微拉曼分析是在 SEM 内部使用耦合装置进行的。这样,在不移动样品或重新定位所分析的微颗粒的情况下,就能获得完全相同的微米点的所有三种信息。因此,可以将这些信息结合起来,对混合物中的每种成分进行表征。在本文中,我们将详细介绍我们开发并优化的方法,该方法可使用 SEM/EDS 和 SRM 组合对微粒进行形态、元素和化学分析。该方法已在两次国际核鉴识演习中应用于粉末状核材料。在名为 CMX-6 的第一次演习中,两种仪器的联合使用确定了两种材料中都存在二氧化铀微粒和几种铀化合物(UO2、U3O8、UO2F2)。在名为 CMX-7 的第二项研究中,所开发的方法使我们能够区分铀的两种化学相,一种是铀酰氧氢氧化物,另一种是铀酰硝酸盐,每种化学相都具有特定的形态特征,并可检测到或检测不到一种次要元素成分(钙)。
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引用次数: 0
On the shape of the simulated infrared spectral density of strongly hydrogen-bonded systems: Mapping and identification of Hadži ABC structure in phosphonic acid dimers in gas phase 论强氢键体系模拟红外光谱密度的形状气相膦酸二聚体中哈德兹 ABC 结构的映射与识别
IF 2.7 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-21 DOI: 10.1016/j.vibspec.2024.103730
Najeh Rekik
<div><p>Herein, we explore the origin of three-peaked structure, referred to as the Hadži ABC structure, illustrated within the absorption bands in infrared (IR) spectra of strongly H-bonded systems. The exploration is particularly elucidated for two phosphinic acid dimers (<em>R</em><sub>2</sub><em>POOH</em>) in gas phase, namely bis-(iodomethyl)-phosphinic acid dimer (i.e., <em>R</em> = <em>CH</em><sub>2</sub><em>I</em>) at 465 K and dibutyl-phosphinic acid dimer (i.e., <em>R</em> = <em>C</em><sub>4</sub><em>H</em><sub>9</sub><em>O</em>) at 425 K. A direct theoretical illustration of this spectral signature, related predominantly to very strongly hydrogen bonded complexes, is proposed. The spectral density, <span><math><mrow><msub><mrow><mi>υ</mi></mrow><mrow><mi>S</mi></mrow></msub><mfenced><mrow><mi>O</mi><mo>−</mo><mi>H</mi></mrow></mfenced></mrow></math></span>,is determined by the aid of an approach describing the high-frequency <em>O</em> − <em>H</em> stretching modes by harmonic potentials. The intermolecular potential modes (<em>O</em>…<em>O</em>) are assumed to be of anharmonic nature. The approach is founded on the strong anharmonic coupling approximation, which prescribes a linear dependency of the <em>O</em> − <em>H</em> frequency on the <em>O</em>…<em>O</em> stretching coordinate as rationalized by the fundamental model of Maréchal and Witkowski. Both direct relaxation of the <em>O</em> − <em>H</em> vibrational mode and its homolog, indirect one, affecting the <em>O</em>…<em>O</em> stretching mode are taken into consideration. The model also considers Davydov coupling, which describes the mutual interaction that takes place in the centrosymmetric dimer between the two existent hydrogen bonds as well as Fermi resonances, which occur between the bending modes arising in- and out-of-plane of the dimer and the fundamental <em>O</em> − <em>H</em> stretching mode. Interestingly, we illustrate how the (<em>A</em>, <em>B</em>, and <em>C</em>) triplet detected in the IR absorption band of phosphonic acids can be generated and discuss how the ABC structure can be numerically simulated. The approach provides a direct explanation of the emergence