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Experimental and Computational Raman and SERS Study of Acid Blue 113 酸性蓝拉曼和SERS的实验与计算研究[j]
IF 1.9 3区 化学 Q2 SPECTROSCOPY Pub Date : 2025-09-23 DOI: 10.1002/jrs.70048
Thayla C. A. Coelho, Flávia C. Marques, Gustavo F. S. Andrade

The Acid Blue 113 dye (AB-113) is widely employed in the textile industry due to its remarkable dyeing capabilities on wool, nylon, and silk, ensuring stability throughout the washing process. While most research has focused on its adsorption, removal, degradation, and discoloration, a gap exists regarding its vibrational characterization. In this study, AB-113 was investigated through FT-IR, Raman, and SERS spectroscopies, analyzed on the basis of DFT computational studies. The SERS spectra were calculated considering an Ag8 cluster interacting with AB-112 as a model for the dye on the Ag nanoparticle surface. The simulated Raman and SERS spectra showed good agreement with experimental spectra, and their vibrational assignments are consistent with analogous parts of the molecules documented in previous studies. Furthermore, we observed that the bands in the 1460–1370-cm−1 range, assigned to vibrational modes of the azo group, had their relative intensity increased depending on the excitation wavelength, maximizing at 532 nm due to the resonance Raman effect. The SERS spectrum also showed higher intensity at excitation wavelengths of 532 and 632.8 nm due to resonance Raman effects of the dye; on the other hand, more significant changes in the relative intensities in the SERS spectrum due to the adsorption process were observed at nonresonance (λ0 = 785 nm) conditions. The interaction between AB-113 and AgNPs was inferred by comparing theoretical and experimental SERS spectra, which helped propose the interaction of the dye through a sulfonate group with the silver surface. Finally, it was demonstrated that AB-113 can be detected by SERS down to a concentration of 1.0 × 10−8 mol L−1 using wavelengths of 532 and 632.8 nm, reinforcing that this molecule could serve as a high-performance probe molecule for SERS applications.

酸性蓝113染料(AB-113)广泛应用于纺织工业,因为它对羊毛、尼龙和丝绸的染色能力显著,确保了整个洗涤过程的稳定性。虽然大多数研究都集中在其吸附、去除、降解和变色方面,但在其振动特性方面存在空白。本研究通过FT-IR、拉曼和SERS光谱对AB-113进行了研究,并在DFT计算研究的基础上进行了分析。以Ag8簇与AB-112相互作用为模型,计算了Ag纳米颗粒表面染料的SERS谱。模拟的拉曼光谱和SERS光谱与实验光谱具有较好的一致性,其振动分配与前人研究中记录的分子类似部分一致。此外,我们观察到,在1460-1370-cm−1范围内,偶氮基团的振动模式,其相对强度随着激发波长的增加而增加,由于共振拉曼效应,在532 nm处最大。在532和632.8 nm激发波长处,由于染料的共振拉曼效应,SERS谱显示出较高的强度;另一方面,在非共振(λ0 = 785 nm)条件下,由于吸附过程,SERS光谱的相对强度发生了更显著的变化。通过比较理论和实验SERS光谱推断AB-113与AgNPs之间的相互作用,这有助于提出染料通过磺酸基与银表面的相互作用。结果表明,在532和632.8 nm波长下,AB-113可以在1.0 × 10−8 mol L−1的浓度下被SERS检测到,这进一步证明了该分子可以作为SERS应用的高性能探针分子。
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引用次数: 0
Chirped-Probe-Pulse Femtosecond Coherent Anti-Stokes Raman Scattering Thermometry Mapping in Turbulent Flames 啁啾探针脉冲飞秒相干反斯托克斯拉曼散射测温在湍流火焰中的映射
IF 1.9 3区 化学 Q2 SPECTROSCOPY Pub Date : 2025-09-20 DOI: 10.1002/jrs.70049
Hui Ge, Kaiyuan Song, Mingze Xia, Yuan Zhang, Yanyan Deng, Yulei Wang, Zhiwei Lv, Sheng Zhang, Yang Zhao, Yuanqin Xia

