Article
Chemistry, Physical
Piotr Gierlich, Sebastian G. Mucha, Emma Robbins, Ligia C. Gomes-da-Silva, Katarzyna Matczyszyn, Mathias O. Senge
Summary: This study utilized the second-generation photosensitizer m-THPC as a starting point to obtain a library of compounds with improved optical properties through substitution, esterification, and Sonogashira coupling reactions. By enhancing the two-photon absorption cross-section through modification of the m-THPC skeleton, tetrafunctionalized m-THPC derivatives showed promise for application in two-photon induced PDT.
Article
Chemistry, Multidisciplinary
Yuming Su, Yiheng Dai, Yifan Zeng, Caiyun Wei, Yangtao Chen, Fuchun Ge, Peikun Zheng, Da Zhou, Pavlo O. Dral, Cheng Wang
Summary: A systematic study was conducted to analyze the key molecular features affecting two-photon absorption (TPA) magnitudes by using interpretable machine learning (ML) and collecting an experimental TPA database of around 900 molecules. A fast ML model was built for predictions, with prediction errors similar to experimental and affordable quantum chemical methods, demonstrating its potential for high-throughput screening. The ML feature analysis confirmed common beliefs and provided quantification and rectification, with conjugation length being the most important feature followed by features reflecting donor and acceptor substitution and coplanarity effects.
Article
Chemistry, Applied
Seifallah Abid, Christophe Nguyen, Morgane Daurat, Denis Durand, Bassem Jamoussi, Mireille Blanchard-Desce, Magali Gary-Bobo, Olivier Mongin, Christine O. Paul-Roth, Frederic Paul
Summary: The synthesis of new fluorenyl phthalocyanines substituted with water-solubilizing triethyleneglycol chains is described. These biocompatible molecules exhibit strong absorption and fluorescence properties, showing more promising biocompatibility in vitro on cancer cells compared to unsubstituted zinc phthalocyanine.
Article
Chemistry, Multidisciplinary
Hongqian Cao, Yanfei Qi, Xibao Gao, Zi Jin Wei, Jiarui Xia, Lei Wang, Hao Wang, Yang Yang, Junbai Li
Summary: The novel peptide nanodrug, consisting of three functional motifs - bis(pyrene), FFVLK and CREKA, is used as a two-photon excited photosensitizer for precise photodynamic therapy (PDT), showing excellent two-photon imaging ability, tumor target effect and high reactive oxygen species productivity to improve treatment precision and efficiency in PDT.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Jodukathula Nagamaiah, Arnab Dutta, Sipra Sucharita Sahoo, Sameeta Sahoo, Pradeepta K. Panda
Summary: Two new 3,6,13,16-tetraalkylporphycenes were successfully synthesized using a rational approach. The lower yield of the desired alpha,alpha'-bipyrroles was explained, as the sigma-donating effect of alkylsubstituents was found to be more significant compared to positional isomeric tetraalkylporphycenes. The tetramethyl derivative exhibited a square-type core, while the tetraethyl and tetrapropyl derivatives displayed a rectangular core due to coordination with the guest. The enhanced basicity of the macrocycles with increasing alkyl chain at the inner beta-positions could explain this phenomenon. Both the tetramethyl and tetraethyl freebase porphycenes showed enhanced fluorescence and singlet oxygen generation ability compared to tetrapropylporphycene.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Lei-Lei Yang, Liang Zhang, Shu-Cheng Wan, Shuo Wang, Zhi-Zhong Wu, Qi-Chao Yang, Yao Xiao, Hexiang Deng, Zhi-Jun Sun
Summary: The combination of immune checkpoint blockade therapy and photodynamic therapy shows promising potential in inducing efficient immunogenic cell death and immune response, offering new hope for cancer treatment.
ADVANCED FUNCTIONAL MATERIALS
(2021)
Review
Polymer Science
Subramaniyan Ramasundaram, Sivasangu Sobha, Gurusamy Saravanakumar, Tae Hwan Oh
Summary: Polymers are carriers used for delivering therapeutic drugs and imaging probes to specific target sites. With appropriate targeting moieties, these carriers can achieve target-specific delivery at the cellular level. Recent attention has been focused on two-photon absorption (2PA)-mediated drug delivery and imaging, which offers better biocompatibility and treatment effects.
Article
Biotechnology & Applied Microbiology
Wenyao Duan, Bo Li, Wen Zhang, Jiaqi Li, Xin Yao, Yupeng Tian, Jun Zheng, Dandan Li
Summary: This study presents a new approach for designing oxygenation nanomaterials to relieve tumor hypoxia and enhance cancer treatment through oxygen-generating strategy. The combination of photodynamic therapy and sonodynamic therapy, along with the conversion of H2O2 into O-2, resulted in improved therapeutic outcome. In addition, the nanomaterial showed two-photon activity and cancer cell specific targeting capability, enabling deeper tissue penetration and precise guidance for cancer therapy.
