Physical Chemistry Chemical Physics最新文献

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Spectroscopic Investigation of Size-Dependent CO2 Binding on Cationic Copper Clusters: Analysis of the CO2 Asymmetric Stretch 阳离子铜簇上尺寸依赖性二氧化碳结合的光谱研究:二氧化碳不对称伸展分析
IF 3.3 3区 化学
Physical Chemistry Chemical Physics Pub Date : 2024-07-12 DOI: 10.1039/d4cp01797h
Anna Maria Reider, Máté Szalay, Johannes Reichegger, Júlia Barabás, Martin Schmidt, Miriam Kappe, Tibor Höltzl, Paul Scheier, Olga Lushchikova
{"title":"Spectroscopic Investigation of Size-Dependent CO2 Binding on Cationic Copper Clusters: Analysis of the CO2 Asymmetric Stretch","authors":"Anna Maria Reider, Máté Szalay, Johannes Reichegger, Júlia Barabás, Martin Schmidt, Miriam Kappe, Tibor Höltzl, Paul Scheier, Olga Lushchikova","doi":"10.1039/d4cp01797h","DOIUrl":"https://doi.org/10.1039/d4cp01797h","url":null,"abstract":"Photofragmentation spectroscopy, combined with quantum chemical computations, was employed to investigate the position of the asymmetric CO2 stretch in cold He-tagged Cun[CO2]+ (n = 1-10) and Cun[CO2][H2O]+ (n = 1-7) complexes. A blue shift in the band position was observed compared to the free CO2 molecule for Cun[CO2]+ complexes. Furthermore, this shift was found to exhibit a notable dependence on cluster size, progressively redshifting with increasing cluster size. The computations revealed that the CO2 binding energy is the highest for the Cu+ and continuously decreases with increasing cluster size. This dependency could be explained by highlighting the role of polarization in electronic structure, according to energy decomposition analysis. Introduction of water to this complex amplified the redshift of the asymmetric stretch, showing a similar dependency on the cluster size as observed for Cun[CO2]+ complexes.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141602750","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
Rotational spectroscopy of 2,4,6-cycloheptatriene-1-carbonitrile: Facilitating the search for complex cyclic molecules in the ISM' 2,4,6-环庚三烯-1-甲腈的旋转光谱学:促进寻找 ISM 中的复杂环状分子
IF 3.3 3区 化学
Physical Chemistry Chemical Physics Pub Date : 2024-07-12 DOI: 10.1039/d4cp01899k
Gayatri Batra, Laura Pille, Benjamin E. Arenas, Melanie Schnell
{"title":"Rotational spectroscopy of 2,4,6-cycloheptatriene-1-carbonitrile: Facilitating the search for complex cyclic molecules in the ISM'","authors":"Gayatri Batra, Laura Pille, Benjamin E. Arenas, Melanie Schnell","doi":"10.1039/d4cp01899k","DOIUrl":"https://doi.org/10.1039/d4cp01899k","url":null,"abstract":"The recent astronomical observations of the simplest aromatic nitrile benzonitrile, c-C6H5CN, fol- lowed by a five-membered and a bicyclic CN-functionalized ring in TMC-1 have provided a significant impetus to the field for searches of cyclic complex organic molecules in space. One such example is 2,4,6-cycloheptatriene-1-carbonitrile, a seven-membered ring with a -CN group attached to the sp3-hybridized carbon atom. With a permanent electric dipole moment of 4.3 D, this molecule is an excellent candidate for laboratory rotational spectroscopy. In this study, experiments were performed in the 2-8 GHz, 18-26 GHz and 75-110 GHz frequency ranges in a supersonic expansion setup and a room temperature flow cell setup. The measurements across the broad frequency range of 2-110 GHz have enabled the identification and assignment of the vibronic ground state, singly substituted rare- atom isotopologues, and vibrationally excited states. Here, we report the precise determination of the rotational constants, quartic centrifugal distortion constants, nitrogen nuclear quadrupole coupling constants, as well as molecular structure in its vibronic ground state. The comprehensive rotational spectroscopy study of this molecule, covering a large frequency range, forms the basis for its future astronomical detection and thus for extending the pool of detected complex cyclic molecules.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141602751","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
Nuclear quantum and H/D isotope effects on aromaticity: path integral molecular dynamics study. 核量子和 H/D 同位素对芳香性的影响:路径积分分子动力学研究。
