Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy最新文献_第3页

Raman imaging uncovers Ebracteolatain A's subtype-selective metabolic reprogramming in luminal versus triple-negative breast cancer cells 拉曼成像揭示了Ebracteolatain A在腔内与三阴性乳腺癌细胞中的亚型选择性代谢重编程。

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-03 DOI: 10.1016/j.saa.2025.127294

Chengjian Li , Wentao Zhang , Haoyu Feng , YanJun Luo , Cheng Chen , Xia Huang , Liang Zhao

Ebracteolatain A (EA), a potential anti-cancer agent, has demonstrated efficacy against breast cancer through protein kinase D1 inhibition. However, its effects on cellular metabolic reprogramming and activity against aggressive cancer subtypes remain poorly understood. Using confocal Raman spectroscopy coupled with machine learning, we investigated spatial and quantitative metabolic alterations induced by EA (0, 5, 10 μM) in luminal (MCF-7) and triple-negative (SUM149) breast cancer cells at single-cell resolution. Our integrated analysis revealed distinct, concentration-dependent metabolic responses between subtypes. While both cell lines exhibited conserved EA-induced increases in glucose (1123 cm⁻¹) and lipid (1440 cm⁻¹) levels with protein depletion (2928 cm⁻¹), MCF-7 cells displayed significantly greater metabolic vulnerability. These proliferative cells showed progressive phenylalanine reduction (1003/1171 cm⁻¹) and developed characteristic perinuclear lipid-protein droplets at 5 μM EA, progressing to complete biomolecular disorganization at cytotoxic concentrations (10 μM). In contrast, SUM149 cells maintained metabolic stability, demonstrating sustained nucleic acid production (1223 cm⁻¹) and preserved subcellular integrity throughout treatment. Multivariate analysis confirmed this differential metabolic remodeling sensitivity, with linear discriminant analysis showing pronounced dose-dependent clustering in MCF-7 cells (Mahalanobis distance = 5.90) compared to SUM149 populations (distance = 3.72). These findings not only elucidate EA's subtype-specific mechanisms of action but also validate the combined Raman spectroscopy-machine learning platform as a powerful tool for pharmacometabolomic assessment. This approach provides spatial and quantitative insights into cancer cell metabolic adaptation, offering new opportunities for targeted therapeutic development.

Ebracteolatain A （EA）是一种潜在的抗癌药物，通过抑制蛋白激酶D1来治疗乳腺癌。然而，其对细胞代谢重编程和抗侵袭性癌症亚型活性的影响仍然知之甚少。利用共聚焦拉曼光谱结合机器学习技术，在单细胞分辨率下研究了EA（0、5、10 μM）诱导的luminal （MCF-7）和三阴性（SUM149）乳腺癌细胞的空间和定量代谢变化。我们的综合分析揭示了不同亚型之间不同的浓度依赖性代谢反应。虽然这两种细胞系都表现出保守的ea诱导的葡萄糖（1123 cm-1）和脂质（1440 cm-1）水平的增加和蛋白质消耗（2928 cm-1），但MCF-7细胞表现出更大的代谢脆弱性。这些增殖细胞表现出渐进的苯丙氨酸还原（1003/1171 cm-1），并在5 μM EA下形成特征性的核周脂蛋白液滴，在细胞毒性浓度（10 μM）下进展到完全的生物分子破坏。相比之下，SUM149细胞保持了代谢稳定性，在整个治疗过程中表现出持续的核酸生成（1223 cm-1）和亚细胞完整性。多变量分析证实了这种差异代谢重塑敏感性，线性判别分析显示，与SUM149群体（距离= 3.72）相比，MCF-7细胞（马氏距离= 5.90）具有明显的剂量依赖性聚类。这些发现不仅阐明了EA亚型特异性的作用机制，而且验证了拉曼光谱-机器学习联合平台作为药物代谢组学评估的强大工具。这种方法为癌细胞代谢适应提供了空间和定量的见解，为靶向治疗的开发提供了新的机会。

