Journal of Photochemistry and Photobiology A-chemistry最新文献_第5页

BiOI/bi-0.002@GDY: A Photocatalyst harnessing synergistic Plasmonic and oxygen-vacancy effects for efficient antibiotic degradation BiOI/bi-0.002@GDY：一种利用协同等离子体和氧空位效应的光催化剂，用于有效降解抗生素

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2026-01-26 DOI: 10.1016/j.jphotochem.2026.117069

Jinglei Yu , Zhao Liu , Mengyuan Yu , Ziqi Pei , Yong Jin , Guixiang Teng , Jie He , Chun Zhang

In response to the environmental risks posed by antibiotic contamination, especially tetracycline (TC), a novel BiOI/Bi-0.002@GDY heterojunction was successfully constructed via a combined hydrothermal and in-situ growth strategy. In this system, BiOI serves as the primary light-absorbing component, metallic bismuth nanoparticles enhance visible-light harvesting through surface plasmon resonance (SPR), while graphdiyne (GDY) acts as an electron transfer medium and structural modulator. Under simulated sunlight, the optimized composite exhibits a photocatalytic degradation rate for TC that is 4 times and 2 times higher than those of pure BiOI and BiOI/Bi-0.002 samples, respectively, along with excellent cycling stability. The remarkable performance enhancement is attributed to the synergistic effect between the heterojunction and the GDY-induced oxygen vacancies (Ov), which effectively facilitates the separation and suppresses the recombination of photogenerated electron-hole pairs, as confirmed by EPR and XPS analyses. Meanwhile, the increased specific surface area (33.04 m²g⁻¹) provides more active sites. The degradation pathway of TC and the evolution of ecological risks were elucidated through response surface methodology-optimized conditions, intermediate analysis, and toxicity assessment. Furthermore, photoelectrochemical measurements and density functional theory (DFT) calculations systematically revealed the charge transfer mechanism. This study provides a novel strategy for designing high-performance bismuth-based photocatalysts for antibiotic wastewater treatment.

为了应对抗生素污染，尤其是四环素（四环素）带来的环境风险，通过水热和原位生长相结合的策略，成功构建了新型BiOI/Bi-0.002@GDY异质结。在该系统中，BiOI作为主要的光吸收成分，金属铋纳米粒子通过表面等离子体共振（SPR）增强可见光捕获，而石墨炔（GDY）作为电子传递介质和结构调制器。在模拟阳光下，优化后的复合材料对TC的光催化降解率分别比纯bii和bii /Bi-0.002样品高4倍和2倍，并且具有良好的循环稳定性。EPR和XPS分析证实，这种显著的性能增强是由于异质结与gdy诱导的氧空位（Ov）之间的协同作用，有效地促进了光生电子-空穴对的分离并抑制了它们的重组。同时，增加的比表面积（33.04 m2−1）提供了更多的活性位点。通过响应面法优化条件、中间分析和毒性评价，阐明了TC的降解途径和生态风险演化。此外，光电化学测量和密度泛函理论（DFT）计算系统地揭示了电荷转移机理。本研究为设计高性能铋基光催化剂处理抗生素废水提供了一种新思路。

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引用次数: 0

Serendipitous discovery of nitrogen bridgehead fused pyridines: photophysical properties and live-cell imaging potential 偶然发现氮桥头堡融合吡啶：光物理性质和活细胞成像潜力

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2026-01-26 DOI: 10.1016/j.jphotochem.2026.117068

Hana Kokot , Aljoša Bolje , Jakob Kljun , Andraž Bevk , Natalija Trunkelj , Lucija Peterlin Mašič , Janez Mravljak , Stane Pajk