IF 2.9 3区 化学
Physical Chemistry Chemical Physics Pub Date : 2024-07-12 DOI: 10.1039/d4cp01331j
Hikaru Tanaka, Kazuaki Kuwahata, Masanori Tachikawa, Taro Udagawa
{"title":"Nuclear quantum and H/D isotope effects on aromaticity: path integral molecular dynamics study.","authors":"Hikaru Tanaka, Kazuaki Kuwahata, Masanori Tachikawa, Taro Udagawa","doi":"10.1039/d4cp01331j","DOIUrl":"https://doi.org/10.1039/d4cp01331j","url":null,"abstract":"<p><p>Aromaticity is an important concept in organic chemistry, and thus, many theoretical and experimental studies have been conducted so far. However, the majority of theoretical studies have concentrated on the aromaticity of the stationary point structures. Herein, the influence of nuclear quantum fluctuation (nuclear quantum effects: NQEs) and thermal fluctuation on the aromaticity of benzene have been analyzed by path integral molecular dynamics (PIMD) simulation. The PIMD simulations revealed that the NQEs affected not only the C-H bonds but also the C-C bonds. The HOMA and NICS calculations demonstrated that the aromaticity decreased due to the NQEs of carbon atoms, attributed to an increase in the contribution from specific vibrational modes strongly correlated with benzene's aromaticity.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588991","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
Cyclohepta[def]fluorene as a Bistable Molecule: First Principles Studies on its Electronic Structure and the Effects of Benzo-Extension, Substitution and Solvation 作为双稳态分子的环庚[def]芴:关于其电子结构以及苯并延伸、取代和溶解影响的第一性原理研究
IF 3.3 3区 化学
Physical Chemistry Chemical Physics Pub Date : 2024-07-12 DOI: 10.1039/d4cp02247e
Robert Toews, Andreas Köhn
{"title":"Cyclohepta[def]fluorene as a Bistable Molecule: First Principles Studies on its Electronic Structure and the Effects of Benzo-Extension, Substitution and Solvation","authors":"Robert Toews, Andreas Köhn","doi":"10.1039/d4cp02247e","DOIUrl":"https://doi.org/10.1039/d4cp02247e","url":null,"abstract":"Cyclohepta[def]fluorene 1 and its derivatives have received considerable attention due to possible technological applications as molecular devices. Despite efforts from both theory and experiment, the electronic structure of 1 has remained unclear. Herein, we report advanced first-principles calculations on 1 using a multireference and a coupled-cluster method. We confirm a bistability of 1 between a polar singlet state and a non-polar triple state. We also study the effects of benzo-extension on the electronic structure and the influences of substitution and solvation on the ground state. Our results suggest that deliberate choice of substituents allows to toggle the multiplicity of the ground state. We also propose that due to its bistability, 1 represents an attractive building block for molecular devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141602747","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
Rapid nucleation and optimal surface-ligand interaction stabilize Wurtzite MnSe 快速成核和最佳表面-配体相互作用稳定了沃特兹态锰硒
IF 3.3 3区 化学
Physical Chemistry Chemical Physics Pub Date : 2024-07-12 DOI: 10.1039/d4cp02294g
Rashmi Khan, Shilendra Kumar Sharma, Vivek Chaudhary, Raj Ganesh S. Pala, Sivakumar Sri
{"title":"Rapid nucleation and optimal surface-ligand interaction stabilize Wurtzite MnSe","authors":"Rashmi Khan, Shilendra Kumar Sharma, Vivek Chaudhary, Raj Ganesh S. Pala, Sivakumar Sri","doi":"10.1039/d4cp02294g","DOIUrl":"https://doi.org/10.1039/d4cp02294g","url":null,"abstract":"Non-native structures (NNS) differ in discrete translational symmetry from the bulk ground state native structure (NS). To explore the extent of deconvolution of various factors relevant to the stabilization of Wurtzite/NNS of MnSe via heat up method, we undertook experiments using various ligands (oleic acid, oleylamine, octadecylamine, stearic acid, and octadecene), solvents (tetraethylene glycol and octadecene), and precursors salts (manganese chloride and manganese acetate). Experiments suggest that oleic acid in the presence of tetraethylene glycol and oleylamine in the presence of octadecene stabilizes