of this unusual feature and mainly reveals that the <em>A</em> peak is due to the Davydov coupling mechanism, whereas the <em>BC</em> diad is found to be generated by Fermi resonances. This was elucidated in a distinctly different approach, rationalized by Sheppard and Claydon, affirming that the provenance of the <em>BC</em> diad is exclusively due to Fermi resonances mechanism. Altogether, our results highlight the congregated effects of both Fermi resonance mechanism and Davydov coupling for the formation of the <em>ABC</em> structure. The model paves the way for a deeper understanding of the <em>ABC</em> structure, characteristic of very toxic strongly hydrogen-bonded dimers. This is of capital importance as it allows one to develop a solid understanding of nerve agents, such as phosphonic acids,
在此,我们探讨了强氢键体系红外光谱吸收带中的三峰结构(即哈德日 ABC 结构)的起源。该研究特别阐明了气相中的两种膦酸二聚体(R2POOH),即 465 K 时的双-(碘甲基)-膦酸二聚体(即 R = CH2I)和 425 K 时的二丁基-膦酸二聚体(即 R = C4H9O)。这种光谱特征主要与氢键非常强的复合物有关,我们提出了一种直接的理论说明。光谱密度 υSO-H 是通过谐波势描述高频 O - H 伸展模式的方法确定的。分子间势模(O...O)被假定为非谐波性质。这种方法建立在强非谐耦合近似的基础上,它规定了 O - H 频率与 O...O 伸展坐标的线性关系,正如 Maréchal 和 Witkowski 的基本模型所合理解释的那样。O - H 振动模式的直接弛豫和影响 O...O 伸展模式的同源间接弛豫都被考虑在内。该模型还考虑了戴维多夫耦合(Davydov coupling),它描述了中心对称二聚体中存在的两个氢键之间的相互影响,以及费米共振(发生在二聚体平面内外的弯曲模式和基本 O - H 拉伸模式之间)。有趣的是,我们说明了在膦酸的红外吸收带中检测到的(A、B 和 C)三重如何产生,并讨论了如何对 ABC 结构进行数值模拟。该方法直接解释了这一不寻常特征的出现,并主要揭示了 A 峰是由于达维多夫耦合机制产生的,而 BC 二重是由费米共振产生的。Sheppard 和 Claydon 用一种截然不同的方法阐明了这一点,并确认 BC 二重性的来源完全是费米共振机制。总之,我们的研究结果凸显了费米共振机制和达维多夫耦合对 ABC 结构形成的共同影响。该模型为深入理解具有剧毒强氢键二聚体特征的 ABC 结构铺平了道路。这一点非常重要,因为它可以让人们仅从理论上就对神经毒剂(如膦酸)有扎实的了解,从而避免进行困难和危险的实验,因为它们具有剧毒。
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引用次数: 0
A comprehensive and innovative chemometric approach: Archaeometric analysis of the sherds from the Neolithic Period to the Chalcolithic and early Bronze Age with the full deployment of FTIR's molecular spectroscopic capabilities 全面创新的化学计量学方法:充分发挥傅立叶变换红外光谱仪的分子光谱能力,对新石器时代到夏石器时代和早期青铜时代的残片进行考古计量分析
IF 2.7 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-07-24 DOI: 10.1016/j.vibspec.2024.103727
İsmail Tarhan , Zafer Derin , Berfin Çelik , Melek Öner , Şahin Menteşe

In this study, the mineralogical composition of 284 sherds obtained from the sites of Yeşilova Höyük and Yassıtepe Höyük, two of the oldest settlements in Western Anatolia, and corresponding to a wide period starting from the Neolithic period to the Chalcolithic and Early Bronze Age (EBA), was studied by attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy. FTIR data was used to classify the sherds and state their firing conditions as a result of determining their mineralogical composition using principal component analysis (PCA), multivariate curve resolution (MCR), and hierarchical cluster analysis (HCA). According to the PCA results, the second-order derivative FTIR spectrum with 19 smoothing points in the range of 1300–400 cm−1 was determined to be the most successful model in