A novel synthetic route to fluorescent nitrogen bridgehead fused pyridines (NBFPs) was discovered serendipitously during attempts to synthesize a thiazole derivative via a Hantzsch-type thiazole reaction from 2-cyanoethanethioamide and chloroacetone. A mechanism was proposed to rationalize the formation of NBFPs, which guided the subsequent expansion of the reaction scope and optimization of reaction conditions. The scope of the reaction was extended to include arylacetonitriles and esters of 2-(heteroaryl)acetic acids bearing an ortho-positioned pyridine-type nitrogen as a starting material. The structures of selected compounds were confirmed by single-crystal X-ray diffraction. All synthesized NBFPs exhibited pH-sensitive fluorescence and Stokes shifts exceeding 100 nm in several cases. Two compounds, methylthiazole derivative 1 and quinoline derivative 8, displayed pH-dependent emission suitable for lysosomal labelling. However, live-cell microscopy revealed limited colocalization with lysosomal probe Lysotracker Red, suggesting that these probes may localize to other acidic environments as well. Both compounds showed pronounced spectral responsiveness and fluorescence lifetime variations, indicating potential for use as environment-sensitive intracellular sensors. The methyl thiazole derivative 1 exhibited particularly favourable properties, including high photostability, low background fluorescence, minimal cytotoxicity and polarity sensitivity. These findings position NBFPs as a promising class of fluorophores for live-cell imaging and intracellular sensing applications, and warrant further investigation into their structure–function relationships and environmental responsiveness.

摘要在以2-氰乙酰胺和氯丙酮为原料，采用hantzsch型噻唑反应合成噻唑衍生物的过程中，偶然发现了一条合成荧光氮桥头堡融合吡啶（nfbp）的新途径。提出了合理形成NBFPs的机理，指导了后续反应范围的扩大和反应条件的优化。该反应的范围扩大到包括芳基乙腈和以邻位吡啶型氮为起始原料的2-（杂芳基）乙酸酯。所选化合物的结构用单晶x射线衍射证实。所有合成的nbps都表现出ph敏感的荧光和在一些情况下超过100 nm的斯托克斯位移。两个化合物甲基噻唑衍生物1和喹啉衍生物8表现出适合溶酶体标记的ph依赖性发射。然而，活细胞显微镜显示与溶酶体探针Lysotracker Red的共定位有限，这表明这些探针也可能定位于其他酸性环境。这两种化合物都表现出明显的光谱响应性和荧光寿命变化，表明有可能用作环境敏感的细胞内传感器。甲基噻唑衍生物1表现出特别有利的性质，包括高光稳定性、低本底荧光、最小的细胞毒性和极性敏感性。这些发现将nbfp定位为一类有前途的荧光团，用于活细胞成像和细胞内传感应用，并值得进一步研究其结构-功能关系和环境响应性。

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引用次数: 0

Crystal structure, vibrational, and electronic characterization and topological analysis of Glycine-Glycinium Pyromellitate (−) Dihydrate 甘氨酸-甘氨酸吡啶酸（−）二水合物的晶体结构、振动、电子表征和拓扑分析

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2026-01-24 DOI: 10.1016/j.jphotochem.2026.117054

B. Shantha Lakshmi , V. Sabari , E. Mohanapriya , Kalpana Sukumar , J. Janczak , V. Ragavendran , N. Kanagathara

The direct reaction of glycine with pyromellitic acid in aqueous solution yields hydrated crystals of {[(NH₃CH₂COOH_0.5)₂]⁺[C₆H₂(COOH)₃COO]–·2H₂O} (DGLYPDH). Single-crystal X-ray diffraction confirms a triclinic crystal system (space group P

\bar{1}

) with a robust three-dimensional hydrogen-bonded network supported by O–H···O and N–H···O interactions and partial proton disorder (0.5 occupancy). Hirshfeld surface and 2D fingerprint analyses of DGLYPDH reveal that O–H···O hydrogen bonds dominate the crystal packing (≈60–65% contribution), supported by H···H dispersive and C···O contacts. Molecular Electrostatic Potential (MESP) analysis provides detailed into the charge distribution within a DGLYPDH molecule, highlighting regions to electrophilic and nucleophilic attacks, and aiding in understanding reactivity and intermolecular interactions. Vibrational spectroscopy, corroborated by DFT (RB3LYP/6-311G (d, p)) calculations, verifies the presence of NH₃⁺, COO⁻, CO, CH₂, and H₂O groups and shows excellent agreement between experimental and theoretical frequencies. Electronic analysis reveals a HOMO–LUMO energy gap of 3.978 eV, moderate electronic stability, and significant electron delocalization. Natural Bond Orbital calculations indicate strong hyper conjugative interactions, while the first-order hyperpolarizability is 96.35 times greater than that of urea, demonstrating remarkable nonlinear optical (NLO) potential. Topological analysis (ELF and LOL) further highlights the localized electron density, covalent bonding within the pyromellitate ring, and an electrostatic landscape conducive to supramolecular assembly. Additionally, molecular docking explores potential binding interaction and possible biological activities of the taken compound. These combined structural, vibrational, electronic, and biological results establish DGLYPDH as a stable hydrogen-bonded crystal with promising applications in NLO and optoelectronic materials.

