Review
Chemistry, Organic
Qing-Hao Xu, Bin Xiao
Summary: This review summarizes the mechanism and applications of four types of organogermanium structures, including acylgermanes, hydrogermanes, tetraalkylgermanes, and digermanes, in photoinduced radical reactions. These compounds have great potential in modern radical systems.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Engineering, Environmental
Chu Chu, Shengye Jin, Richard Spinney, Dionysios D. Dionysiou, Haijun Zhang, Ruiyang Xiao
Summary: This article introduces the application of laser flash photolysis (LFP) in transient radical processes. By introducing the development process, principles, and compositions of LFP, comparing the specificity and suitability of different spectral modes, and discussing the generation, detection, and environmental implications of hydroxyl radicals, sulfate radicals, and reactive chlorine species, a critical review of the implementation of LFP for kinetic quantification and mechanism elucidation is conducted. The remaining challenges and future perspectives are highlighted.
Article
Chemistry, Physical
Hirona Takahashi, Hiroki Hirano, Kyohei Nomura, Kenta Hagiwara, Akio Kawai
Summary: The addition reaction of radicals to C-60 was investigated using time-resolved Electron Paramagnetic Resonance (TR-EPR) and pulsed EPR methods, revealing high rate constants and diffusion-controlled reactions. The activation energy was discussed based on the charge transfer effect and enthalpy change.
CHEMICAL PHYSICS LETTERS
(2021)
Article
Environmental Sciences
Mikhail V. Novikov, Olga A. Snytnikova, Roman G. Fedunov, Vadim V. Yanshole, Vyacheslav P. Grivin, Victor F. Plyusnin, Jing Xu, Ivan P. Pozdnyakov
Summary: The mechanism of direct UV photolysis of the tricyclic antidepressant carbamazepine (CBZ) at neutral pH was revealed for the first time, combining nanosecond laser flash photolysis, steady-state photolysis with high resolution LC-MS, and DFT quantum-chemical calculations. Short-lived intermediates and final products were detected and identified. The quantum yield of CBZ photodegradation was found to be about 0.1-0.18% in different solution conditions. The primary stage involves photoionization and rapid nucleophilic attack by a solvent molecule, leading to the formation of several primary photoproducts including 10-oxo-9-hydro-carbamazepine and various hydroxylated CBZ isomers. Prolonged irradiation results in the accumulation of acridine derivatives, potentially increasing the toxicity of photolyzed CBZ solutions. These findings are important for understanding the fate of tricyclic antidepressants in UVC disinfection and natural waters under sunlight exposure.
Article
Optics
Suwat Romphosri, Phyu Sin Oo, Pornpawee Karanyasopon, Rakchart Traiphhol, Tanant Waritanant
Summary: It is found that Michler's ketone (MK) can be used for two-photon polymerization under near-infrared irradiation, and it has a large absorption cross-section, proving MK as a promising photoinitiator for low-cost two-photon polymerization.
APPLIED PHYSICS B-LASERS AND OPTICS
(2022)
Article
Polymer Science
Thu Anh Nguyen, Shota Ichise, Kenji Kinashi, Wataru Sakai, Naoto Tsutsumi, Satoko Okubayashi
Summary: The thermal degradation mechanism of poly(propylene) fabric was analyzed using the electron spin resonance (ESR) spin-trapping technique. The results showed that the degradation of poly(propylene) starts from the tertiary carbon positions and involves various pathways of radical formation, which further participate in the degradation process of poly(propylene).
POLYMER DEGRADATION AND STABILITY
(2022)
Article
Polymer Science
Tomoki Hayashi, Kenji Kinashi, Wataru Sakai, Naoto Tsutsumi, Ayaka Fujii, Seisuke Inada, Hiroshi Yamamoto
Summary: Spin-trapping ESR and GPC analyses were used to study the thermal degradation mechanisms of PVA, revealing the production of radical intermediates and the occurrence of cross-linking reactions at temperatures above 100°C. Main chain scission was also observed significantly around 200°C, indicating the importance of the elimination of .OH in PVA degradation.
Article
Polymer Science
Sevnur Keskin Dogruyol, Zekeriya Dogruyol, Elif Ozcelik Kazancioglu, Hasniye Gokcek, Nergis Arsu
Summary: Thioxanthonation of naphthalene thioacetic acid resulted in a visible light photoinitiator with high molar absorptivity and low fluorescence quantum yield and triplet energy, making it suitable for free radical polymerization reactions. The photopolymerization of methyl methacrylate with this photoinitiator and a tertiary amine yielded a significant conversion of monomer to polymer.