Wurtzite/NNS. Further, density functional theory (DFT) computations explore the interaction between functional groups in ligands and the most exposed surfaces of Wurtzite/NNS and Rocksalt/NS polymorphs. Computations suggest that interactions between relevant surface facets with carboxylic acid and the double bond functional groups suppress phase transformation from NNS to NS. In addition, the ionizability of precursor salt also determines the rate of formation of metal-ligand complex and the rate of nucleation. Consequently, the formation rate of Mn-ligand complex is expected to be greater in the case of chloride salt than acetate salt because the chloride salt has higher ionizability in ethylene glycol. From the above, we conclude that the kinetics of Wurtzite/NNS to Rocksalt/NS phase transformation depends majorly on two factors: 1) Nucleation/growth kinetics which is controlled by ionizability of the precursor salt, solvent, and stability of metal-ligand complex, and 2) activation energy barrier of the NNS to NS conversion which is controlled by surface energy minimization with the ligand.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141602819","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
Photophysical and redox properties of new donor-acceptor-donor (DAD) compounds containing benzothiadiazole (A) and dimethyldihydroacridine (D) units - a combined experimental and theoretical study 含有苯并噻二唑(A)和二甲基二氢吖啶(D)单元的新型供体-受体-供体(DAD)化合物的光物理和氧化还原特性--实验与理论的综合研究
IF 3.3 3区 化学
Physical Chemistry Chemical Physics Pub Date : 2024-07-11 DOI: 10.1039/d4cp02322f
Emilia Polesiak, Malgorzata Makowska-Janusik, Jakub Drapała, Malgorzata Zagorska, Marzena Banasiewicz, Boleslaw Kozankiewicz, Irena Kulszewicz-Bajer, Adam Pron
{"title":"Photophysical and redox properties of new donor-acceptor-donor (DAD) compounds containing benzothiadiazole (A) and dimethyldihydroacridine (D) units - a combined experimental and theoretical study","authors":"Emilia Polesiak, Malgorzata Makowska-Janusik, Jakub Drapała, Malgorzata Zagorska, Marzena Banasiewicz, Boleslaw Kozankiewicz, Irena Kulszewicz-Bajer, Adam Pron","doi":"10.1039/d4cp02322f","DOIUrl":"https://doi.org/10.1039/d4cp02322f","url":null,"abstract":"Four donor-acceptor-donor compounds consisting of 9,9-dimethyl-9,10-dihydroacridine donors differently linked to benzothiadiazole acceptor were designed using DFT calculations and synthesized, namely 4,7-bis(4-(9,9-dimethyl-9,10-dihydroacridine)phenyl)benzo[c][1,2,5]thiadiazole (1), 4,7-Bis(2,5-dimethyl-4-(9,9-dimethyl-9,10-dihydroacridine)phenyl)benzo[c][1,2,5]thiadiazole (2), 4,7-Bis(3,5-di(9,9-dimethyl-9,10-dihydroacridine)phenyl)benzo[c][1,2,5]thiadiazole (3), 4-(3,5-di(9,9-dimethyl-9,10-dihydroacridine)phenyl)-7-(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (4). As predicted theoretically all studied compounds were electrochemically active both in the reduction as well as in the oxidation modes. They underwent one electron quasi-reversible reduction. Oxidation of 1 and 2 involved two electron process transforming them into dications and in parallel their dimerization. Oxidation of 3 and 4 resulted in their oligomerization (polymerization). The electrochemically determined ionisation potentials (IP) of 1 - 4 were similar, covering a narrow range of 5.28 eV - 5.33 eV and consistent with DFT calculations. Larger differences were found for experimentally determined electron affinity (EA) values, being significantly lower for 2 (|EA| = 2.59 eV) as compared to 1, 3 and 4 whose |EA| values were by 0.15 – 0.25 eV higher, again consistent with DFT calculations. DFT calculations predict positive values of ∆E(S1-T1) for all compounds i.e. in the range of 0.18 eV to 0.43 eV for 1, 3 and 4 and a significantly lower value for 2 (0.06 eV), indicating possible RISC process in this case. DFT calculations of ∆E(S1-T2) lead to negative and very small values for 2 - 4 implying possible involvement of higher lying triplets in the generation of singlet excitons. The investigated derivatives exhibited fluorescence in the orange-red spectral range (550 nm – 770 nm), strongly dependent on the solvent polarity. The highest PLQY value of 37% was measured for 1 in toluene. The PLQY values significantly improved upon deoxygenation of the studied solutions. Solid state samples also exhibited higher PLQY values as compared to those determined for DCM solutions. These findings were rationalized by partial suppression of the vibrationally induced emission quenching in the solid state due to the intermolecular interactions confinement.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141602754","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