Femtosecond chirped-probe-pulse (CPP) CARS technology has become a powerful tool for measuring complex high-temperature combustion temperatures due to its interference-free characteristics, high accuracy, and excellent time resolution. The experiment uses a specific energy-matching method to effectively separate the signal light from the background light and thus improve the accuracy of the measurement. The optimization was confirmed in the inner and outer flames of the butane Bunsen burner, with the best accuracy of 3.2% and 1.7% at 1385 and 1411 K, respectively. The two-dimensional temperature distribution at the outlet of the heat gun was experimentally measured using the aforementioned energy-matching method. The results show that the average accuracy can be below 2% at temperatures exceeding 700 K and that the temperature distribution corresponds to the nozzle structure at the air outlet. The experimental results demonstrate the successful acquisition of spatially resolved 2D temperature distributions under challenging high-temperature turbulent combustion conditions using femtosecond CPP CARS, providing valuable reference data for turbulent combustion studies.

飞秒啁啾探针脉冲(CPP) CARS技术由于其无干扰、高精度和优异的时间分辨率,已成为测量复杂高温燃烧温度的有力工具。实验采用特定的能量匹配方法,有效地将信号光与背景光分离,提高了测量精度。优化结果在丁烷本生灯的内、外火焰中得到了验证,在1385 K和1411 K温度下,优化精度分别为3.2%和1.7%。利用上述能量匹配方法,实验测量了热风枪出口的二维温度分布。结果表明,当温度超过700 K时,平均精度可低于2%,且温度分布与出气口喷嘴结构相对应。实验结果表明,利用飞秒CPP CARS成功获取了具有挑战性的高温湍流燃烧条件下空间分辨的二维温度分布,为湍流燃烧研究提供了有价值的参考数据。
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引用次数: 0
ArDI: Machine-Learning-Driven Raman Phase Analysis for Decoding Complex Mineral Assemblages in Fluid Inclusions 机器学习驱动的拉曼相位分析用于解码流体包裹体中复杂矿物组合
IF 1.9 3区 化学 Q2 SPECTROSCOPY Pub Date : 2025-09-16 DOI: 10.1002/jrs.70047
S. Smirnov, R. Shendrik, A. Myasnikova, P. Plechov

Fluid and melt inclusions serve as invaluable micro-scale archives of geochemical processes, preserving snapshots of mineral-forming fluids and melts across a broad range of pressures and temperatures in natural environments. Their analysis provides critical insights into crystallization histories, metasomatic events, and volatile cycling in geological systems. However, the automated identification of minerals within these inclusions has long been hindered by spectral complexities arising from phase coexistence, host-mineral interference, and orientation-dependent Raman signatures. This study introduces the web-based tool Advanced spectRa Deconvolution Instrument (ArDI) (https://ardi.fmm.ru), which integrates fast search algorithms (Faiss), convolutional neural networks, and recursive spectral decomposition to analyze complex Raman spectra. Using pegmatitic quartz as a case study, we demonstrate that the method allows effective identification of minerals within fluid inclusions, e.g., sassolite and ramanite-(Rb), even when their spectra are integrated with host and other minerals. The developed approach unlocks new possibilities for nondestructive analysis of mineral assemblages in microscopic objects.

流体和熔体包裹体是地球化学过程的宝贵微观档案,保存了自然环境中各种压力和温度下形成矿物的流体和熔体的快照。他们的分析为地质系统中的结晶历史、交代事件和挥发性循环提供了关键的见解。然而,长期以来,这些包裹体中矿物的自动识别一直受到相共存、宿主-矿物干扰和取向相关拉曼特征引起的光谱复杂性的阻碍。本研究引入了基于web的工具Advanced spectRa Deconvolution Instrument (ArDI) (https://ardi.fmm.ru),该工具集成了快速搜索算法(Faiss)、卷积神经网络和递归光谱分解来分析复杂的拉曼光谱。以伟晶岩石英为例,我们证明了该方法可以有效地识别流体包裹体中的矿物,例如橄榄石和拉幔石-(Rb),即使它们的光谱与宿主和其他矿物相结合。开发的方法为微观物体中矿物组合的无损分析提供了新的可能性。
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引用次数: 0
Unveiling the Crystal Structure of Sanidine: A Polarized Raman and Ab Initio Simulation Exploration 揭示Sanidine的晶体结构:偏振拉曼和从头算模拟探索
IF 1.9 3区 化学 Q2 SPECTROSCOPY Pub Date : 2025-09-16 DOI: 10.1002/jrs.70043
Michele Cassetta, Luca Bellucci, Sabrina Nazzareni, Francesco Vetere, Marco Giarola, Gino Mariotto

