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Keggin-type Polyoxometalate-modified BiOI heterostructures for enhanced photocatalytic oxidation of hazardous organic pollutants keggin型多金属氧酸盐修饰的BiOI异质结构增强光催化氧化有害有机污染物
IF 4.7 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-20 DOI: 10.1016/j.jphotochem.2026.117056
Nurseli Görener Erdem , Nergiz Kanmaz , Özlem Tuna , Esra Bilgin Simsek
Herein, we designed an interface-engineered heterojunction between bismuth oxyiodide (BiOI) and a Keggin-type polyoxometalate (H3PW12O40, PW, POM) to accelerate interfacial charge transfer for dual photocatalytic functions: pollutant degradation and green H2 evolution. The BiOI/PW composites were prepared by a hydrothermal route, and comprehensively characterized (XRD, SEM/EDS, XPS, BET, UV–vis DRS, PL, EIS, and Mott–Schottky). Morphological changes and elemental analysis from SEM/EDS together with XPS shifts and BET results, verified the integration of PW and robust its interfacial bonding with BiOI. The coupling of PW preserved the BiOI crystal phase while modulating its optoelectronic properties. EIS analysis revealed a reduced interfacial resistance consistent with faster carrier transport. Mott–Schottky analysis confirmed n-type behavior and the calculated band positions proposed direct Z-scheme charge migration across the interface. In the photocatalytic remediation tests, the optimized BiOI/PW (1: 4) achieved 84.7% degradation of crystal violet (CV) under visible light (vs 55.1% for BiOI) with a 2.72-fold higher apparent rate constant (0.00942 min−1). Beyond CV, the composite exhibited notable versatility against structurally diverse dyes (e.g., 86.5% for allura red, 79.5% for sunset yellow) and pharmaceutical contaminants, such as doxycycline (82.8% vs 72.3% for BiOI), ciprofloxacin (58.1% vs 29.0%), and tetracycline (74.7% vs 70.0%), demonstrating broad-spectrum pollutant removal capability. Moreover, acute Daphnia magna bioassays revealed that the photocatalytic treatment markedly reduced ecotoxicity, with immobilization decreasing to below 50%Finally, the photocatalytic hydrogen evolution reached 6101 μmol g−1 h−1 for BiOI/PW (1, 4), 1.3-times greater than that of BiOI, underscoring the merit of POM-assisted interfacial design for multifunctional photocatalysis.
在此,我们设计了一个界面工程的氧化铋(BiOI)和keggin型多金属氧酸盐(H3PW12O40, PW, POM)之间的异质结,以加速界面电荷转移,实现双重光催化功能:污染物降解和绿色H2演化。采用水热法制备了BiOI/PW复合材料,并对其进行了XRD、SEM/EDS、XPS、BET、UV-vis DRS、PL、EIS、Mott-Schottky等综合表征。SEM/EDS的形态变化和元素分析以及XPS位移和BET结果验证了PW的集成及其与BiOI的界面结合。PW的耦合保留了BiOI晶体相位,同时调制了其光电性能。EIS分析显示界面阻力降低与载流子传输速度加快一致。Mott-Schottky分析证实了n型行为,计算出的能带位置提出了直接的Z-scheme电荷跨界面迁移。在光催化修复试验中,优化后的BiOI/PW(1:4)在可见光下对结晶紫(CV)的降解率为84.7% (BiOI为55.1%),表观速率常数(0.00942 min−1)提高了2.72倍。除CV外,该复合材料对结构不同的染料(例如,对紫红色的去除率为86.5%,对日落黄的去除率为79.5%)和药物污染物(如强力霉素(82.8%对72.3%对BiOI),环丙沙星(58.1%对29.0%)和四环素(74.7%对70.0%))表现出显著的多功能性,表现出广谱污染物去除能力。此外,急性大水蚤生物实验表明,光催化处理显著降低了生态毒性,固定化率降至50%以下。最后,BiOI/PW(1,4)的光催化析氢量达到6101 μmol g−1 h−1,是BiOI的1.3倍,突出了pom辅助界面设计用于多功能光催化的优点。
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引用次数: 0
Excited-state isomerization and spectral reassignment of resveratrone induced by internal conversion 内转化诱导白藜芦酮的激发态异构化和光谱重分配
IF 4.7 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-19 DOI: 10.1016/j.jphotochem.2026.117052
Mai-Ning Li , Si-Ying Lu , Ya-Jing Peng , Yu Zhao , Yu-Hui Liu , Jun Gao , Chaoyuan Zhu
