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Front Cover: Design, Synthesis, and Photochemical Properties of Gene-directed Caged RyR Probes for Photopharmacological Studies (ChemPhotoChem 8/2024) 封面:用于光药理学研究的基因定向笼型 RyR 探针的设计、合成和光化学特性(ChemPhotoChem 8/2024)
IF 3 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-08-13 DOI: 10.1002/cptc.202480801
Aika Yokoyama, Hanami Aoki, Mizuki Funayama, Ryo Shinozaki, Hiroto Yoshida, Dr. Akinobu Z. Suzuki, Prof. Dr. Toshiaki Furuta

The Front Cover illustrates the molecular structures of coumarin-caged ryanodine receptor (RyR) agonists and blockers. Photo-irradiation of a (6-bromo-7-hydroxycoumarin-4-yl)methyl (Bhc)-caged agonist released the active form, activated RyRs, and promoted Ca2+ release from the endoplasmic reticulum in mammalian cells. The photoreactivity of the caged RyR probes by 405 nm light was masked by the enzyme substrates, allowing cell-type-selective, enzyme gene-directed delivery of the caged RyR probes. More information can be found in the Research Article by A. Yokoyama, H. Aoki, T. Furuta et al. (DOI 10.1002/cptc.202400140).

封面展示了香豆素笼型雷诺丁受体(RyR)激动剂和阻断剂的分子结构。光照射(6-溴-7-羟基香豆素-4-基)甲基(Bhc)笼状激动剂可释放出活性形式,激活 RyR,并促进哺乳动物细胞内质网释放 Ca2+。酶底物掩盖了笼型 RyR 探针在 405 纳米光下的光活性,从而实现了笼型 RyR 探针的细胞类型选择性酶基因定向传递。更多信息请参阅 A. Yokoyama、H. Aoki、T. Furuta 等人的研究文章(DOI 10.1002/cptc.202400140)。
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引用次数: 0
Asymmetric π‐Extension Design of Long Wavelength Rhodamine Derivatives for Imaging and Phototherapy 用于成像和光疗的长波长罗丹明衍生物的不对称 π 延伸设计
IF 3.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-08-01 DOI: 10.1002/cptc.202400191
Long He, Jing Huang, Xingxing Zhang, Tianbing Ren, Lin Yuan
Rhodamine dyes have been extensively explored for bioimaging and therapeutic applications over the past few decades. However, it remains a challenge to design long‐wavelength and large Stokes shift rhodamine derivatives to meet the requirements of fluorescence imaging and phototherapy in deep living tissues. In this work, a pyridine aromatic unit was inserted into the ACF skeleton to prepare a series of stable rhodamine derivatives, ACFPs, to achieve long emission wavelength (> 650 nm) and large Stokes shift (~ 60 nm) by tuning the conjugated systems and electronic symmetry. More significantly, ACFPs are capable of continuously producing superoxide radical (O2‐•) under long wavelength irradiation. This study presents a novel paradigm for improving the optical properties of rhodamine, which has led to the development of a novel tool for image‐guided phototherapy for cancer treatment.
过去几十年来,罗丹明染料在生物成像和治疗应用方面得到了广泛的探索。然而,如何设计长波长和大斯托克斯位移的罗丹明衍生物,以满足深部活体组织的荧光成像和光疗要求,仍然是一个挑战。在这项工作中,通过调整共轭体系和电子对称性,在 ACF 骨架中插入吡啶芳香单元,制备出一系列稳定的罗丹明衍生物--ACFPs,从而实现长发射波长(> 650 nm)和大斯托克斯位移(~ 60 nm)。更重要的是,ACFPs 能够在长波长照射下持续产生超氧自由基(O2--)。这项研究为改善罗丹明的光学特性提供了一种新的范例,从而开发出一种用于癌症治疗的图像引导光疗的新型工具。
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引用次数: 0
Optimization of the Structural Rigidity of a Deep‐NIR Scaffold for Bioimaging 优化用于生物成像的深近红外支架的结构刚性
IF 3.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-07-31 DOI: 10.1002/cptc.202400156
Xinru Hu, Yan Dong, Yuyang Zhang, Xiaohua Chen, Chuanbao Yuan, Danyang Wang, Xuhong Qian, Xiao Luo, Youjun Yang
Bright deep‐NIR dyes are actively sought after for their potential in fluorescence‐guided surgery and disease theranostics. The major bottleneck lies with the rigidification of the conjugative backbone to suppress non‐radiative deactivation. EC5 is a notable deep‐NIR absorbing/emitting scaffold, which we first reported in 2017. We recently discovered that its diphenyl ether moiety exhibited structural freedom, which was detrimental to its fluorescence brightness. We proposed to enhance the structural rigidity of EC5 via ring‐contraction, i.e., changing the diphenyl ether moiety of EC5E into a biphenyl of EC5B, its low‐frequency normal modes were largely suppressed as predicted by theoretical calculations, and a 55.0% increase of fluorescence brightness in CH2Cl2 was rendered experimentally. The bright EC5B was feasible for high‐contrast in vivo imaging. EC5B has broad potential in practical biomedical applications.