classifying sherds. As a result of MCR, which allows comparison of standard minerals obtained within the scope of the study, it was determined that kaolinite, illite, chlorite, and some feldspar types were dominant in the sherds. According to HCA analysis, all sherds except five of them exhibited a similar mineralogical structure. According to the derivative spectra, it was seen that the sherds had a composition consisting of kaolinite, illite, hematite, chlorite, and some feldspar types at different rates. Upon examining the data, it becomes evident that the sherds are composed of nearly identical minerals and might have been fired in an oxidizing atmosphere. Even while 279 sherds had many mineralogical traits, N-061, EB-030, N-043, C-068, and N-059 were found to have distinct proportions of comparable minerals, including more kaolinite, illite, calcite, and chlorite. Regarding color, additives, and the amount of ceramic pastes present, these five sherds differ from the others. This suggests that there might have been attempts at manufacture or pots brought in from outside the Yeşilova Höyük-Yassıtepe Höyük sites. The results provided from the derivative spectra showed that all sherds except five of them have been fired at about at temperatures slightly above 450–500 °C due to their relatively low kaolinite character, but below 800 °C because diopside and similar high-temperature minerals could not be detected. The five sherds may have been fired at a temperature of around 450–500 °C due to the presence of a high character of kaolinite, illite, and chlorite. It was understood that the residents of the sites of Yeşilova Höyük and Yassıtepe Höyük produced their ceramics using the same raw materials and the same production methods from the Neolithic period to EBA thanks to FTIR and chemometrics, which are very good tools for analyzing large numbers of sherds with low cost and fast analysis time.

本研究采用衰减全反射(ATR)傅立叶变换红外(FTIR)光谱法研究了从叶西罗瓦霍尤克和亚西特佩霍尤克遗址(安纳托利亚西部最古老的两个定居点)出土的 284 件陶器的矿物成分,这些陶器对应的时期从新石器时代到旧石器时代和青铜时代早期(EBA)。傅立叶变换红外光谱数据用于对陶片进行分类,并通过主成分分析(PCA)、多变量曲线解析(MCR)和分层聚类分析(HCA)确定其矿物成分,从而说明其烧制条件。根据 PCA 结果,二阶导数傅立叶变换红外光谱在 1300-400 cm-1 范围内的 19 个平滑点被确定为最成功的碎片分类模型。通过 MCR(可对研究范围内获得的标准矿物进行比较),确定高岭石、伊利石、绿泥石和一些长石类型在陶片中占主导地位。根据 HCA 分析,除 5 个碎片外,其他所有碎片都呈现出类似的矿物结构。根据衍射光谱分析,可以看出陶片的成分由高岭石、伊利石、赤铁矿、绿泥石和一些长石类型组成,其比例各不相同。对这些数据进行研究后发现,这些陶片由几乎相同的矿物组成,可能是在氧化气氛中烧制的。尽管 279 个碎片具有许多矿物学特征,但 N-061、EB-030、N-043、C-068 和 N-059 被发现具有不同比例的可比矿物,包括更多的高岭石、伊利石、方解石和绿泥石。在颜色、添加剂和陶瓷浆料的含量方面,这五件碎片与其他碎片有所不同。这表明,这些陶器可能是尝试制造的,也可能是从叶西罗瓦霍尤克-亚西特佩霍尤克遗址以外的地方运来的。衍射光谱提供的结果显示,由于高岭石含量相对较低,除五件陶器外,所有陶器的烧制温度都略高于 450-500 °C,但低于 800 °C,因为无法检测到透辉石和类似的高温矿物。由于高岭石、伊利石和绿泥石的特征较高,这五件陶器可能是在大约 450-500 °C 的温度下烧制的。傅立叶变换红外光谱和化学计量学是分析大量陶器碎片的非常好的工具,成本低,分析时间短,因此可以理解叶西罗瓦霍裕克遗址和亚西特佩霍裕克遗址的居民从新石器时代到 EBA 时代使用相同的原材料和相同的生产方法生产陶瓷。
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引用次数: 0
期刊
Vibrational Spectroscopy
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