The excited-state isomerization of resveratrone (RES) is computationally investigated in order to reinterpret the spectral features associated with the excited-state proton transfer (ESPT) reaction dynamics in methanol solvents (MeOH). The calculations reveal that the anti-RES:MeOH is more stable than syn-RES:MeOH in the ground state (S0). Upon excitation of anti-RES:MeOH to the first excited state (S1), an ESPT reaction is taken place to generate the anionic species anti-1-anion:MeOH that undergoes an isomerization to syn-1-anion:MeOH due to a thermodynamically favorable energy pathway. Both anionic conformers contribute to the observed fluorescence emission. During the isomerization process, an intermediate state characterized by a twisted intramolecular charge transfer (TICT) configuration is encountered, which facilitates efficient non-radiative internal conversion (IC) owing to the small energy gap between the excited and ground states. Overall, hydrogen bonding plays a crucial role in enhancing the isomerization of both RES:MeOH in the S₀ state and 1-anion:MeOH in the S₁ state. These findings confirm the ESPT mechanism of RES:MeOH in methanol, involving the coexistence of radiative and non-radiative decay pathways. The experimentally observed absorption and emission spectra are successfully reassigned, leading to the proposal of a novel fluorescence mechanism for RES:MeOH in methanol.
为了重新解释与激发态质子转移(ESPT)反应动力学相关的光谱特征,计算研究了白藜芦醇(RES)的激发态异构化。计算结果表明,在基态(so0)下,反res:MeOH比顺res:MeOH更稳定。当anti-RES:MeOH被激发到第一激发态(S1)后,发生ESPT反应生成阴离子类anti-1-阴离子:MeOH,由于热力学上有利的能量途径,该阴离子类anti-1-阴离子:MeOH会异构化成syn1 -阴离子:MeOH。这两种阴离子构象都有助于观察到的荧光发射。在异构化过程中,会遇到以扭曲分子内电荷转移(TICT)构型为特征的中间态,由于激发态和基态之间的能量间隙小,有利于有效的非辐射内转换(IC)。总的来说,氢键在S 0状态的RES:MeOH和S₁状态的1-阴离子:MeOH的异构化过程中起着至关重要的作用。这些发现证实了RES:MeOH在甲醇中的ESPT机制,涉及辐射和非辐射衰变途径的共存。实验观察到的吸收和发射光谱被成功地重新分配,从而提出了一种新的RES:MeOH在甲醇中的荧光机制。
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引用次数: 0
Structure-property relationships in D-π-D hole transport materials: Insights into conjugation, planarity, and interfacial charge dynamics D-π-D空穴输运材料的结构-性质关系:共轭、平面性和界面电荷动力学的见解
IF 4.7 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-17 DOI: 10.1016/j.jphotochem.2026.117051
Yu Zhang , Long Zhang , Xuefei Pan , Xueling Zhang , Zifu Zang , Yuanzuo Li
We conducted a systematic investigation on the experimental hole transport material 4,8-bis(N-(4-(methylthio)phenyl)diphenylamino)-O-alkyl-BDT (BM) and three designed D-π-D type molecules (BM1, BP1, and A-BP1) using density functional theory and time-dependent density functional theory. The research content includes geometric structure, frontier molecular orbitals, stability, reorganization energy, excited state properties, hole mobility and interface characteristics. The research results show that compared with BM, the BM1, BP1, and A-BP1 are more compatible with that of the perovskite. Designed molecules exhibit two characteristic absorption peaks, and the charge transfer character was analyzed to reveal the electron-hole coherence in the D-π-D area and electron transfer direction from the two-sided diphenylamine donors to the π bridge. Analysis of the interface between molecules and perovskites shows BP1 and A-BP1 exhibit better interface character than BM, and A-BP1 possesses the highest hole mobility among all studied molecules. This study elucidates how the variation in the length of the π-bridge and the introduction of thiophene groups regulate the charge transport mechanism, providing a useful design guideline for high-performance HTMs in perovskite solar cells.