JOURNAL OF NANOBIOTECHNOLOGY
(2022)
Article
Chemistry, Applied
Xue Wei, Wei-Bo Cui, Feng-Yi Sun, Hui Li, Jing-Fu Guo, Xue-Li Hao, Ai-Min Ren
Summary: In this paper, density functional theory (DFT) and timedependent density functional theory (TDDFT) calculations were used to study the properties of Pt(II) and Pd(II) complexes. The designed Pd(II) complex showed a large two-photon absorption cross section and long triplet excited state lifetime, making it a potential candidate for an effective two-photon absorption photosensitizer.
Article
Chemistry, Multidisciplinary
Fangmian Wei, Johannes Karges, Jinchao Shen, Lina Xie, Kai Xiong, Xiting Zhang, Liangnian Ji, Hui Chao
Summary: Photodynamic therapy (PDT) is a medical technique used for the treatment of cancer that has gained attention for its selectivity and non-invasiveness. However, the hypoxic environment in solid tumors limits its effectiveness. In this study, graphitic carbon nitride nanosheets functionalized with mitochondria-targeting iridium complexes were used to achieve oxygen self-sufficient two-photon PDT, effectively treating hypoxic tumors in a mouse model. This is the first example of using iridium complex functionalized graphitic carbon nitride nanosheets for the treatment of hypoxic tumors under clinically relevant two-photon irradiation.
Article
Engineering, Biomedical
Hongzhi Cao, Bin Fang, Jiejie Liu, Yu Shen, Jie Shen, Pan Xiang, Qin Zhou, Senio Campos De Souza, Dandan Li, Yupeng Tian, Lei Luo, Zhongping Zhang, Xiaohe Tian
Summary: The study designed multi-photon responsive photosensitizers for photodynamic therapy, demonstrating that one of the compounds could induce multiple types of cell death under three-photon exposure, providing a new strategy for developing competitive multi-photon PDT functional materials.
ADVANCED HEALTHCARE MATERIALS
(2021)
Review
Biochemistry & Molecular Biology
Emma Robbins, Stephanie Leroy-Lhez, Nicolas Villandier, Marek Samoc, Katarzyna Matczyszyn
Summary: This review discusses strategies for improving the TPA properties of photosensitizers, including promising organic and organometallic structures, and complex systems involving organic and inorganic nanoparticles. Focus is on studies providing TPA cross-section values, singlet oxygen (or other ROS), and luminescence quantum yields, crucial for potential use in PDT and diagnostics. The aim is to aid in the design and modification of novel TPA photosensitizers to exploit the features of nonlinear absorption processes.
Article
Chemistry, Applied
Rodrigo M. Barba-Barba, Marwa Chammam, Gabriel Ramos-Ortiz, Dymytrii Listunov, Jayaramakrishnan Velusamy, Mario Rodriguez, Ramon Carriles, Carlos Silva, Carine Duhayon, Brice Kauffmann, Valerie Maraval, Remi Chauvin
Summary: The study compares the optical properties of different structures of carbo-benzenes, finding that the carbomerization leads to lower energy electronic excitations and higher molar extinction coefficients compared to the parent molecules. Additionally, the carbomers exhibit a broad photoluminescence band with transitions from multiple excited states contrary to Kasha's rule.
Article
Chemistry, Medicinal
Kotaro Nishimura, Risako Shimada, Keita Yamana, Riku Kawasaki, Toshimi Nakaya, Atsushi Ikeda
Summary: In this study, lipid-membrane incorporated porphyrins were prepared as aqueous solutions. Porphyrins with proton-donor groups at the meso position formed stable aqueous solutions, while tetrakis(carboxyphenyl)porphyrin was soluble in water. The photodynamic activity of tetrakis(hydroxyphenyl)porphyrin was higher than that of tetrakis(aminophenyl)porphyrin, attributed to the self-aggregation of the latter in liposomes.
Review
Engineering, Biomedical
Sathishkumar Gnanasekar, Gopinath Kasi, Xiaodong He, Kai Zhang, Liqun Xu, En-Tang Kang
Summary: This review assesses recent advancements in polymer-photosensitizer hybrid materials developed for antibacterial photodynamic therapy (APDT) applications. The review discusses the integration and functionalization of photosensitizers with polymers, the use of photosensitizer coatings to eliminate healthcare-associated infections, and the application of photosensitizers in films, scaffolds, and hydrogels for regenerative medicine.