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引用次数: 0

Highly sensitive and selective dual-signal ratiometric fluorescent sensor based on N, S co-doped carbon dots and rhodamine B for Pb2+ ions detection in industrial wastewater 基于N， S共掺杂碳点和罗丹明B的高灵敏度和选择性双信号比例荧光传感器用于工业废水中Pb2+离子的检测。

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-03 DOI: 10.1016/j.saa.2025.127295

Yi-Xi Chen , Zhenhua Tang , Le-Yan Feng , Liu-Ling Liang , Deng-Hui Shang , Hui-Qing Li , Xiao-Hai Chen , Feng-Ming Li , Xin-Gui Tang , Shang-Xian Chen

Nowadays, heavy metal pollutants have emerged as a significant global environment affecting human health. Herein, in this work, a highly sensitive and selective dual-signal ratiometric fluorescent sensor for heavy metal Pb²⁺ ions detection in aquatic environments was developed by employing the combined highly fluorescent nitrogen and sulfur co-doped carbon dots (N,S-CDs) with rhodamine B (RhB) as a new dual-signal fluorescent probe. The nanostructure, optical properties and a self-calibration mechanism based on the intensity ratio of dual emission peaks were discussed, and, the co-doping of nitrogen and sulfur increased the electron transfer rate and enhanced the coordination interaction between the N,S-CDs and Pb²⁺ ions were revealed in the dual-signal ratiometric fluorescent sensor. Moreover, the new sensor exhibited a robust linear response to Pb²⁺ ions within the 0–180 μM range, achieving a limit of detection (LOD) of 0.45 μM (93 μg/L) in the actual measurement environment, which is observed to be commensurate with the Grade I standard limit for lead as prescribed in China's “Integrated Wastewater Discharge Standard” (100 μg/L). Furthermore, specificity experiments demonstrated the sensor's superior recognition of Pb²⁺ ions over other common metal ions (e.g., Cu²⁺, Fe³⁺, Al³⁺). In practical industrial wastewater analysis, spike recoveries of 94.20–97.53 % were achieved, with relative standard deviations (RSDs) below 1.32 %, thus validating the method's reliability. This work has been recognized to provide significant potential for environmental monitoring applications.

目前，重金属污染物已成为影响人类健康的重要全球环境问题。本文采用高荧光氮硫共掺杂碳点（N,S-CDs）与罗丹明B （RhB）作为新型双信号荧光探针，研制了一种用于水生环境中重金属Pb2+检测的高灵敏度、高选择性双信号比例荧光传感器。讨论了双信号比率荧光传感器的纳米结构、光学性质和基于双发射峰强度比的自校准机制，揭示了氮和硫共掺杂提高了电子传递速率，增强了N、S-CDs和Pb2+离子之间的配位相互作用。此外，该传感器在0 ~ 180 μM范围内对Pb2+离子表现出良好的线性响应，在实际测量环境中，检测限（LOD）为0.45 μM (93 μg/L)，符合中国《污水综合排放标准》中铅的一级标准限值（100 μg/L）。此外，特异性实验表明，该传感器对Pb2+离子的识别优于其他常见金属离子（如Cu2+， Fe3+, Al3+）。在实际工业废水分析中，峰回收率为94.20 ~ 97.53%，相对标准偏差（rsd）小于1.32%，验证了方法的可靠性。这项工作已被认为为环境监测应用提供了巨大的潜力。

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引用次数: 0

Effect of Sm3+ ions on structure and reactivity of S53P4 and 13–93 bioactive glasses Sm3+离子对S53P4和13-93生物活性玻璃结构和反应性的影响

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-03 DOI: 10.1016/j.saa.2025.127299

Agata Baranowska , Marcin Kochanowicz , Aleksandra Wajda , Magdalena Leśniak , Piotr Miluski , Dawid Łysik , Piotr Jeleń , Maciej Sitarz , Zbigniew Olejniczak , Dominik Dorosz