利用密度泛函理论和时变密度泛函理论对实验空穴输运材料4,8-双(N-(4-(甲基硫)苯基)二苯胺)- o -烷基- bdt (BM)和三个设计的D π-D型分子(BM1、BP1和a -BP1)进行了系统的研究。研究内容包括几何结构、前沿分子轨道、稳定性、重组能、激发态性质、空穴迁移率和界面特性。研究结果表明,与BM相比,BM1、BP1和A-BP1与钙钛矿的相容性更好。设计的分子具有两个特征吸收峰,并分析了电荷转移特性,揭示了D-π-D区域的电子-空穴相干性以及从双面二苯胺给体到π桥的电子转移方向。分子与钙钛矿的界面分析表明,BP1和A-BP1比BM具有更好的界面特性,并且A-BP1具有最高的空穴迁移率。本研究阐明了π桥长度的变化和噻吩基团的引入如何调控电荷输运机制,为钙钛矿太阳能电池中高性能HTMs的设计提供了有用的指导。
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引用次数: 0
Influence of solvent polarity on excited-state proton transfer reaction for 2,5-diethyl-bis(benzoxazolyl)-2,6-dihydroxynaphthalene fluorophore: A theoretical study 溶剂极性对2,5-二乙基-双(苯并恶唑)-2,6-二羟基萘荧光基团激发态质子转移反应影响的理论研究
IF 4.7 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-17 DOI: 10.1016/j.jphotochem.2026.117055
Han Wang , Jinfeng Zhao , Jiahe Chen
To address the theoretical gaps in the regulatory mechanism of excited-state double proton transfer (ESDPT) of 2,5-diethyl-bis(benzoxazolyl)-2,6-dihydroxynaphthalene (DBBD) – including the existence of ESDPT behaviors, reaction pathway, and how solvent polarity impacts intramolecular hydrogen bonds - this study selected four solvents with increasing polarity (heptane, toluene, tetrahydrofuran, and acetonitrile) to conduct relevant research. Findings demonstrated that in comparison to the ground state (S0), DBBD in the first excited state (S1) exhibited markedly strengthened intramolecular hydrogen bonds, evidenced by extended OH bond lengths, shortened HN bond lengths, and enlarged bond angles of Δ(O1H2N3) and Δ(O4H5N6); the stretching vibration frequency of OH bonds in the S₁ state showed a notable redshift, and the redshift degree increased with solvent polarity, facilitating the breaking of OH covalent bonds. Analysis of the core-valence bifurcation (CVB) index and bond critical point (BCP) parameter analysis further confirmed that hydrogen bonds in S₁ state were more robust than those in S₀ state, and solvent polarity could further amplify this effect. Frontier molecular orbital analysis revealed that the S₀ → S₂ transition of DBBD followed the HOMO-1 → LUMO transition (the ππ* type), and photoexcitation induced charge transfer from hydroxyl O atoms to N atoms, providing the core driving force for ESDPT reaction. Potential energy surface (PES) analysis suggested that the S₀ state possessed a high energy barrier for proton transfer, rendering excited-state intramolecular proton transfer (ESIPT) hardly feasible; in contrast, the S₁ state had prominent low-energy regions and low-energy barrier transition zones, and ESDPT proceeded in a stepwise pathway (DBBD → single-proton transfer state DBBD-PT1 → double-proton transfer state DBBD-PT2) with low energy barriers. With the increase of solvent polarity, the solvation effect more significantly stabilized the polar intermediate (DBBD-PT1) and product (DBBD-PT2) in the S₁ state, reduced the energy barriers of each ESDPT step, and improved product stability. This study clearly verifies the mechanism by which solvent polarity regulates the stepwise ESDPT of DBBD, providing a theoretical basis for understanding the environmental response mechanism of double proton transfer systems and offering guidance for the design of solvent polarity-responsive fluorescent materials.