Sanidine, the high-temperature polymorph of potassic feldspar, plays a crucial role in the formation of volcanic rocks. Despite extensive research, the complexity of K-feldspar polymorphs remains poorly understood. This study, by combining polarized Raman spectroscopy with ab initio calculations, aims to definitively assign the vibrational modes predicted by theory to those observed experimentally. A sanidine megacryst from the rhyo-dacite sub-intrusive body of Terlano (Ora mega-caldera complex, Southern Alps, Italy) was used for this purpose. Polarized Raman spectra were collected in six scattering geometries, allowing for precise mode selection within the 40–1200 cm−1 range. Our vibrational analysis, based on density functional theory, provides wave-numbers and normal modes having trends that largely align with experimental data. The combination of experimental data and theoretical calculations also indicated that the models in which aluminum is located at the T1 tetrahedral site are more stable than those with aluminum at the T2 site. This finding provides further insight into the order–disorder phase transition in K-feldspar, a phenomenon that is difficult to replicate under laboratory conditions. These results further improve our understanding of the relationship between theoretical models and the actual spectral characteristics of this disordered mineral. The full assignment of normal modes presented here lays the foundation for future studies of phase transitions in K-feldspars using Raman spectroscopy.

钾长石的高温多晶岩在火山岩的形成中起着至关重要的作用。尽管广泛的研究,钾长石多晶的复杂性仍然知之甚少。本研究将偏振拉曼光谱与从头计算相结合,旨在明确地将理论预测的振动模式与实验观察到的振动模式相匹配。一种来自Terlano(意大利南阿尔卑斯山的Ora巨型火山口复合体)流纹英安岩亚侵入体的水晶石巨晶被用于此目的。偏振拉曼光谱以六种散射几何形状收集,允许在40-1200 cm−1范围内进行精确的模式选择。我们的振动分析,基于密度泛函理论,提供波数和正常模式的趋势很大程度上与实验数据一致。实验数据和理论计算的结合也表明,在T1四面体位置放置铝的模型比在T2四面体位置放置铝的模型更稳定。这一发现为k长石的有序-无序相变提供了进一步的见解,这种现象在实验室条件下很难复制。这些结果进一步提高了我们对这种无序矿物的理论模型与实际光谱特征之间关系的理解。本文提出的正常模式的完全赋值为今后利用拉曼光谱研究k长石的相变奠定了基础。
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引用次数: 0
Graphene Raman G Scattering Kinematics 石墨烯拉曼G散射运动学
IF 1.9 3区 化学 Q2 SPECTROSCOPY Pub Date : 2025-09-11 DOI: 10.1002/jrs.70046
Sargis Melkonyan, Tigran Zalinyan, Slavik Melkonyan

In this theoretical study, focusing on the single resonant Raman G mode, new details of Raman radiation from monolayer graphene are presented. The propagation direction of the emitted photon is discussed, explicitly considering the momenta of the incident photon, the scattered photon, and the phonon. It is demonstrated that graphene should be regarded as a quasi-two-dimensional system in light scattering phenomena, and the electron confined motion along the z-direction, perpendicular to the atomic monolayer plane, must be taken into account. It is established that the out-of-plane nature of the emitted photon arises from the uncertainty of the electron momentum along the z-direction. It is theoretically shown that at Raman G scattering, the wavenumber of the emitted iLO or iTO phonon is limited to a certain range, with boundaries determined by the crystal sizes and the wavenumber of the incident photon. Two-sided limitation of the Raman-active optical phonon wavenumber, in turn, restricts the propagation direction of the emitted photon. The developed approach is general and can also be applied to the analysis of other Raman lines of graphene.