BIOACTIVE MATERIALS
(2023)
Article
Chemistry, Physical
Mohamed Yahya, Deniz Cakmaz, Sylvain Achelle, Estelle le Gall, Ertan Sahin, Zeynel Seferoglu
Summary: Organic conjugated compounds with various substituents, including 3-amino-2,4-dicyano-1-aryl-9H-fluorene and 1-dicyanomethylene-2-aryl-indone derivatives, were successfully synthesized using different routes and methods, characterized using spectroscopic techniques. X-ray analysis and thermogravimetric analysis were performed to further study the compounds, while UV-vis and fluorescence were used to investigate their photophysical properties.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2021)
Article
Engineering, Manufacturing
Caroline Arnoux, Luis A. Perez-Covarrubias, Alexandre Khaldi, Quentin Carlier, Patrice L. Baldeck, Kevin Heggarty, Akos Banyasz, Cyrille Monnereau
Summary: This paper investigates the proximity effects in additive manufacturing and proposes a parallel write approach to overcome the limitations caused by these effects. Through experiments and computer simulations, the authors successfully model the effects and demonstrate the effectiveness of the parallel write approach in fabricating structures with submicronic inter-object distances.
ADDITIVE MANUFACTURING
(2022)
Article
Nanoscience & Nanotechnology
Rodrigo Plaza-Pedroche, M. Paz Fernandez-Liencres, Sonia B. Jimenez-Pulido, Nuria A. Illan-Cabeza, Sylvain Achelle, Amparo Navarro, Julian Rodriguez-Lopez
Summary: The photophysical properties of a series of original compounds were investigated, and the emission control through proton transfer and protonation was demonstrated, showing potential applications in chemical sensing and anti-counterfeiting.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Applied
Sylvain Achelle, Maxime Hodee, Julien Massue, Arnaud Fihey, Claudine Katan
Summary: Diazines are widely used in the design of push-pull chromophores for organic electronics and optoelectronics, with a current focus on the third generation of OLED based on TADF. This technology has attracted increasing attention for its potential to reduce energy waste and harvest both triplet and singlet excitons.
Article
Biochemistry & Molecular Biology
Egor V. Verbitskiy, Pascal le Poul, Filip Bures, Sylvain Achelle, Alberto Barsella, Yuriy A. Kvashnin, Gennady L. Rusinov, Valery N. Charushin
Summary: In this study, a series of novel V-shaped derivatives were designed and investigated for their electrochemical, photophysical and nonlinear optical properties. The [1,2,5]oxadiazolo[3,4-b]pyrazine fragment was found to be a strong electron-withdrawing group. All compounds exhibited emissions in the solid state, while only the quinoxaline derivatives emitted in a DCM solution. The quinoxaline derivatives demonstrated solvatochromism and extra-large Stokes shifts, indicating twisted intramolecular charge transfer excited states and aggregation induced emission.
Article
Chemistry, Analytical
Chih-Lang Lin, Shyang-Guang Wang, Meng-Tsung Tien, Chung-Han Chiang, Yi-Chieh Lee, Patrice L. Baldeck, Chow-Shing Shin
Summary: This paper presents a novel methodology for detecting variations in cell surface antigens through optical cell-tearing and dilution regulations. The study found that higher dilution required lower power to tear off the cell binding, indicating antigenic variation. The proposed relative-quantitative analysis theory can provide an intuitive estimation of antigenic variation.
Article
Chemistry, Physical
Olivier Aleveque, Sylvain Achelle, Lionel Sanguinet
Summary: In this study, a class of multi-modal systems based on the association of a triphenylamine core with vinylpyrimidine units was developed. These systems exhibit nice acido and electrochromic properties, with the most performant ones capable of presenting up to three different forms, allowing modulation of their absorption and luminescence properties. The switching behaviors of these systems were rationalized using DFT and TD-DFT calculations.
Article
Chemistry, Inorganic & Nuclear
Mariia Hruzd, Samia Kahlal, Nicolas le Poul, Laurianne Wojcik, Marie Cordier, Jean-Yves Saillard, Julian Rodriguez-Lopez, Francoise Robin-le Guen, Sebastien Gauthier, Sylvain Achelle
Summary: A series of phosphorescent platinum(ii) complexes with various phenyldiazine-type bidentate N<^>C ligands were synthesized and characterized. Structural modifications were made to the ligands, including changes in the nature of the diazine ring and the substituent groups. X-ray diffraction studies revealed a distorted square-planar geometrical environment for the complexes. The complexes exhibited phosphorescence emission ranging from green to red/near-infrared in both solution and solid state.