为了解决2,5-二乙基-双(苯并恶唑基)-2,6-二羟基萘(DBBD)激发态双质子转移(ESDPT)调控机制的理论空白,包括ESDPT行为的存在、反应途径以及溶剂极性对分子内氢键的影响,本研究选择了极性逐渐增大的四种溶剂(庚烷、甲苯、四氢呋喃和乙腈)进行了相关研究。结果表明:与基态(S0)相比,DBBD在第一激发态(S1)表现出明显增强的分子内氢键,表现为OH键长度延长,HN键长度缩短,Δ(O1H2N3)和Δ(O4H5N6)键角增大;S₁状态下OH键的伸缩振动频率出现了明显的红移,且红移程度随溶剂极性的增加而增大,有利于OH共价键断裂。核价分岔(CVB)指数分析和键临界点(BCP)参数分析进一步证实了S₁状态下的氢键比S₀状态下的氢键更坚固,溶剂极性进一步放大了这一效应。前沿分子轨道分析表明,DBBD的S 0→S 2跃迁顺序为HOMO-1→LUMO跃迁(ππ*型),光激发诱导电荷从羟基O原子向N原子转移,为ESDPT反应提供了核心驱动力。势能面(PES)分析表明,S 0态具有较高的质子转移能垒,使得激发态分子内质子转移(ESIPT)难以实现;S₁态具有明显的低能区和低能势垒跃迁区,ESDPT以低能垒的方式逐步进行(DBBD→单质子转移态DBBD- pt1→双质子转移态DBBD- pt2)。随着溶剂极性的增加,溶剂化效应更加显著地稳定了极性中间体(DBBD-PT1)和生成物(DBBD-PT2)在S₁状态,降低了ESDPT各步的能垒,提高了生成物的稳定性。本研究明确验证了溶剂极性调控DBBD逐步ESDPT的机理,为理解双质子转移体系的环境响应机制提供了理论基础,并为溶剂极性响应荧光材料的设计提供了指导。
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引用次数: 0
An ultrasensitive Split-Aptasensor for L-selectin: Integrating nicking enzyme-assisted 3D DNA Walker with CRISPR-Cas12a signal amplification 一种超灵敏的l -选择素分裂-适体传感器:整合nick酶辅助的3D DNA Walker与CRISPR-Cas12a信号放大
IF 4.7 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-14 DOI: 10.1016/j.jphotochem.2026.117053
Li Zhou , Xianwei Jiao , Yuting Zhang , Changling Yan
L-selectin, a leukocyte adhesion receptor, is essential in the early step of the adhesion cascade, facilitating the migration of leukocytes into surrounding tissues during inflammation and immune surveillance. Clinical studies have identified L-selectin as a prospective treatment option for many both acute and ongoing inflammatory conditions. Clarifying the cellular signaling pathways that function in the immediate vicinity of L-selectin may yield unique treatments tailored to certain cell types or illnesses. The study describes the development of a precise and sensitive fluorescence biosensor designed for the detection of L-selectin using a split aptamer specific to L-selectin. This biosensor utilizes nicking enzyme-assisted DNA walking together CRISPR-Cas12a for dual-signal multiplication. The calibration curve for L-selectin demonstrates a detection limit of 0.45 ng/mL, with an extensive linear range spanning from 10 to 1280 ng/mL. The fluorometric sensors effectively identified L-selectin in human blood samples, producing excellent outcomes. The fluorometric sensors effectively identified L-selectin in human blood samples, producing excellent outcomes. The original appearance not only validates the concept but also possesses substantial possibilities for identifying diverse targets.