在本理论研究中,聚焦于单共振拉曼G模式,给出了单层石墨烯拉曼辐射的新细节。考虑入射光子、散射光子和声子的动量,讨论了发射光子的传播方向。结果表明,在光散射现象中,石墨烯应被视为准二维系统,并且必须考虑电子沿垂直于原子单层平面的z方向的受限运动。确定了发射光子的面外性质是由电子动量沿z方向的不确定性引起的。理论上表明,在拉曼G散射下,发射的iLO或iTO声子的波数被限制在一定范围内,其边界由晶体尺寸和入射光子的波数决定。拉曼有源光学声子波数的双面限制反过来又限制了发射光子的传播方向。该方法具有通用性,也可应用于石墨烯其他拉曼谱的分析。
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引用次数: 0
Fabrication of Ferrum-Doped TiO2 Nanocomposite for SERS Detection of Crystal Violet in Shrimp 铁掺杂TiO2纳米复合材料用于对虾晶体紫SERS检测的制备
IF 1.9 3区 化学 Q2 SPECTROSCOPY Pub Date : 2025-09-04 DOI: 10.1002/jrs.70044
Qi Zhang, Qingyi Wei, Hongbin Pu

The residues of crystal violet (CV) in shrimp were easily absorbed by biological tissues and caused serious damage to human health. In this study, doped TiO2 SERS substrates were fabricated with three doping metals including Fe, Cu, and Co by sol-hydrothermal method. The SERS intensities reached the optimum at a Fe3+ doping ratio of 5% with probe molecules of 4-MBA and CV. The 5% Fe-TiO2 SERS substrates for monitoring CV residues obtained the best performance with LOD of 0.016 ppm and 0.03 ppm for standard solutions and shrimp protein extract solutions, respectively. The results indicated suitable doping metals could effectively modulate the energy bands of the semiconductor and improve the charge transfer between the substrate and analyte for a stronger SERS signal. The study would enrich the SERS technique for the fast test of CV in the actual samples.

结晶紫(CV)在虾体内的残留容易被生物组织吸收,对人体健康造成严重危害。本研究采用溶胶-水热法制备了Fe、Cu和Co三种掺杂金属的TiO2 SERS衬底。当Fe3+掺杂率为5%时,4-MBA和CV探针分子的SERS强度达到最佳。5% Fe-TiO2 SERS底物在标准溶液和虾蛋白提取物溶液的LOD分别为0.016 ppm和0.03 ppm时表现最佳。结果表明,适当的金属掺杂可以有效地调制半导体的能带,改善衬底和分析物之间的电荷转移,从而获得更强的SERS信号。本研究为实际样品中CV的快速检测提供了丰富的SERS技术。
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引用次数: 0
Phonon Dispersion in Molybdenum Chalcogenides Explained 硫化物钼中的声子色散解释
IF 1.9 3区 化学 Q2 SPECTROSCOPY Pub Date : 2025-09-02 DOI: 10.1002/jrs.70026
Daniel Olguín, Roberto D'Agosta, Andrés Cantarero

Molybdenum chalcogenides are one of the most studied layered materials. They have hexagonal symmetry in the single layer case as many other van der Waals materials. Thus, they can serve as a model for the analysis of many physical properties, in particular the phonon modes, the appearance of new low wave number modes when going from the single layer to the bulk, the existence of a flexural acoustic mode and the grouping of the optical modes into pairs whose difference comes from the interlayer coupling. In this work, to address some of these points, we have calculated the phonon dispersion of MoS2, MoSe2, and MoTe2 in bulk and in a single layer using Density Functional Perturbation Theory and discuss the evolution of the energy branches along the different directions of the Brillouin zone. The calculated values are in very good agreement with Raman data reported in the literature. We have also calculated the static and optical dielectric constants, as well as the reflectance, which has been compared with available infrared reflectance data available in the literature. Finally, we discuss the activity of the optical modes in the bulk and single layer case.