Bioactive glasses are widely recognized for their ability to bond with living tissues and stimulate regenerative processes, making them a cornerstone in the development of advanced biomaterials. Incorporating rare earth (RE) elements enables the integration of optical functionalities with biological activity while modifying network connectivity. However, previous studies have mainly focused on luminescent performance, and the structural mechanisms by which individual REE dopants influence dissolution kinetics and bioactivity remain insufficiently investigated. This study investigates the influence of samarium (Sm³⁺) doping on the structural and in vitro bioactive behavior of two Hench-type glasses, S53P4 and 13–93, containing 0.2 and 2 mol% Sm₂O₃.

Structural characterization by MAS-NMR, FTIR, and Raman spectroscopy reveals that Sm³⁺ promotes silicate network depolymerization by generating non-bridging oxygens. Despite this depolymerization, Sm-doped glasses show reduced ion release (up to 20 % reduction in Ca and Si after 24 h), and lower pH changes (maximum pH 7.8 vs. 8.4 in the undoped glass), and a delayed hydroxycarbonate apatite (HCA) formation in simulated body fluid (SBF). These effects are attributed to strong SmO bonding and restricted ion mobility in the glass network.

The findings indicate that Sm³⁺ modifies the glass network and influences dissolution kinetics, providing clearer insight into the structure–bioactivity relationship in REE-doped silicate glasses. This combined behavior may be used to guide the design of compositions with controlled degradation for regenerative applications.

生物活性玻璃因其与活体组织结合和刺激再生过程的能力而被广泛认可，使其成为先进生物材料发展的基石。加入稀土元素可以将光学功能与生物活性结合起来，同时改变网络连接。然而，以往的研究主要集中在发光性能上，对稀土掺杂物影响溶解动力学和生物活性的结构机制研究不足。本文研究了钐（Sm3+）掺杂对含0.2 mol% Sm2O3的S53P4和13-93两种hench型玻璃的结构和体外生物活性的影响。通过MAS-NMR、FTIR和拉曼光谱的结构表征表明Sm3+通过生成非桥氧促进硅酸盐网络解聚。尽管发生了解聚，但sm掺杂玻璃显示出离子释放减少（24小时后Ca和Si最多减少20%），pH变化降低（最大pH 7.8 vs.未掺杂玻璃8.4），模拟体液（SBF）中羟基碳酸盐磷灰石（HCA）形成延迟。这些效应归因于玻璃网络中SmO键强和离子迁移受限。研究结果表明，Sm3+改变了玻璃网络并影响了溶解动力学，为ree掺杂硅酸盐玻璃的结构-生物活性关系提供了更清晰的认识。这种组合行为可用于指导可再生应用的降解控制组合物的设计。

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引用次数: 0

Highly sensitive detection of diethylstilbestrol based on a dual-mode membrane sensor of molecular imprinted nanozymes 基于分子印迹纳米酶双模膜传感器的己烯雌酚高灵敏度检测。

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-03 DOI: 10.1016/j.saa.2025.127303

Yongfei Zhou , Ning Li , Li Ming , Dongyang Li , Xiaobo Zou , Can Zhang

Environmental endocrine disruptors like diethylstilbestrol (DES), prevalent in livestock and the environment, pose significant ecological and health risks through biomagnification. In the study, a visual and rapid detection method for diethylstilbestrol in milk was achieved by constructing a molecularly imprinted nanozyme-loaded PVDF membrane sensor integrated with smartphone analysis. The sensor was fabricated through in situ growth of ZIF-8 on a PVDF membrane, followed by loading of copper nanoparticles (CuNPs) and formation of a molecularly imprinted polymer layer via dopamine self-polymerization. The catalytic activity of CuNPs oxidizes OPD to generate the chromogenic/fluorogenic product DAP, whose absorbance and fluorescence intensity decrease with increasing DES concentration. The colorimetric mode demonstrated a linear range of 0.5–200 μM with a LOD of 0.38 μM. Spiked recoveries ranged from 94.3 % to 108.4 %, showing good agreement with validation results obtained by HPLC.