l -选择素是一种白细胞粘附受体,在粘附级联的早期阶段至关重要,在炎症和免疫监视期间促进白细胞向周围组织的迁移。临床研究已经确定l -选择素作为许多急性和持续炎症条件的前瞻性治疗选择。明确在l -选择素附近发挥作用的细胞信号通路可能会产生针对某些细胞类型或疾病的独特治疗方法。该研究描述了一种精确和敏感的荧光生物传感器的开发,该传感器设计用于检测l -选择素,使用l -选择素特异性的分裂适体。这种生物传感器利用酶辅助DNA行走CRISPR-Cas12a进行双信号增殖。L-selectin的检出限为0.45 ng/mL,线性范围为10 ~ 1280 ng/mL。荧光传感器有效地识别了人类血液样本中的l -选择素,产生了良好的结果。荧光传感器有效地识别了人类血液样本中的l -选择素,产生了良好的结果。原始外观不仅验证了概念,而且具有识别不同目标的实质性可能性。
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引用次数: 0
A-site doping modulates Mn2+ energy level splitting for green luminescence in Cs3MnBr5 perovskites under blue excitation and stacking solar cell application a位掺杂调节Cs3MnBr5钙钛矿中Mn2+在蓝色激发和堆叠太阳能电池应用下的绿色发光能级分裂
IF 4.7 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-13 DOI: 10.1016/j.jphotochem.2026.117048
Ru-Ping Wang , Xiao-Song Zhang , Xiu-Rong Yuan , Xiao-Kai Gong , Hai-Bo Ma , Bao-Zeng Zhou , Li-Na Kong , Jian-Ping Xu , Lan Li
Due to their high carrier mobility, tunable bandgaps, narrow emission linewidths and solution-processability, metal halide perovskites demonstrate exceptional promise in photovoltaics, optoelectronics and photodetection. But the toxicity of lead has hindered its practical applications significantly. A series of lead-free perovskites materials have received great attention from researchers, there remains substantial scope for advancing research into the narrowband tunability of such lead-free perovskite materials compared to CsPbBr3. Bromo‑manganese cesium perovskites can achieve red and green luminescence, but there are still unsatisfactory luminescence efficiency, poor stability, limited green light tunability, and the mechanism by which alkali metal ion doping affects the regulation of energy level splitting by the manganese crystal field remains unclear. This study prepares Cs3MnBr5 via thermal injection. A-site doping (partially substituting Cs with Na, K ions) preserves its crystal structure. Doping with Na+ and K+ enhances the luminescence intensity of the material and enables effective spectral modulation, while also providing insights into the underlying mechanism. Specifically, modifications to the lattice structure tune the electronic properties, induce splitting of the Mn2+ energy levels, and increase the splitting energy of the 3d orbitals. The energy required for the electronic transition from the 4T1(G) state to the (Wang et al., 20246)A1(S) energy level increases, leading to the occurrence of a blue shift and achieving the spectral tunability within the green light range. Silicon solar cells exhibit enhanced power conversion efficiency (PCE) when undoped Cs3MnBr5 and Na/K-doped Cs3MnBr5 are employed as the down-conversion layer. Thus, this material exhibits broad application prospects in lighting, display technology, optoelectronic devices, biomedical.
由于其高载流子迁移率、可调带隙、窄发射线宽和溶液可加工性,金属卤化物钙钛矿在光伏、光电子和光探测方面表现出非凡的前景。但铅的毒性极大地阻碍了其实际应用。一系列无铅钙钛矿材料受到了研究人员的高度关注,与CsPbBr3相比,这些无铅钙钛矿材料的窄带可调性研究仍有很大的推进空间。溴锰铯钙钛矿可以实现红光和绿光发光,但发光效率不理想,稳定性差,绿光可调性有限,碱金属离子掺杂影响锰晶体场对能级分裂调节的机理尚不清楚。本研究采用热注入法制备Cs3MnBr5。a位掺杂(用Na、K离子部分取代Cs)保留了其晶体结构。Na+和K+的掺杂增强了材料的发光强度,实现了有效的光谱调制,同时也提供了对潜在机制的见解。具体来说,晶格结构的改变调整了Mn2+的电子性质,诱导了Mn2+能级的分裂,并增加了三维轨道的分裂能。电子从4T1(G)态跃迁到(Wang et al., 20246)A1(S)能级所需的能量增加,导致蓝移的发生,实现了光谱在绿光范围内的可调性。采用未掺杂的Cs3MnBr5和Na/ k掺杂的Cs3MnBr5作为下转换层时,硅太阳能电池的功率转换效率(PCE)有所提高。因此,该材料在照明、显示技术、光电器件、生物医学等方面具有广阔的应用前景。
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引用次数: 0