明亮的深近红外染料因其在荧光引导手术和疾病治疗学方面的潜力而备受追捧。主要瓶颈在于共轭骨架的刚性化,以抑制非辐射失活。EC5 是一种显著的深近红外吸收/发射支架,我们于 2017 年首次报道了它。我们最近发现,其二苯醚分子具有结构自由度,这不利于其荧光亮度。我们提出通过缩环来增强EC5的结构刚性,即把EC5E的二苯醚分子变为EC5B的联苯,其低频法向模态在很大程度上被理论计算所预测的那样被抑制,在CH2Cl2中的荧光亮度在实验中呈现出55.0%的增长。明亮的 EC5B 可用于高对比度的体内成像。EC5B 在实际生物医学应用中具有广泛的潜力。
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引用次数: 0
H+/X– Co‐Transport Driven by Azobenzene Containing Aromatic Amides 由含偶氮苯的芳香族酰胺驱动的 H+/X- 协同传输
IF 3.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-07-31 DOI: 10.1002/cptc.202400179
Sameer Ahmad Malik, Nandita Madhavan
Natural ion‐transporters in cellular membranes play a critical role in maintaining cell homeostasis. Synthetic ion‐transporters are attractive model systems for understanding and addressing dysfunction of natural transporters. Herein, a simple amide derived from azobenzene and m‐aminobenzoic acid achieves photoregulated ion transport across lipid membranes. The amide forms pores or channels that selectively co‐transport H+/X– across the lipid membrane. Photoisomerization from the trans to cis form results in a 2‐fold increase in ion‐transport rates due to the higher proton affinity of the cis isomer.
细胞膜上的天然离子转运体在维持细胞平衡方面发挥着关键作用。合成离子转运体是了解和解决天然转运体功能障碍的极具吸引力的模型系统。在这里,一种由偶氮苯和间氨基苯甲酸衍生的简单酰胺实现了脂膜上的光调节离子转运。这种酰胺能形成孔隙或通道,选择性地共同传输 H+/X- 跨脂膜。由于顺式异构体的质子亲和力更高,因此从反式到顺式的光异构化会使离子传输速率提高 2 倍。
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引用次数: 0
Classification and summary of photocatalytic chemical reactions driven by triplet‐triplet annihilation upconversion 三重-三重湮灭上转换驱动的光催化化学反应的分类和总结
IF 3.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-07-27 DOI: 10.1002/cptc.202400184
Wen Yao, Xiaojuan Song, Lin Xue, Shanshan Liu, Linglong Tang, Heyuan Liu, Yanli Chen, Xiyou Li
Triplet‐triplet annihilation upconversion (TTA‐UC) technology could convert low‐energy light into high‐energy light, and it is a very promising one of the upconversion technologies due to its non‐coherent excitation light, low required excitation optical power density and sensitizer/annihilator flexible adjustability. The application of TTA‐UC into photocatalysis could not only broaden the range of solar energy spectrum utilization, but also bring mild reaction conditions and higher product yields via avoiding the side reaction. However, the detailed catalytic mechanism of TTA‐UC is unclear. Therefore, in this review, we summarized and classified TTA‐UC photocatalytic chemical reactions in terms of mechanism.