EUROPEAN POLYMER JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Till J. B. Zaehringer, Max Wienhold, Ryan Gilmour, Christoph Kerzig
Summary: This study provides a rigorous mechanistic investigation of the photoisomerization of alkenylboronates. The detection and characterization of the perpendicular triplet generated by energy transfer through a combination of experiments, spectroscopic studies, kinetic modeling, and DFT calculations have been achieved. The findings have not only served as a blueprint for challenging mechanistic studies but also allowed for the development of more sustainable reaction conditions, enabling efficient organocatalytic isomerization under sunlight irradiation for the first time.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Olesya Daikos, Sergej Naumov, Wolfgang Knolle, Katja Heymann, Tom Scherzer
Summary: The study found that pentabrominated and pentachlorinated phenyl methacrylate can effectively act as initiators for a photoinduced radical polymerization reaction. Different experimental techniques and quantum chemical modeling were used to elucidate the distinct initiation pathways of these halogenated monomers.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2022)
Article
Nuclear Science & Technology
Ufuk Paksu, Birol Engin
Summary: This study used paramagnetic defects induced by gamma radiation in modern paper samples to determine the dosimetric properties of ancient papers. The results showed that free radicals induced in mineral CaCO3 filler grains within papers have the potential to be used for retrospective dosimetry.
RADIATION MEASUREMENTS
(2022)
Article
Polymer Science
Nikola Babic, Simon Pondaven, Herve Vezin
Summary: Autoxidation is a common spontaneous oxygen-mediated radical reaction in the degradation processes of hydrocarbon-based materials. In this study, EPR spin-trapping technique was used to investigate radical species involved in the autoxidation of synthetic base oil. The difference in generating radical species between aged and non-aged samples of the same base oil was studied by introducing oxygen and aging the samples at 140 degrees C.
POLYMER DEGRADATION AND STABILITY
(2021)
Article
Chemistry, Multidisciplinary
Caroline J. Aschendorf, Mawuli Degbevi, Keaton V. Prather, Emily Y. Tsui
Summary: The participation of the surfaces of colloidal semiconductor nanocrystal quantum dots in QD-mediated photocatalytic reactions is crucial and should be considered in the design of photocatalysis. The study explores the reactivity of surface sulfides and selenides of metal chalcogenide QDs and demonstrates the importance of QD surfaces beyond tuning their band gaps.
Article
Chemistry, Physical
Yadong Hu, Jianzhong Ma, Mengyu Zhu, Yijun Zhao, Shuchuan Peng, Chengzhu Zhu
Summary: The study on the photochemical reaction of o-dichlorobenzene in the presence of nitrite revealed that the degradation efficiency is influenced by the concentration of N(III), initial concentration of o-DCB, and pH value. The hydroxyl radicals generated by the photolysis of N(III) attack the benzene ring of o-DCB to form a new compound, leading to the formation of different products.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2021)
Article
Chemistry, Applied
Joaquin Velasco, Mogens L. Andersen, Leif H. Skibsted
Summary: ESR spin trapping can be useful for evaluating the oxidative susceptibility of dried microencapsulated oils (DMOs), but caution is needed in interpreting the data due to the complexity of reactions involved. Availability of oxygen can impact the rates of spin trapping and spin-adduct quenching, affecting the levels of radicals observed. Understanding the kinetics of oxidation, spin trapping, and spin-adduct decay in bulk oils is crucial for accurate data interpretation in DMOs.
Article
Chemistry, Multidisciplinary
Katrina Tait, Samuel Koh, Nicolas Blanchard, William Tam
CANADIAN JOURNAL OF CHEMISTRY
(2019)
Article
Chemistry, Multidisciplinary
Vincent Le Fouler, Yu Chen, Vincent Gandon, Vincent Bizet, Christophe Salome, Thomas Fessard, Fang Liu, K. N. Houk, Nicolas Blanchard
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Biochemistry & Molecular Biology
Yangyi Qi, Shu Ting Chan, Lin Lin, Tsun Lam Shek, Tsz Fung Tsang, Yufeng Zhang, Margaret Ip, Paul Kay-sheung Chan, Nicolas Blanchard, Gilles Hanquet, Zhong Zuo, Xiao Yang, Cong Ma
BIOORGANIC CHEMISTRY
(2019)
Article
Chemistry, Applied
Yanpeng Liu, Long Yin Lam, Jiqing Ye, Nicolas Blanchard, Cong Ma
ADVANCED SYNTHESIS & CATALYSIS
(2020)
Article
Chemistry, Applied
Nicolas Brach, Vincent Le Fouler, Vincent Bizet, Marian Lanz, Fabrice Gallou, Corinne Bailly, Pascale Hoehn, Michael Parmentier, Nicolas Blanchard
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2020)
Article
Chemistry, Multidisciplinary
Vincent Debrauwer, Aneta Turlik, Lenaic Rummler, Alessandro Prescimone, Nicolas Blanchard, K. N. Houk, Vincent Bizet
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Infectious Diseases