Simulation-guided modulation of organic photothermal conversion based on pH-responsive molecular photorotation for photothermal antibacterial applications 基于ph响应分子光旋转的有机光热转化模拟引导调制光热抗菌应用
IF 4.7 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-13 DOI: 10.1016/j.jphotochem.2026.117049
Huajing Zhang, Yi Li, Weiqi Yu, Tong Zheng, Xiujun Han, Conghui Si, Mingzhi Wei, Shunwei Chen
Stimulus-responsive photothermal materials hold great promise for precise and targeted biomedical applications, including tumor photothermal therapy and photothermal antibacterial treatment. In this work, a pH-sensitive small organic photothermal molecule (HNID) that features a CN-bridged donor-acceptor (D-A) structure stabilized by an intramolecular OH···O hydrogen bond was designed by adopting a photorotation-driven non-radiative decay strategy, guided by both static theoretical calculations and excited-state dynamics simulations. This strategy is based on pH-controlled access to a non-radiative decay channel via a conical intersection (CI) resulting from photoinduced CN rotation. Validated by experiments, HNID exhibits pH-sensitive photothermal conversion, achieving a remarkable two-fold enhancement in photothermal conversion efficiency (PTCE) from 16.8% (pH 7) to 50.8% (pH 10.5). Furthermore, HNID demonstrates significantly improved photothermal antibacterial performance under alkaline conditions compared to that in the neutral environment. This study offers molecular-level insights into the rational design of pH-responsive photothermal materials for relevant applications.
刺激响应光热材料在精确和有针对性的生物医学应用中具有很大的前景,包括肿瘤光热治疗和光热抗菌治疗。在这项工作中,采用光旋驱动的非辐射衰变策略,在静态理论计算和激发态动力学模拟的指导下,设计了一个ph敏感的有机光热小分子(HNID),该分子具有cn桥接的供体-受体(D-A)结构,由分子内OH···O氢键稳定。该策略基于ph控制,通过光诱导CN旋转产生的锥形交叉(CI)进入非辐射衰减通道。实验证实,HNID具有pH敏感性光热转换,光热转换效率(PTCE)从16.8% (pH 7)提高到50.8% (pH 10.5),显著提高了两倍。此外,与中性环境相比,HNID在碱性条件下的光热抗菌性能显著提高。该研究为ph响应光热材料的合理设计提供了分子水平的见解。
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引用次数: 0
Novel spectrofluorimetric method to determine warfarin sodium in serum, urine, and tablets using Eu3+-doxycycline optical sensor 用Eu3+-强力霉素光学传感器测定血清、尿液和片剂中华法林钠的新型荧光光谱法
IF 4.7 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-13 DOI: 10.1016/j.jphotochem.2026.117034
Amal A. Mohamed
A sensitive, simple, and selective spectrofluorimetric approach was created and validated to detect Warfarin sodium (WF) in serum, pharmaceutical, and urine samples. The method was based on utilizing a change in luminescence intensity of europium doxycycline (Eu3+-DOX) as an optical sensor. The WF can effectively quench the luminescence intensity of Eu3+-DOX in acetonitrile at λex = 395 nm and in a buffered medium at pH 8.0. This quenching, particularly the distinctive peak at λem = 616.5 nm, is used to quantify WF in pharmaceutical tablets and biological samples. Under the optimum conditions, the concentration of WF can be determined within a dynamic range of (6.0 × 10−7-1.9 × 10−5) mol L−1 and a high correlation coefficient (0.999). The limit of detection (LOD) is 1.86 × 10−7 mol L−1 and the limit of quantification (LOQ) is 5.6 × 10−7 mol L−1, respectively. Spectroscopic characterization, including emission and absorption spectra, validated the acquired sensor. Several properties validate the enhanced method, including linearity, precision, robustness, and accuracy.