DALTON TRANSACTIONS
(2023)
Review
Chemistry, Organic
Sylvain Achelle, Julian Rodriguez-Lopez, Francoise Robin-le Guen
Summary: The incorporation of electron-withdrawing pyrimidine rings within pi-extended systems allows access to a wide variety of fluorescent push-pull molecules that display emission properties highly sensitive to external stimuli. These molecules have been extensively studied and applied in sensors and luminescent materials, showing great potential in optoelectronic applications.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Physical
Teresa Anton-Canovas, Sylvain Achelle, M. Paz Fernandez-Liencres, Amparo Navarro, Francisco Alonso, Julian Rodriguez-Lopez
Summary: In this study, new push-pull indolizines with amino and electron-withdrawing groups were synthesized, and their optical response in acidic medium was investigated. Protonation on the amino group led to a hypsochromic shift in the emission spectra. Adjusting the amount of acid allowed for white photoluminescence due to color complementarity between neutral and charged species. Density Functional Theory (DFT) calculations supported the experimental results and provided insights into the electronic and optical properties of these compounds.
JOURNAL OF MOLECULAR LIQUIDS
(2023)
Article
Chemistry, Physical
Julien Massue, Lacina Diarra, Ioannis Georgoulis, Arnaud Fihey, Francoise Robin-le Guen, Gilles Ulrich, Mihalis Fakis, Sylvain Achelle
Summary: A pyrimidine chromophore with an acridan fragment was synthesized and its photophysical properties were investigated. It exhibits important positive emission solvatochromism in solution, with large Stokes shifts and different fluorescence decay patterns in polar solvents. Furthermore, aggregation-induced enhanced emission was observed in THF/water mixtures, and a triplet state was observed in a PMMA thin film but not in solution. Finally, chromophore protonation in thin film results in panchromatic dual emission.
Article
Chemistry, Physical
Maxime Hodee, Julien Massue, Sylvain Achelle, Arnaud Fihey, Denis Tondelier, Gilles Ulrich, Francoise Robin-le Guen, Claudine Katan
Summary: This study investigates the absence of thermally activated delayed fluorescence (TADF) in styrylpyrimidines with bulky electron-donating substituents. The experimental and theoretical investigations reveal that efficient spin-orbit coupling between the energy states cannot be achieved, resulting in the lack of TADF.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Inorganic & Nuclear
Mariia Hruzd, Nicolas le Poul, Marie Cordier, Samia Kahlal, Jean-Yves Saillard, Sylvain Achelle, Sebastien Gauthier, Francoise Robin-le Guen
Summary: In this article, a series of cyclometalated platinum(ii) complexes with various tridentate N^C^N-cyclometalated ligands derived from 1,3-bis(pyrimidin-2-yl)benzene were reported. The optical properties of these complexes in solution and solid state were found to be dependent on the substituents. In addition, the DFT calculations correlated well with the experimental data.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Maxime Hodee, Augustin Lenne, Julian Rodriguez-Lopez, Francoise Robin-le Guen, Claudine Katan, Sylvain Achelle, Arnaud Fihey
Summary: In this study, seven new push-pull systems were designed by combining a protonable diazine heterocycle with a deprotonable phenol unit through various pi-conjugated linkers. (De)protonation in solution resulted in a systematic bathochromic shift in both absorption and emission maxima. Computational analysis revealed that (de)protonation affects the energy and nature of vertical transitions, increasing the Intramolecular Charge Transfer (ICT) character of the excitations. Some compounds remained luminescent after (de)protonation, allowing for white light emission.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Raphael J. Durand, Sylvain Achelle, Francoise Robin-Le Guen, Elsa Caytan, Nicolas Le Poul, Alberto Barsella, Patricia Guevara Level, Denis Jacquemin, Sebastien Gauthier
Summary: A series of four new V-shaped binuclear platinum(ii) complexes (D-(pi-Pt-pi-A)(2)) with diphenylpyranylidene ligands as pro-aromatic donors (D) and various electron-attracting groups (A) separated by platinum bis-acetylide fragments have been synthesized, characterized, and studied for their electrochemical, photophysical, and second-order nonlinear optical (NLO) properties. The complexes' NLO responses were determined using the Electric-Field-Induced Second Harmonic (EFISH) generation technique, and their optical properties were rationalized using Time-Dependent Density Functional Theory (TD-DFT) calculations based on a range-separated hybrid. All complexes exhibited positive mu beta(0) values, and their second-order NLO responses could be easily modulated by incorporating various end-capped electron-attracting groups such as malononitrile, indane-1,3-dione, pyrimidine, and pyrimidinium. Notably, complex 7 with a pyrimidinium fragment displayed the highest mu beta(0) value among the series, showing a NLO response twice as high as the mononuclear analogue complex RD2, as confirmed experimentally and theoretically.
DALTON TRANSACTIONS
(2021)