三重-三重湮灭上转换(TTA-UC)技术可将低能光转换为高能光,具有非相干激发光、所需激发光功率密度低、敏化剂/湮灭剂可灵活调节等特点,是一种非常有前景的上转换技术。将 TTA-UC 应用于光催化,不仅能拓宽太阳能光谱的利用范围,还能避免副反应,带来温和的反应条件和更高的产物产率。然而,TTA-UC 的详细催化机理尚不清楚。因此,在本综述中,我们从机理方面对 TTA-UC 光催化化学反应进行了总结和分类。
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引用次数: 0
Eco‐friendly Visible Wavelength PhotodetectorsBasedon Colloidal Molybdenum Trioxide Nanobelt Arrays 基于胶体三氧化钼纳米带阵列的环保型可见光波长光电探测器
IF 3.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-07-26 DOI: 10.1002/cptc.202400038
D. S. Ivan Jebakumar, Vallabha Rao Rikka
In an era marked by growing emphasis on sustainability and innovation, the quest for eco‐friendly energy conversion devices capable of harnessing visible light has gained paramount importance. In response to this critical demand, we demonstrate visible light‐responsive photoswitching from molybdenum trioxide nanobelt arrays in the photoconductive device fabricated using solution‐processing technique. We exploit the visible light‐driven modulation of conductivity in the reversibly switchable photochromic state of MoO3 to fabricate a photochromism‐assisted photoconductive photodetector with fast response (< 0.1 s), significant on/off ratio and excellent responsivity (41 AW‐1) at 5 V. The light harvesting strategy presented herein holds the potential for efficient energy generation by harnessing visible light, even under low‐light conditions.
在这个日益强调可持续发展和创新的时代,寻求能够利用可见光的生态友好型能源转换设备变得至关重要。为了满足这一关键需求,我们在利用溶液处理技术制造的光电导器件中展示了三氧化钼纳米带阵列的可见光响应光开关。我们利用可见光驱动的 MoO3 可逆切换光致变色态的电导率调制,制造出一种光致变色辅助光电导光电探测器,在 5 V 电压下具有快速响应(0.1 秒)、显著的开/关比和出色的响应率(41 AW-1)。本文介绍的光收集策略有望通过利用可见光实现高效能源生产,即使在弱光条件下也是如此。
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引用次数: 0
A Photoinduced Annulation Strategy Towards a Novel Polycyclic Heteroaromatic Chromophore: Scope, Mechanism, Properties and Applications. 实现新型多环杂芳香族发色团的光诱导环化策略:范围、机理、特性和应用。
IF 3.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-07-25 DOI: 10.1002/cptc.202400199
Marine Labro, Audrey Pollien, Maëlle Mosser, Delphine Pitrat, Jean-Christophe Mulatier, Mathilde Seinfeld, Tangui Le Bahers, Bruno Baguenard, Stéphan Guy, Cyrille Monnereau, Laure Guy
This article reports a detailed mechanistic and kinetic study of an unusual photoreaction leading to the (diazonia)tetrabenzonaphthacene skeleton. The photo‐triggered double intramolecular nucleophilic aromatic substitution (SNAr∗) has been investigated by varying the leaving groups. Photoreaction quantum yields have been determined and mechanistic insights have been supported by theoretical calculations using DFT and TD‐DFT methods. Additionally, we show that this light‐triggered formed diazonia constitutes a potent photosentitizer with a singlet oxygen generation quantum yield of 55 %, both in organic solvents and in water, which is an extremely relevant value in view of PDT applications or use as an oxidation photocatalyst in aqueous media. Once again, the experimental observations were supported by TD‐DFT calculations showing a large density of triplet states below the S1 excited state along with large spin‐orbit couplings. The reaction is not restricted to solutions but can also occur in solid PDMS matrices thus allowing for photochemical encoding of information that will progressively vanish upon prolonged UV‐exposure.