建立并验证了一种灵敏、简单、选择性荧光光谱法检测血清、药物和尿液样品中的华法林钠(WF)的方法。该方法基于利用多西环素铕(Eu3+-DOX)发光强度的变化作为光学传感器。WF能有效猝灭Eu3+-DOX在λex = 395 nm的乙腈中和pH为8.0的缓冲介质中的发光强度。这种猝灭,特别是λem = 616.5 nm处的独特峰,可用于定量药物片剂和生物样品中的WF。在最优条件下,WF的测定浓度在(6.0 × 10−7 ~ 1.9 × 10−5)mol L−1的动态范围内,相关系数为0.999。检测限(LOD)为1.86 × 10−7 mol L−1,定量限(LOQ)为5.6 × 10−7 mol L−1。光谱表征,包括发射和吸收光谱,验证了所获得的传感器。几个特性验证了改进的方法,包括线性,精度,鲁棒性和准确性。
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引用次数: 0
Combined photothermal effect with built-in electric field enhances tetracycline degradation: Mechanism and ecological risks 光热效应与内置电场联合增强四环素降解机制及生态风险
IF 4.7 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-13 DOI: 10.1016/j.jphotochem.2026.117050
Rongyu Zhang , Yibo Xin , Qiaozhi Yan , Xuemin Yin , Xueying Wang , Changyu Lu
Photothermal-assisted photocatalysis and interfacial bonding have been validated as efficient strategies to modulate charge carrier transfer dynamics within heterojunctions, consequently facilitating the enhancement of photocatalytic performance of the catalysts. In this study, we produced a 0D/3D ZnFe2O4/ZnIn2S4 heterojunction exhibiting a “superposition-enhanced” photothermal effect. This structure effectively degrades tetracycline (TC) through photothermal-assisted photocatalysis. Density functional theory (DFT) calculations and temperature-controlled experimental analyses demonstrated that the photothermal effects, S-Zn-O bonding, facilitated the interfacial transport of photo-generated carriers. When exposed to visible light, the photothermally assisted photocatalytic system constructed using ZFO/ZIS achieved a degradation rate of 81.18% of TC in 110 min. The TOC removal rates of 3% ZFO/ZIS was 56.31%. Additionally, the ecological risk associated with TC degradation products was assessed using the Ecological Structure Activity Relationship (ECOSAR) model, and the results were further confirmed through a bean sprout cultivation experiment, which demonstrated that the TC degradation products posed a low environmental risk. Additionally, the heterojunction exhibited a low metal ion leaching rate. This research introduced an innovative and practical approach for designing and developing photocatalysts aimed at photothermal-assisted photocatalysis and the breakdown of organic pollutants.
光热辅助光催化和界面键合已被证实是调节异质结内载流子转移动力学的有效策略,从而促进催化剂光催化性能的增强。在这项研究中,我们制作了一个0D/3D ZnFe2O4/ZnIn2S4异质结,表现出“叠加增强”的光热效应。该结构通过光热辅助光催化有效降解四环素(TC)。密度泛函理论(DFT)计算和温控实验分析表明,S-Zn-O键的光热效应促进了光生成载流子的界面输运。在可见光下,ZFO/ZIS构建的光热辅助光催化体系在110 min内对TC的降解率达到81.18%。3% ZFO/ZIS的TOC去除率为56.31%。利用生态结构活性关系(ECOSAR)模型评价了TC降解产物的生态风险,并通过豆芽栽培试验进一步证实了TC降解产物具有较低的环境风险。此外,异质结表现出较低的金属离子浸出率。本研究为设计和开发光热辅助光催化和分解有机污染物的光催化剂提供了一种创新和实用的方法。
{"title":"Combined photothermal effect with built-in electric field enhances tetracycline degradation: Mechanism and ecological risks","authors":"Rongyu Zhang ,&nbsp;Yibo Xin ,&nbsp;Qiaozhi Yan ,&nbsp;Xuemin Yin ,&nbsp;Xueying Wang ,&nbsp;Changyu Lu","doi":"10.1016/j.jphotochem.2026.117050","DOIUrl":"10.1016/j.jphotochem.2026.117050","url":null,"abstract":"<div><div>Photothermal-assisted photocatalysis and interfacial bonding have been validated as efficient strategies to modulate charge carrier transfer dynamics within heterojunctions, consequently facilitating the enhancement of photocatalytic performance of the catalysts. In this study, we produced a 0D/3D ZnFe<sub>2</sub>O<sub>4</sub>/ZnIn<sub>2</sub>S<sub>4</sub> heterojunction exhibiting a “superposition-enhanced” photothermal effect. This structure effectively degrades tetracycline (TC) through photothermal-assisted photocatalysis. Density functional theory (DFT) calculations