环境内分泌干扰物，如己烯雌酚（DES），普遍存在于牲畜和环境中，通过生物放大造成重大的生态和健康风险。本研究通过构建与智能手机分析相结合的分子印迹纳米酶负载PVDF膜传感器，实现了牛奶中己烯雌酚的视觉快速检测方法。该传感器是通过在PVDF膜上原位生长ZIF-8，然后加载铜纳米颗粒（CuNPs）并通过多巴胺自聚合形成分子印迹聚合物层来制备的。CuNPs的催化活性氧化OPD生成显色/荧光产物DAP，其吸光度和荧光强度随DES浓度的增加而降低。该比色模式线性范围为0.5 ~ 200 μM， LOD为0.38 μM。加标回收率为94.3% ~ 108.4%，与HPLC验证结果吻合较好。

引用次数: 0

Rapid and ultrasensitive detection of quinolone antibiotics by ratiometric fluorescence sensing integrated with redox cycling signal amplification 结合氧化还原循环信号放大的比例荧光传感技术快速超灵敏检测喹诺酮类抗生素

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-02 DOI: 10.1016/j.saa.2025.127291

Hu Chen , Fangling Li , Zhengdong Gui, Silai Xu, Jianjian Yang, Shengjie Sun, Aiming Sun, Jianxin Luo, Lijuan Ou

Abuse of quinolones, especially enrofloxacin (ENR), has caused unexpected accumulation of antibiotics in food, soil and water, and various sensing platforms and methods have been employed for quinolone detection. Nevertheless, quinolone detection by conventional approaches is limited by tedious process and insufficient sensitivity (reflected as narrow linear ranges). In this study, a ratiometric fluorescence probe (GSH-CuNCs/DAP, wherein GSH = glutathione, CuNCs = Cu nano-clusters, DAP = 2,3-diaminophenazine) was developed for rapid and ultrasensitive detection of quinolone antibiotics based on redox cycling signal amplification and internal filtration effect (IFE). The effects of preparation conditions on the fluorescence intensity of GSH-CuNCs and the effects of detection conditions on the ENR detection using GSH-CuNCs were investigated. Meanwhile, quantitative detection of ENR by GSH-CuNCs/DAP was demonstrated. Additionally, the specificity was explored using seven potential interfering substances and real samples. The results demonstrated that the proposed assay has a broad linear range (1–100 μmol/L, correlation coefficient = 0.9984) and excellent spike-and-recovery rates (94.3 %–103.1 %). This can be attributed to: (1) Cu²⁺/Cu⁺ redox cycling is facilitated by H₂O₂, resulting in significant signal amplification and eventually high sensitivity; (2) specific complexation of ENR and Cu²⁺ hinders the Cu²⁺/Cu⁺ redox cycling, resulting in degraded IFE efficiency and eventually high specificity. This study paves the way for development of ultrasensitive and portable sensors for various antibiotics.

喹诺酮类药物，尤其是恩诺沙星（ENR）的滥用导致抗生素在食物、土壤和水中的意外积累，各种传感平台和方法被用于喹诺酮类药物的检测。然而，传统的喹诺酮类药物检测方法由于过程繁琐和灵敏度不足（反映为线性范围窄）而受到限制。本研究基于氧化还原循环信号放大和内过滤效应（IFE），研制了一种比例荧光探针（GSH-CuNCs/DAP, GSH =谷胱甘肽，CuNCs = Cu纳米簇，DAP = 2,3-二氨基吩嗪），用于喹诺酮类抗生素的快速超灵敏检测。研究了制备条件对GSH-CuNCs荧光强度的影响以及检测条件对GSH-CuNCs检测ENR的影响。同时，验证了GSH-CuNCs/DAP对ENR的定量检测。此外，利用7种潜在干扰物质和实际样品探讨了特异性。结果表明，该方法具有较宽的线性范围（1 ~ 100 μmol/L，相关系数= 0.9984）和良好的加标回收率（94.3% ~ 103.1%）。这可以归结为：(1)H2O2促进Cu2+/Cu+氧化还原循环，使信号放大显著，最终具有高灵敏度；(2) ENR与Cu2+的特异性络合阻碍了Cu2+/Cu+氧化还原循环，导致IFE效率下降，最终导致高特异性。本研究为各种抗生素的超灵敏便携式传感器的开发奠定了基础。