Emma Colucci-Guyon, Aline Rifflet, Sarah Saint-Auret, Anaelle da Costa, Laurent Boucontet, Thomas Laval, Christophe Prehaud, Nicolas Blanchard, Jean-Pierre Levraud, Ivo G. Boneca, Caroline Demangel, Laure Guenin-Mace
PLOS NEGLECTED TROPICAL DISEASES
(2020)
Article
Chemistry, Multidisciplinary
Lucas Popek, Jorge Juan Cabrera-Trujillo, Vincent Debrauwer, Nicolas Blanchard, Karinne Miqueu, Vincent Bizet
Summary: This article describes a fully regio- and stereoselective hydroelementation reaction of SF5-alkynes with N, O, and S-nucleophiles, and the further functionalization of the resulting Z-(hetero)vinyl-SF5 intermediates. This reaction provides a suitable platform for accessing alpha-SF5 ketones and esters, as well as beta-SF5 amines and alcohols under mild reaction conditions. Experimental and computational comparative studies between SF5- and CF3-alkynes have been conducted to highlight and explain the observed differences in reactivity and selectivity between these two fluorinated motifs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Samuel Itskanov, Laurie Wang, Tina Junne, Rumi Sherriff, Li Xiao, Nicolas Blanchard, Wei Q. Shi, Craig Forsyth, Dominic Hoepfner, Martin Spiess, Eunyong Park
Summary: The Sec61 complex forms a protein-conducting channel in the endoplasmic reticulum membrane that is essential for protein secretion. Various small molecules have been identified as specific inhibitors of Sec61, but their inhibitory mechanisms are not well understood. This study presents detailed structures of human Sec61 bound to a variety of small molecule inhibitors, revealing a common binding pocket that stabilizes the closed state of the protein-translocation pore. These findings provide valuable insights for further pharmacological studies and drug design targeting Sec61.
NATURE CHEMICAL BIOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Thi Mo Nguyen, Claude Y. Legault, Nicolas Blanchard, Vincent Bizet, Dominique Cahard
Summary: In the vibrant field of SF5 chemistry, SF5X reagents (X=F, Cl, Br) are at the heart of current investigations in radical pentafluorosulfanylation reactions. SF5I, as a potential SF5 donor, has not been reported before. This study successfully reports the formal addition of SF5I reagent to alkynes, leading to the synthesis of unprecedented compounds. Computational and mechanistic studies reveal the involvement of SF5- anion and iodine radicals in the reaction.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Jiaqi Fang, Oumaima Bekkouch, Guilhem Zeiser, Yurii Zubchuk, Vincent Bizet, Nicolas Blanchard, Gwilherm Evano
Summary: This study reports a general copper-catalyzed ligand-controlled Chan-Lam-Evans arylation of cyanamides, leading to regioselective reactions at N(sp(3)) or N(sp) sites, resulting in N-aryl cyanamides or dissymmetric carbodiimides. The choice of ligand, either a bipyridine or a diamine, controls the distribution of products and provides a versatile approach to useful building blocks from readily available cyanamides.
Article
Chemistry, Organic
Nicolas Brach, Lucas Popek, Mathieu Truong, Claire Laurent, Vincent Bizet, Krishna P. Kaliappan, Nicolas Blanchard
Summary: Pyrazines can undergo intramolecular cascade reactions at room temperature, leading to the formation of specific compounds. The study also revealed the significant influence of substituents on the distribution of reaction products.
Article
Chemistry, Organic
Jiaqi Fang, Oumaima Bekkouch, Guilhem Zeiser, Yurii Zubchuk, Vincent Bizet, Nicolas Blanchard, Gwilherm Evano
Summary: In this study, a copper-catalyzed ligand-controlled arylation reaction of cyanamides is reported, which can selectively proceed at the N-(sp(3)) or N-(sp) atoms, leading to N-aryl cyanamides or dissymmetric carbodiimides. The choice of ligand, either a bipyridine or a diamine, determines the product distribution and provides a divergent entry to useful building blocks from readily available cyanamides.
Article
Chemistry, Multidisciplinary
Vincent Debrauwer, Ivo Leito, Mart Lokov, Sofja Tshepelevitsh, Michael Parmentier, Nicolas Blanchard, Vincent Bizet
Summary: This study presents a novel strategy for the synthesis of 2-SF5-(aza)indoles, utilizing radical addition of SF5CI and cyclization reaction. The flexible and reproducible telescoped sequence allows for downstream functionalizations, highlighting the strategic advantages of a C2-pentafluorosulfanylated motif in indole scaffolds.
Article
Chemistry, Multidisciplinary
Vincent Debrauwer, Ivo Leito, Mart Lokov, Sofja Tshepelevitsh, Michael Parmentier, Nicolas Blanchard, Vincent Bizet
Summary: The study presents a method for the first time access to 2-SF5(aza)indoles using radical addition of SF5Cl and cyclization reaction. A telescoped sequence is proposed for gram scale application and easy diversification of N- and C3-positions..analysis of fluorinated 2-Rf-indoles are disclosed to highlight the strategic advantages of a C2-pentafluorosulfanylated motif in indole scaffold.
ACS ORGANIC & INORGANIC AU
(2021)