本文报告了对产生 (重氮) 四并四苯骨架的不寻常光反应的详细机理和动力学研究。通过改变离去基团,研究了光触发的双分子内亲核芳香取代反应(SNAr∗)。利用 DFT 和 TD-DFT 方法进行的理论计算确定了光反应量子产率,并支持了机理见解。此外,我们还表明,这种由光触发形成的重氮鎓是一种强效光引发剂,在有机溶剂和水中的单线态氧生成量子产率均为 55%,这一数值与光引发脱色疗法的应用或用作水介质中的氧化光催化剂极为相关。TD-DFT 计算再次支持了实验观察结果,该计算显示 S1 激发态以下的三重态密度很大,同时自旋轨道耦合也很大。这种反应并不局限于溶液,也可以发生在固体 PDMS 基质中,从而允许对信息进行光化学编码,这些信息将在长时间紫外线照射后逐渐消失。
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引用次数: 0
Excimer‐Induced Efficient Luminescence by Discrete Intermolecular π–π Stacking of Naphthalimide‐Based Dimer 萘二甲酰亚胺基二聚体分子间离散的 π-π 堆积诱导的准分子高效发光
IF 3.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-07-24 DOI: 10.1002/cptc.202400097
Shiyin Wang, Daojie Yang, Haichao Liu, Shi-Tong Zhang, Bing Yang
π–π stacking interactions are generally thought to reduce the luminescence of materials. Here, a systematic investigation is conducted using a π–π stacking dimer with varying steric hindrance substituents as a model to illustrate how π–π stacking structure affects the luminescence efficiency of materials. Four naphthalimide (NI) derivative molecules were designed and synthesized by incorporating sterically hindered unilateral groups to achieve NIPH, NIP1C, NIP2C, and NIP3C. It was figured out that side group modification did affect their crystal packing structures and luminescent properties. On the one hand, the excimer state formed by strongly interacted π−π NI‐based dimer (NIPH and NIP3C) enhances luminescence efficiency compared to the monomer state based on weakly interacted π−π NI‐based dimers (NIP1C and NIP2C). On the other hand, the discrete stacking of NI‐based dimers (NIP3C) further promotes luminescence efficiency compared to the nondiscrete stacking of NI‐based dimers (NIPH). Among these four compounds, NIP3C exhibits discrete stacking of π−π NI‐based dimer due to the large steric hindrance generated by propyl benzene, resulting in the highest photoluminescence quantum efficiency of the NIP3C crystal. This work will provide further insight into the underlying mechanisms behind the high luminescence efficiency induced by π–π dimer stacking.
π-π堆积相互作用通常被认为会降低材料的发光性能。在此,我们以具有不同立体阻碍取代基的π-π堆积二聚体为模型进行了系统研究,以说明π-π堆积结构如何影响材料的发光效率。通过加入立体受阻的单侧基团,设计并合成了四种萘二甲酰亚胺(NI)衍生物分子,实现了 NIPH、NIP1C、NIP2C 和 NIP3C。研究发现,侧基修饰确实会影响它们的晶体堆积结构和发光特性。一方面,与基于弱相互作用π-π NI 的二聚体(NIP1C 和 NIP2C)的单体状态相比,基于强相互作用π-π NI 的二聚体(NIPH 和 NIP3C)形成的准分子状态提高了发光效率。另一方面,与非离散堆积的 NI 基二聚体(NIPH)相比,离散堆积的 NI 基二聚体(NIP3C)可进一步提高发光效率。在这四种化合物中,NIP3C 因丙基苯产生的巨大立体阻碍而表现出π-π NI 基二聚体的离散堆积,从而使 NIP3C 晶体的光量子效率最高。这项工作将使人们进一步了解π-π二聚体堆积诱导高发光效率背后的潜在机制。
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引用次数: 0
Synthesis of Ternary Photoactive Heterojunction B/CN@rGO for Visible Light Driven Selective Photooxidation of Benzyl Alcohol 合成三元光活性异质结 B/CN@rGO,用于可见光驱动的苯甲醇选择性光氧化反应
IF 3.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-07-12 DOI: 10.1002/cptc.202400171
Komal Trivedi, Bhanupriya Yadav, Rohit Shrivastav, Chetan K. Modi
This work introduces a novel ternary heterostructure as a photocatalyst to selectively produce benzaldehyde from benzyl alcohol through photooxidation. We have synthesized bismuth vanadate functionalized graphitic carbon nitride decorated reduced graphene oxide B/CN@rGO ternary composite and subsequently subjected it to several characterization methodologies like XRD, FE‐SEM, HR‐TEM, XPS, FT‐IR, TGA, UV‐vis DRS, and EIS. The synthesized B/CN@rGO was effectively used in the photooxidation process to produce benzaldehyde from benzyl alcohol, employing a cost‐effective white LED light of 200 W. Remarkable selectivity (100%) towards the benzaldehyde was attained employing green oxidant H2O2. In addition, the synthesized photocatalyst showed unique thermal stability and could be reused for over five cycles without compromising the selectivity of the resulting product. Based on our comprehensive review of the existing study, the present work introduces a unique approach for the photooxidation of benzyl alcohol, employing B/CN@rGO ternary heterostructure as the photocatalyst.