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引用次数: 0

Meeting of the International Association for Spectral Imaging IASIM-2024 国际光谱成像协会会议IASIM-2024：西班牙毕尔巴鄂，2024年7月6日至10日。

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-02 DOI: 10.1016/j.saa.2025.127290

José Manuel Amigo , Giulia Gorla , Sergey Kucheryavskiy

引用次数: 0

Chirality discrimination of D/L-malic acid and its diethyl ester based on terahertz polarization time-domain spectroscopy 基于太赫兹极化时域光谱的D/ l -苹果酸及其二乙酯手性鉴别

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-02 DOI: 10.1016/j.saa.2025.127296

Huanlin Li, Wei Shi, Yusong Zhang

Terahertz time-domain spectroscopy (THz-TDS) technology offers unique advantages for biomedical applications and non-destructive testing. Unlike X-rays, THz technology does not damage the materials being tested, especially active substances. However, traditional THz-TDS techniques still struggle to distinguish between chiral substances. This study presents a terahertz polarization time-domain spectroscopy system (THz-PTDS) that utilizes a 2 × 2 GaAs photoconductive array to detect the polarization of terahertz waves. This system enables the non-destructive and rapid identification of chiral forms of malic acid and its diethyl ester enantiomers. The results indicated that the polarization parameter curves for both solid and solution forms of malic acid showed significant chiral differences at frequency of 0.6 THz. Moreover, the polarization parameter curve of a malic acid diethyl ester-ethanol solution displayed significant chiral differences at 0.93 THz, while the pure malic acid diethyl ester showed significant chiral differences at 1.013 THz. Furthermore, the rotation direction of the polarization ellipse at the corresponding THz frequencies can be used to distinguish between enantiomers. This method provides an innovative approach for the rapid identification of chiral enantiomers in food and pharmaceuticals, with significant application prospects and potential benefits.

太赫兹时域光谱（THz-TDS）技术为生物医学应用和无损检测提供了独特的优势。与x射线不同，太赫兹技术不会损坏被测试的材料，尤其是活性物质。然而，传统的太赫兹- tds技术仍然难以区分手性物质。本研究提出一种太赫兹偏振时域光谱系统（THz-PTDS），该系统利用2 × 2 GaAs光导阵列来探测太赫兹波的极化。该系统能够无损和快速地识别苹果酸及其二乙酯对映体的手性形式。结果表明，苹果酸固溶极化参数曲线在0.6 THz频率下存在显著的手性差异。此外，苹果酸二乙酯-乙醇溶液的极化参数曲线在0.93 THz处存在显著的手性差异，而纯苹果酸二乙酯在1.013 THz处存在显著的手性差异。此外，极化椭圆在相应太赫兹频率下的旋转方向可以用来区分对映体。该方法为食品和药品中手性对映体的快速鉴定提供了一种创新的方法，具有重要的应用前景和潜在效益。

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引用次数: 0

Contrastive learning-based fusion of NIR spectroscopy and visual cues for molecular discrimination of Chinese herbal species 基于对比学习的近红外光谱与视觉线索融合在中药物种分子鉴别中的应用。

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-02 DOI: 10.1016/j.saa.2025.127289

Yu Yang , Miao Li , Xuehai Zhang , Yao Qin , Chengxin Cai , Zelong Liu , Dandan Zhai , Peng Li , Jiafen Shang