Isothermal and non-isothermal transport properties of diluted fullerene binary and ternary aromatic solvent mixtures. 稀释富勒烯二元和三元芳香族溶剂混合物的等温和非等温传输特性。
IF 2.9 3区 化学
Physical Chemistry Chemical Physics Pub Date : 2024-07-11 DOI: 10.1039/d4cp01504e
A Errarte, D Sommermann, V Shevtsova, W Köhler, M M Bou-Ali
{"title":"Isothermal and non-isothermal transport properties of diluted fullerene binary and ternary aromatic solvent mixtures.","authors":"A Errarte, D Sommermann, V Shevtsova, W Köhler, M M Bou-Ali","doi":"10.1039/d4cp01504e","DOIUrl":"https://doi.org/10.1039/d4cp01504e","url":null,"abstract":"<p><p>We present mass transport properties of C<sub>60</sub> fullerene in five aromatic solvents, methylnaphthalene, toluene and three xylene isomers. Optical beam deflection and thermogravitational column techniques were used to determine molecular diffusion, thermodiffusion and Soret coefficients. All thermo-optical properties necessary to determine the abovementioned coefficients are also given at a mean working temperature of 298.15 K and an atmospheric pressure of 0.101 MPa. The magnitude of all transport properties is governed by the molecular weight ratio. In the particular case of the isomers, experiments revealed that movement under isothermal conditions (described by molecular diffusion) is dominated by density, while under non-isothermal conditions viscous forces affect the displacement (thermodiffusion depends on the dynamic viscosity). In the case of the Soret coefficients, as a combination of both, density is the dominant parameter and also the moment of inertia.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578329","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
Dynamic of non-covalent interactions during the P–O bond cleavage by ribonuclease A 核糖核酸酶 A 裂解 P-O 键过程中的非共价相互作用动态
IF 3.3 3区 化学
Physical Chemistry Chemical Physics Pub Date : 2024-07-11 DOI: 10.1039/d4cp01888e
Mark V. Kaplanskiy, Maxim L. Kruglov, Aleksandr A. Vanin, Elena Yu. Tupikina
{"title":"Dynamic of non-covalent interactions during the P–O bond cleavage by ribonuclease A","authors":"Mark V. Kaplanskiy, Maxim L. Kruglov, Aleksandr A. Vanin, Elena Yu. Tupikina","doi":"10.1039/d4cp01888e","DOIUrl":"https://doi.org/10.1039/d4cp01888e","url":null,"abstract":"In this work, an atomistic-scale investigation of the phosphodiester P–O bond cleavage reaction by the enzyme ribonuclease A was carried out by computer simulation techniques. It is shown that during the reaction the network of non-covalent interactions in the active center of the ribonuclease changes significantly, while the role of these non-covalent interactions is different – coordination of the corresponding groups, electron density transfer, and ligand holding in the active center. It is shown that the process of proton transfer from Asp121 to His119 is the first stage of this reaction; at the same time, the hydrogen bond between the phosphate ligand and the imino group of Arg39 is broken, which, although it keeps the ligand in the active center, does not allow the ligand to orient itself more conveniently for subsequent proton transfers. Further, the key step of this reaction occurs – proton transfer with the participation of imidazole rings His12 and His119, in which the guiding role is played by several hydrogen bonds with the participation of Phe120, and the role of electron density carrier is played by the chalcogen bond between the oxygen of the phosphate ligand and the pyridine-like nitrogen of the imidazole ring His119, which was detected for the first time.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141584444","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