硫族钼是研究最多的层状材料之一。它们和其他范德华材料一样在单层情况下具有六角形对称性。因此,它们可以作为分析许多物理性质的模型,特别是声子模式,从单层到体时新的低波数模式的出现,弯曲声学模式的存在以及光学模式的分组成对,其差异来自层间耦合。在这项工作中,为了解决这些问题,我们计算了MoS 2, MoSe 2,利用密度泛函微扰理论,讨论了布里渊带不同方向上的能量分支的演化。计算值与文献报道的拉曼数据非常吻合。我们还计算了静态和光学介电常数以及反射率,并将其与文献中可用的红外反射率数据进行了比较。最后,我们讨论了在大块和单层情况下光学模式的活度。
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引用次数: 0
Modular and Automated Workflow for Streamlined Raman Signal Analysis 简化拉曼信号分析的模块化和自动化工作流程
IF 1.9 3区 化学 Q2 SPECTROSCOPY Pub Date : 2025-09-02 DOI: 10.1002/jrs.70042
Mykyta Kizilov, Vsevolod Cheburkanov, Joseph Harrington, Vladislav V. Yakovlev

Raman spectroscopy is a powerful tool for material characterization. However, careful preprocessing is required for the identification and handling of noise, baseline drift, and random spikes. This paper presents a comprehensive approach to generating and preprocessing Raman spectra. Additionally, we describe methods for fitting Voigt peaks to the spectrum to determine peak parameters. The effectiveness of these methods is demonstrated using both synthetic and real Raman spectra, with code provided in an open-source GitHub repository.

拉曼光谱是材料表征的有力工具。然而,需要仔细的预处理来识别和处理噪声、基线漂移和随机尖峰。本文提出了一种生成和预处理拉曼光谱的综合方法。此外,我们描述了将Voigt峰拟合到光谱以确定峰参数的方法。这些方法的有效性通过合成拉曼光谱和真实拉曼光谱进行了验证,并在开源的GitHub存储库中提供了代码。
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引用次数: 0
Raman Spectra of Natural Carbonaceous Materials and Associated Minerals From the Kular Range (Yakutia, Russia) 俄罗斯雅库特Kular山脉天然碳质物质及其伴生矿物的拉曼光谱
IF 1.9 3区 化学 Q2 SPECTROSCOPY Pub Date : 2025-08-20 DOI: 10.1002/jrs.70040
Tatyana N. Moroz, Sergey M. Zhmodik, Howell G. M. Edwards, Sergey V. Goryainov, Petr O. Ivanov

Carbonaceous materials (CMs) in black-shale rock specimens from the Kular Range, Sakha Republic, Yakutia, Russia, were investigated by micro-Raman spectroscopy. Studies of CM in Permian rock samples from the Ulakhan-Sis anticline collected from various boreholes in the Kular gold-bearing area, and CM in nodular monazite (NM) samples from alluvial sediments of different creeks of the Yana River basin revealed similar spectral features. Micro-Raman spectra excited at a wavelength of 532 nm exhibited characteristic CM bands together with bands of quartz, muscovite, anatase, rutile, carbonate, and pyrite. In the first-order Raman spectra of CM, G-bands were observed in the wavenumber range of ~1584–1597 cm−1, and D1 bands at ~1347–1351 cm−1 for black shale specimens, whereas for NM, G bands appeared between ~ 1572 cm−1 and 1594 cm−1, and D1 bands between ~1340 cm−1 and 1351 cm−1. NM grains consist of monazite containing numerous mineral inclusions of various sizes (from several to 10–20 μm). The Raman spectral characteristics of these associated minerals are discussed. Temperature ranges for metamorphic transformations derived from the Raman data are estimated to be 300–360 °C for CM bedrock and 346–430 °C for CM NM.