Accurate identification of Chinese medicinal herbs is essential for ensuring quality control and clinical safety. However, conventional visual inspection and machine vision techniques often struggle to distinguish morphologically similar herbs. This study proposes a cross-modal neural framework, named as CNRP, which integrates RGB imaging and near-infrared (NIR) spectroscopy through contrastive learning to enhance fine-grained herbal classification. CNRP is designed as a dual-stream architecture, which extracts key features from RGB images and NIR spectra through image encoder and spectral encoder respectively, then enhances the global information in the features through the multi-head attention modules, and finally performs semantic alignment of the dual stream data features. RGB and NIR are used simultaneously to train the CNRP network and construct the NIR feature set; in the inference stage, it is only necessary to extract features from the input RGB image and match the features with similar features in the NIR feature set to complete the classification of the input RGB image. Experimental results on 8 categories of visually confusing herb demonstrate that the proposed method achieves overall accuracy of 97.32 %, which is at least 16.11 % higher than the conventional vision baselines. This work provides a cost-effective and scalable solution for intelligent herbal authentication.

准确的中药材鉴别是保证中药材质量控制和临床安全的关键。然而，传统的视觉检测和机器视觉技术往往难以区分形态相似的草药。本研究提出了一种名为CNRP的交叉模态神经框架，该框架通过对比学习将RGB成像和近红外（NIR）光谱相结合，以增强细粒度草药分类。CNRP设计为双流架构，分别通过图像编码器和光谱编码器从RGB图像和近红外光谱中提取关键特征，然后通过头部关注模块增强特征中的全局信息，最后对双流数据特征进行语义对齐。同时使用RGB和NIR来训练CNRP网络并构建NIR特征集；在推理阶段，只需要从输入RGB图像中提取特征，并将特征与近红外特征集中相似的特征进行匹配，即可完成输入RGB图像的分类。对8类视觉混淆草药的实验结果表明，该方法总体准确率达到97.32%，比传统视觉基线提高至少16.11%。这项工作为智能草药认证提供了一种具有成本效益和可扩展性的解决方案。

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引用次数: 0

A ratiometric fluorescent nanoprobe for formaldehyde imaging in Arabidopsis thaliana 拟南芥甲醛成像的比例荧光纳米探针

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-02 DOI: 10.1016/j.saa.2025.127292

Xiaoqing Wang, Beibei Cui, Zhangtao Min, Li Xu

Formaldehyde (FA), a highly reactive carbonyl species, plays essential roles in cellular metabolism but can induce cytotoxicity when present at elevated levels. Sensitive and reliable detection of FA in biological systems is therefore crucial for understanding its physiological functions and pathological implications. In this study, a fluorescent nanoprobe (DR-NP_647/573) was constructed by co-encapsulating two fluorophores—dicyanoisophorone-based DISE as the FA-responsive unit and Rhodamine B as the internal reference—within pluronic F-127. This design enables ratiometric fluorescence detection, providing improved resistance to environmental fluctuations and instrumental variation compared with single-emission probes. DR-NP_647/573 displays a pronounced ratiometric response toward FA, with high sensitivity (detection limit: 0.81 μM) and a rapid reaction within 6 min. The probe also exhibits excellent stability and selectivity under physiological conditions. Importantly, when applied to Arabidopsis thaliana root tip tissues, DR-NP_647/573 enabled clear ratiometric imaging of FA, demonstrating its suitability for visualizing endogenous FA in plant systems. These findings highlight the potential of this nanoprobe as a robust analytical tool for investigating FA dynamics in complex biological environments.