甘氨酸与邻苯二甲酸在水溶液中直接反应生成{[(NH3CH2COOH0.5)2]+[C6H2(COOH)3COO] -·2H2O} （DGLYPDH）水合晶体。单晶x射线衍射证实了一个三斜晶体体系（空间群P1¯），具有由O - h··O和N-H··O相互作用和部分质子无序（占比0.5）支持的坚固的三维氢键网络。DGLYPDH的Hirshfeld表面和二维指纹图谱分析表明，O - H··O氢键主导了晶体填充（贡献约60-65%），并由H··H色散和C··O接触支撑。分子静电势（MESP）分析提供了DGLYPDH分子内电荷分布的详细信息，突出了亲电和亲核攻击的区域，并有助于理解反应性和分子间相互作用。DFT （RB3LYP/6-311G (d, p)）计算证实了NH3+、COO−、CO、CH2和H2O基团的存在，并且实验频率与理论频率非常吻合。电子分析表明，HOMO-LUMO的能隙为3.978 eV，电子稳定性中等，电子离域明显。天然键轨道计算表明其具有很强的超共轭相互作用，一阶超极化率是尿素的96.35倍，具有显著的非线性光学（NLO）潜力。拓扑分析（ELF和LOL）进一步强调了局域电子密度，焦镍酸盐环内的共价键，以及有利于超分子组装的静电景观。此外，分子对接探讨了所取化合物的潜在结合相互作用和可能的生物活性。这些结合了结构、振动、电子和生物学的结果表明，DGLYPDH是一种稳定的氢键晶体，在NLO和光电子材料中具有广阔的应用前景。

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引用次数: 0

A dual-mode optical thermometric strategy based on a Dy3+-activated tellurate double perovskite phosphor 基于Dy3+活化碲酸盐双钙钛矿磷光体的双模光学测温策略

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2026-01-23 DOI: 10.1016/j.jphotochem.2026.117057

Xiangyan Yun , Haizhe Zhong , Xueping Zang , Mingjun Chen , Qingqing Cheng , Wei Tao , Heng Li , Zaifa Yang

Developing down-conversion phosphors with stable luminescence and high temperature sensitivity is essential for non-contact optical thermometry. Herein, a Dy³⁺-activated SrGdLiTeO₆ (SGLT:Dy³⁺) phosphor was synthesized via a conventional solid-state reaction. Rietveld refinement confirms the phase-pure monoclinic double perovskite structure, revealing that Dy³⁺ ions preferentially occupy the Gd³⁺ sites. Upon near-UV excitation, the phosphor exhibits distinct blue (⁴F_9/2 → ⁶H_15/2) and yellow (⁴F_9/2 → ⁶H_13/2) emissions with tunable intensity and stable emission color as a function of dopant concentration. Notably, the anomalous enhancement of the 458 nm band with temperature enables the construction of two fluorescence intensity ratio (FIR) modes, yielding maximum relative sensitivities of 2.75% K⁻¹ and 2.87% K⁻¹, respectively. Moreover, the phosphor maintains over 70% of its room-temperature emission intensity at 500 K, indicating robust thermal stability. This work offers a practical approach for developing Dy³⁺-activated phosphors with reliable optical thermometry performance and potential applicability in non-contact temperature sensing devices.

研制发光稳定、温度灵敏度高的下转换荧光粉是实现非接触式光学测温的关键。本文通过常规固相反应合成了Dy3+活化的SrGdLiTeO6 （SGLT:Dy3+）荧光粉。Rietveld细化证实了相纯单斜双钙钛矿结构，揭示了Dy3+离子优先占据Gd3+位点。在近紫外激发下，荧光体呈现出明显的蓝色（4F9/2→6H15/2）和黄色（4F9/2→6H13/2）发光，发光强度可调，发光颜色随掺杂剂浓度的变化而稳定。值得注意的是，458nm波段随温度的异常增强可以构建两种荧光强度比（FIR）模式，最大相对灵敏度分别为2.75% K−1和2.87% K−1。此外，在500 K时，荧光粉保持了超过70%的室温发射强度，表明了强大的热稳定性。这项工作为开发具有可靠的光学测温性能和潜在的非接触式温度传感器件的Dy3+激活荧光粉提供了一种实用的方法。