用微拉曼光谱研究了俄罗斯雅库特萨哈共和国Kular山脉黑色页岩样品中的碳质物质。在库拉金矿区不同钻孔采集的乌拉汗-西斯背斜二叠系岩石样品中的CM,以及雅纳河流域不同流域冲积物中结核性独辉石(NM)样品中的CM,均显示出相似的光谱特征。532 nm激发的微拉曼光谱显示出典型的CM波段,石英、白云母、锐钛矿、金红石、碳酸盐和黄铁矿也有相应的波段。在CM的一阶拉曼光谱中,G波段出现在~1584 ~ 1597 CM−1的波数范围内,D1波段出现在~1347 ~ 1351 CM−1的波数范围内,而NM的G波段出现在~ 1572 ~ 1594 CM−1之间,D1波段出现在~1340 CM−1 ~ 1351 CM−1之间。纳米颗粒由独居石组成,内含许多大小不等的矿物包裹体(从几μm到10-20 μm不等)。讨论了这些伴生矿物的拉曼光谱特征。根据拉曼数据估计,CM基岩的变质作用温度范围为300-360°C, CM NM的变质作用温度范围为346-430°C。
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引用次数: 0
Preparation and Identification of Heavy Minerals for Archaeometrical Studies: Villa of Fiumana (FC), Italy 用于考古研究的重矿物制备和鉴定:意大利富马纳别墅(FC)
IF 1.9 3区 化学 Q2 SPECTROSCOPY Pub Date : 2025-08-18 DOI: 10.1002/jrs.70037
S. Andò, G. Vezzoli, M. Barbarano, L. Fornasini, L. Saviane, R. Villicich, D. Bersani

A new protocol for the laboratory preparation of archaeological samples, aimed at concentrating and analysing heavy minerals by optical microscope and Raman spectroscopy, is presented. The potential of heavy-mineral studies in geoarchaeology could be enhanced conspicuously by using a state-of-the-art protocol for sample preparation, analysing potteries, tempers and archaeological items, by high-resolution mineralogical analyses in medium silt and fine sand (15–250 μm). This method is repeatable by different operators, achievable in reasonable times, applicable also with a few grams of materials, and it is conceived to remove the abundant clayey and fine and very fine silt and liberate minerals from the ground mass. To test the proposed protocol, the mineralogical composition of 5 samples (common wares, red-painted ceramics and amphorae), collected in a Roman Villa sited in Fiumana, Forlì-Cesena, Italy, was investigated. The grain size analysed is representative (63%–75% in weight), and the amount of the ‘heavy fraction’ is very low (0.35%–0.72%), but sufficient to prepare a grain mount. Metamorphic versus magmatic minerals were quantified using a transmitted light, polarizing microscope, coupled with a Raman spectrometer and the presence of opaque and semi-opaque grains using an oblique light. This quantitative study allows us to differentiate samples that have been hand-crafted using different sediments as raw materials, discussing the source from the Alps and collected from the modern Po River depositional area; the sedimentary rocks of the Apennines; the volcanic source rocks from the Roman Province. This protocol is conceived to help improve the quality of heavy-mineral separation for applications in geoarchaeology.

提出了一种新的考古样品实验室制备方案,旨在通过光学显微镜和拉曼光谱集中和分析重矿物。通过对中淤泥和细砂(15-250 μm)进行高分辨率矿物学分析,采用最先进的样品制备方案,分析陶器、陶器和考古物品,可以显著增强地质考古中重矿物研究的潜力。这种方法可以由不同的操作者重复使用,在合理的时间内实现,也适用于几克的材料,它被认为可以去除大量的粘土和细粉和极细粉,并从地面块体中释放矿物质。为了测试提议的协议,研究人员调查了意大利Fiumana (Forlì-Cesena)罗马别墅中收集的5个样品(普通陶器、红漆陶瓷和双耳罐)的矿物成分。所分析的晶粒尺寸具有代表性(占重量的63%-75%),“重组分”的含量非常低(0.35%-0.72%),但足以制备晶粒堆积。利用透射光、偏光显微镜、拉曼光谱仪和斜光源对变质矿物和岩浆矿物进行了定量分析。这项定量研究使我们能够区分使用不同沉积物作为原材料手工制作的样品,讨论来自阿尔卑斯山脉的来源和来自现代波河沉积区的收集;亚平宁山脉的沉积岩;来自罗马行省的火山烃源岩该协议旨在帮助提高重矿物分离的质量,以用于地质考古。
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引用次数: 0
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Journal of Raman Spectroscopy
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