甲醛（FA）是一种高活性羰基物质，在细胞代谢中起着重要作用，但当甲醛水平升高时可引起细胞毒性。因此，灵敏可靠地检测生物系统中的FA对于了解其生理功能和病理意义至关重要。本研究通过在pluronic F-127中共包封两种荧光基团（基于二氰异膦酮的dis作为fa响应单元，罗丹明B作为内参）构建了一种荧光纳米探针（DR-NP647/573）。与单发射探针相比，这种设计使比率荧光检测能够更好地抵抗环境波动和仪器变化。DR-NP647/573对FA有明显的比例响应，灵敏度高（检测限为0.81 μM）， 6 min内反应迅速。该探针在生理条件下也表现出良好的稳定性和选择性。重要的是，当将DR-NP647/573应用于拟南芥根尖组织时，DR-NP647/573能够对FA进行清晰的比例成像，证明其适用于植物系统中内源FA的可视化。这些发现突出了这种纳米探针作为研究复杂生物环境中FA动力学的强大分析工具的潜力。

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引用次数: 0

Engineering multifunctional Cyclen fluorophores for metal ion sensing, self-assembly and Nanocolloid applications 工程多功能循环荧光团金属离子传感，自组装和纳米胶体的应用

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-12-01 DOI: 10.1016/j.saa.2025.127285

Frederico Duarte , Cristián Cuerva , Georgi M. Dobrikov , Atanas Kurutos , Nikolay G. Vassilev , Javier Fernández-Lodeiro , José Luis Capelo-Martinez , Hugo M. Santos , Carlos Lodeiro

We report the design, synthesis, and comprehensive characterization of three novel monodansylated cyclen derivatives (L1−L3), each bearing alkyl side chains of varying lengths (n = 8, 12, 16), developed as multifunctional fluorophores. Polarized optical microscopy (POM) and differential scanning calorimetry (DSC) were employed to evaluate mesomorphism, a property often associated with extended alkyl chains. These compounds exhibited pronounced solvatochromic behavior and high fluorescence quantum yields, reaching up to 55 % in chloroform. The influence of solvent polarity on their photophysical properties was quantitatively analyzed using the Kamlet–Taft equation. Self-assembly behavior in THF–water mixtures revealed aggregation-induced emission (AIE), with emission profiles varying according to alkyl chain length, as confirmed by dynamic light scattering (DLS) and fluorescence lifetime measurements. Selective detection of Cu²⁺ and Hg²⁺ ions by L1 was demonstrated through significant fluorescence quenching, with detection limits of 2 μM and 40 μM, respectively. Speciation amount Cu²⁺/Cu⁺ and Hg²⁺/Hg⁺ was observed. Additionally, L3 functioned effectively as a stabilizing agent in the colloidal synthesis of platinum nanoparticles, resulting in spherical nanostructures with low polydispersity, as confirmed by transmission electron microscopy (TEM) and DLS. These results highlight the versatile utility of alkylated dansyl–cyclen hybrids as fluorescent probes with self-assembly properties useful as nanomaterial stabilizers for advanced functional applications.

我们报道了三种新型单酰基环衍生物（L1−L3）的设计、合成和综合表征，每种衍生物都具有不同长度的烷基侧链（n = 8、12、16），作为多功能荧光团。偏振光学显微镜（POM）和差示扫描量热法（DSC）被用来评估介形性，这一性质通常与延伸的烷基链有关。这些化合物表现出明显的溶剂化变色行为和高荧光量子产率，在氯仿中达到55%。利用Kamlet-Taft方程定量分析了溶剂极性对其光物理性质的影响。动态光散射（DLS）和荧光寿命测量证实，thf -水混合物中的自组装行为显示出聚集诱导发射（AIE），发射曲线根据烷基链长度而变化。L1对Cu2+和Hg2+离子的选择性检测通过显著的荧光猝灭，检测限分别为2 μM和40 μM。观察到Cu2+/Cu+和Hg2+/Hg+的形成量。此外，通过透射电镜（TEM）和DLS证实，L3在铂纳米颗粒的胶体合成中有效地发挥了稳定剂的作用，形成了具有低多分散性的球形纳米结构。这些结果突出了烷基化丹基环杂化物作为具有自组装特性的荧光探针的多功能用途，可作为先进功能应用的纳米稳定剂。

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引用次数: 0