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引用次数: 0

Hydrogen bond sensitive molecular switch for dual emission from 5-(5-(4-methoxyphenyl)thiophen-2-yl)picolinamidine: An approach to white light emitters (III) 5-（5-（4-甲氧基苯基）噻吩-2-基）吡啶双发射的氢键敏感分子开关：白光发射体的研究（III）

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2026-01-23 DOI: 10.1016/j.jphotochem.2026.117058

Robeir Youssef , Maha M. Khaled , Mohamed A. Ismail , Hesham S. Abdel-Samad , Ayman A. Abdel-Shafi

The photophysical properties of a novel flexible fluorophore, 5-(5-(4-methoxyphenyl)thiophen-2-yl)picolinamidine, were investigated using steady-state and time-resolved fluorescence spectroscopy combined with multiparametric solvent analysis. TD-DFT calculations reveal a non-planar ground-state geometry that undergoes significant planarization in the excited state, facilitating charge transfer process. The compound exhibits intriguing excitation dependent dual emission, characterized by a high-energy band (local excited state, LE) and a strongly red shifted band indicative of an intramolecular charge-transfer (ICT) process. Time resolved decay analysis revealed universally bi-exponential kinetics, with the short lifetime component (τ₁, 0.2–1.7 ns) highly sensitive to solvent viscosity and hydrogen bonding, and the longer component (τ₂, 1.7–4.5 ns) representing the lifetime of a relaxed ICT state. A critical finding is the persistence of bi-exponential decay at long excitation wavelengths exclusively in protic solvents, attributed to pronounced hydrogen bonding excited state. Catalán's and Laurence's solvent parameter analyses quantitatively deconvoluted these effects, revealing that the fluorescence quantum yield is dominated by solvent rigidity (SP/DI >80%), while the ICT state energy is stabilized by dipolarity and hydrogen-bond acidity. Notably, Laurence's model demonstrated that the ICT state lifetime is governed by specific hydrogen-bond donation to the acceptor moiety (α = 66%). The ability to tune the relative intensity of the dual emission bands through solvent polarity and excitation wavelength demonstrates the potential of this single-component system for white-light-emitting applications. This study provides a profound understanding of how solvent interactions act as a molecular switch to gate excited-state pathways in flexible D-π-A architectures.

采用稳态和时间分辨荧光光谱结合多参数溶剂分析研究了一种新型柔性荧光团5-（5-（4-甲氧基苯基）噻吩-2-基）吡啶脒的光物理性质。TD-DFT计算揭示了一个非平面的基态几何，在激发态中经历了显著的平面化，促进了电荷转移过程。该化合物表现出有趣的激发依赖双发射，其特征是高能量带（局部激发态，LE）和强红移带，表明分子内电荷转移（ICT）过程。时间分辨衰变分析显示了普遍的双指数动力学，其中短寿命成分（τ₂，0.2-1.7 ns）对溶剂粘度和氢键高度敏感，而长寿命成分（τ₂，1.7-4.5 ns）代表弛豫ICT状态的寿命。一个关键的发现是双指数衰减的持久性在长激发波长的质子溶剂，归因于明显的氢键激发态。Catalán和Laurence的溶剂参数定量分析了这些影响，揭示了荧光量子产率由溶剂刚性（SP/DI >80%）主导，而ICT状态能量由双极性和氢键酸度稳定。值得注意的是，劳伦斯的模型表明，ICT的状态寿命是由特定的氢键捐赠给受体部分（α = 66%）。通过溶剂极性和激发波长调节双发射带相对强度的能力证明了这种单组分系统在白光发射应用中的潜力。本研究提供了一个深刻的理解如何溶剂相互作用作为一个分子开关门激发态途径在柔性D-π-A结构。

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引用次数: 0

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

Journal of Photochemistry and Photobiology A-chemistry

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

Journal of Photochemistry and Photobiology A-chemistry

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

Journal of Photochemistry and Photobiology A-chemistry

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

Journal of Photochemistry and Photobiology A-chemistry

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

Journal of Photochemistry and Photobiology A-chemistry

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