and temperature-controlled experimental analyses demonstrated that the photothermal effects, S-Zn-O bonding, facilitated the interfacial transport of photo-generated carriers. When exposed to visible light, the photothermally assisted photocatalytic system constructed using ZFO/ZIS achieved a degradation rate of 81.18% of TC in 110 min. The TOC removal rates of 3% ZFO/ZIS was 56.31%. Additionally, the ecological risk associated with TC degradation products was assessed using the Ecological Structure Activity Relationship (ECOSAR) model, and the results were further confirmed through a bean sprout cultivation experiment, which demonstrated that the TC degradation products posed a low environmental risk. Additionally, the heterojunction exhibited a low metal ion leaching rate. This research introduced an innovative and practical approach for designing and developing photocatalysts aimed at photothermal-assisted photocatalysis and the breakdown of organic pollutants.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"475 ","pages":"Article 117050"},"PeriodicalIF":4.7,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035515","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
Bis-(phenylselenide) based turn-on fluorescent probe for rapid, perceptible and selective detection of superoxide anion in human colon cancer cells 基于双(苯硒化物)的开启荧光探针用于快速、可感知和选择性检测人结肠癌细胞中的超氧阴离子
IF 4.7 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-11 DOI: 10.1016/j.jphotochem.2026.117033
Snehal S. Salunkhe , Divyesh S. Shelar , Pratik P. Dhavan , Ray J. Butcher , Sudesh T. Manjare
Superoxide anion is a type of reactive oxygen species (ROS) obtained by one-electron reduction of an oxygen molecule. It temporarily resides in the mitochondria before spreading throughout the cell and in human it regulates many signal transduction processes. Since increased levels of superoxide can cause permanent destruction to human bodies, the discovery of an effective method is significantly important for its selective and sensitive detection. This work explores a new “turn-on” fluorescence probe, Se-BODIPY-Se, which was synthesized and characterized by 1H, 13C, 77Se, 11B, and 19F NMR spectroscopy, LCMS, and single-crystal XRD. The strategy of the probe was based on the photo-induced electron transfer (PET) mechanism between phenylselenide as an electron donor and BODIPY as an electron acceptor moiety. The fluorescence could be restored as a result of the termination of the PET process by the oxidation of selenium when treated with superoxide. The probe presented a high selectivity toward superoxide rather than other ROS, metal ions, biothiols, and amino acids, with a 63-fold marked fluorescence enhancement at 518 nm. The probe operates at physiological pH (7.4), achieving a detection limit down to 31 nM. Furthermore, it selectively detects superoxide anion in the HCT-116 cell line with a 7.4-fold increase in fluorescence intensity, indicating its potential application in live cancer cell imaging.
超氧阴离子是氧分子单电子还原得到的一种活性氧(ROS)。在扩散到整个细胞之前,它暂时驻留在线粒体中,并在人类中调节许多信号转导过程。由于超氧化物水平的增加会对人体造成永久性的破坏,因此发现一种有效的方法对其选择性和灵敏度的检测具有重要意义。本文探索了一种新的“开启”荧光探针Se-BODIPY-Se,并通过1H, 13C, 77Se, 11B和19F NMR波谱,LCMS和单晶XRD进行了合成和表征。探针的策略是基于苯硒化物作为电子供体和BODIPY作为电子受体片段之间的光诱导电子转移(PET)机制。用超氧化物处理后,由于PET过程的终止,硒的氧化作用可以恢复荧光。该探针对超氧化物、金属离子、生物硫醇和氨基酸具有较高的选择性,在518 nm处荧光增强63倍。该探针在生理pH值(7.4)下工作,检测限低至31 nM。此外,在HCT-116细胞系中选择性检测超氧阴离子,荧光强度增加7.4倍,表明其在活癌细胞成像中的潜在应用。
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Journal of Photochemistry and Photobiology A-chemistry
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