A High-Performance Flexible Humidity Sensor based on TiO2-MWCNTs Nanocomposite for Human Healthcare 基于 TiO2-MWCNTs 纳米复合材料的高性能柔性湿度传感器,用于人类医疗保健
IF 3.3 3区 化学
Physical Chemistry Chemical Physics Pub Date : 2024-07-11 DOI: 10.1039/d4cp01148a
Ankit Kumar, Parvesh Kumari, Muthusamy Senthil Kumar, Gaurav Gupta, D. D. Shivagan, komal bapna
{"title":"A High-Performance Flexible Humidity Sensor based on TiO2-MWCNTs Nanocomposite for Human Healthcare","authors":"Ankit Kumar, Parvesh Kumari, Muthusamy Senthil Kumar, Gaurav Gupta, D. D. Shivagan, komal bapna","doi":"10.1039/d4cp01148a","DOIUrl":"https://doi.org/10.1039/d4cp01148a","url":null,"abstract":"The present work shows the improved humidity sensing characteristics of TiO2 nanoparticles in the form of nanocomposite with multiwalled carbon nanotubes (MWCNTs) prepared by hydration-dehydration method. The structural and morphological characterizations of TiO2-MWCNTs confirm the nanocomposite formation without any other impurities and improved surface area. The TiO2 and nanocomposite were deposited on the IDEs coated flexible Poly-ethylene terephthalate (PET) substrate by drop casting method. The nanocomposite shows improved sensitivity (1246.2 MΩ/%RH), and ultrafast response/recovery time (2 s/1 s) with minimal hysteresis of 0.27 %RH. Further, the flexible nanocomposite sensor is tested for human healthcare applications including respiratory monitoring, apnea like situation, and skin moisture detection. The sensor can distinguish different breath patterns like normal, fast, deep and apnea like situations, significantly. Skin moisture detection can also be performed by the nanocomposite sensor in a non-invasive manner. Overall, this study represents an environmentally friendly, easy to fabricate, flexible TiO2-MWCNTs nanocomposite based improved humidity sensor for human healthcare and wearable devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141584445","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
Theoretical investigation of the reaction mechanism of THP oxidative rearrangement catalysed by BBOX BBOX 催化 THP 氧化重排反应机理的理论研究
IF 3.3 3区 化学
Physical Chemistry Chemical Physics Pub Date : 2024-07-11 DOI: 10.1039/d4cp01661k
Fanqi Meng, Lu Sun, YueYing Liu, Xiang Li, Hongwei Tan, Chang Yuan, Xichen Li
{"title":"Theoretical investigation of the reaction mechanism of THP oxidative rearrangement catalysed by BBOX","authors":"Fanqi Meng, Lu Sun, YueYing Liu, Xiang Li, Hongwei Tan, Chang Yuan, Xichen Li","doi":"10.1039/d4cp01661k","DOIUrl":"https://doi.org/10.1039/d4cp01661k","url":null,"abstract":"γ-butyrobetaine hydroxylase (BBOX) is a non-heme Fe<small><sup>II</sup></small>/2OG dependent enzyme that is able to perform two different kinds of catalytic reactions on 3-(2,2,2-trimethylhydrazinium) propionate (THP) to produce distinct catalytic products. Although the structure of BBOX complexed with THP has been resolved, the details of its catalytic mechanism are still elusive. In this study, by employing molecular dynamics (MD) simulations and density functional theory (DFT) calculations, the mechanism of the THP oxidative rearrangement reactions catalysed by BBOX was investigated. Our calculations revealed how the enzyme undergoes a conformational conversion to initiate the catalytic reactions. In the first catalytic step, BBOX performs hydrogen abstraction from the substrate THP as a common non-heme iron enzyme. Due to the structure of the substrate stabilizes the radical species and polarizes the adjacent N-N bond, in the next step, THP takes the pathway for N-N bond homolysis but not regular hydroxyl rebounding. The cleaved ammonium radical could either react with the hydroxyl group on the iron centre of the enzyme or recombine with the other cleaved fragment of the substrate to generate the rearranged product. This study revealed the detailed catalytic mechanism of BBOX in which how the enzyme and the substrate regulated the hydroxyl rebound process to generate various products.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141584442","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
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