本研究介绍了一种新型三元异质结构光催化剂,可通过光氧化作用从苯甲醇中选择性地生成苯甲醛。我们合成了钒酸铋官能化的氮化石墨装饰还原氧化石墨烯 B/CN@rGO 三元复合材料,并随后对其进行了多种表征方法,如 XRD、FE-SEM、HR-TEM、XPS、傅立叶变换红外光谱、TGA、紫外可见 DRS 和 EIS。合成的 B/CN@rGO 被有效地用于光氧化过程,利用 200 W 的高性价比白光 LED 灯从苯甲醇中生成苯甲醛。此外,合成的光催化剂还表现出独特的热稳定性,可重复使用五次以上,而不会影响所得产物的选择性。在全面回顾现有研究的基础上,本研究采用 B/CN@rGO 三元异质结构作为光催化剂,为苯甲醇的光氧化引入了一种独特的方法。
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引用次数: 0
High‐Efficiency Deep Red Fluorescent Material with Aggregation Induced Emission and the Application in Organic Light‐Emitting Diodes 具有聚集诱导发射功能的高效深红色荧光材料及其在有机发光二极管中的应用
IF 3.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-07-11 DOI: 10.1002/cptc.202400098
Hui Liu, Hanyuan Zhang, Yuanyuan Pu, Zhi Li, Liang Wan, Shuyuan Ge, Xiaobo Ma, Futong Liu, Ping Lu
The development of highly efficient deep red materials with emission wavelength beyond 650 nm remains a big challenge due to the constraints imposed by the energy gap rule. In this work, a donor‐acceptor‐donor type emitter, 4,7‐bis(10‐(4‐(tert‐butyl)phenyl)‐10H‐phenothiazin‐3‐yl)benzo[c][1,2,5]thiadiazole (TBPPTZ) is designed and synthesized. Resulting from the slight twist angle between the donor and acceptor units, TBPPTZ exhibits nearly planar conformation and an extended conjugated structure. TBPPTZ shows a deep red emission peak at 687 nm and aggregation induced emission property with a high photoluminescence quantum yield of 45% in neat thin film. The optimized organic light‐emitting diode (OLEDs) utilizing TBPPTZ as the non‐doped emissive layer obtains a high external quantum efficiency (EQE) up to 2.51% with an electroluminescence (EL) peak at 676 nm, aligning with the Commission Internationale de L’Eclairage (CIE) coordinates (0.68, 0.31), which shows a small EQE roll‐off of only 5.6% at 100 cd m‐2. Additionally, the doped OLED achieves an EQE up to 5.09%, with an EL peak at 656 nm and CIE coordinates of (0.65, 0.34). The findings of this research not only contribute to achieve highly efficient deep red OLEDs but also offer a novel and effective deep red molecular strategy to realize high‐quality OLEDs.
由于能隙规则的限制,开发发射波长超过 650 纳米的高效深红色材料仍然是一个巨大的挑战。本研究设计并合成了一种供体-受体-供体型发射体--4,7-双(10-(4-(叔丁基)苯基)-10H-吩噻嗪-3-基)苯并[c][1,2,5]噻二唑(TBPPTZ)。由于供体和受体单元之间存在微小的扭转角度,TBPPTZ 显示出接近平面的构象和扩展的共轭结构。TBPPTZ 在 687 纳米波长处显示出深红色发射峰和聚集诱导发射特性,纯薄膜的光致发光量子产率高达 45%。利用 TBPPTZ 作为非掺杂发射层的优化有机发光二极管(OLED)获得了高达 2.51% 的外部量子效率(EQE),电致发光(EL)峰值在 676 nm 处,与国际照明委员会(CIE)坐标(0.68, 0.31)一致,在 100 cd m-2 时,EQE 小幅衰减仅为 5.6%。此外,掺杂 OLED 的 EQE 高达 5.09%,EL 峰值为 656 纳米,CIE 坐标为(0.65, 0.34)。这项研究成果不仅有助于实现高效的深红色有机发光二极管,还为实现高质量的有机发光二极管提供了一种新颖有效的深红色分子策略。
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引用次数: 0
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ChemPhotoChem
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