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Determining the Molecular Shape of Progesterone: Insights from Laser Ablation Rotational Spectroscopy.
IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-27 DOI: 10.1021/acs.jpclett.4c03618
Aran Insausti, Elena R Alonso, Sofía Municio, Iker León, Lucie Kolesniková, Santiago Mata

Herein, we present the first experimental observation of isolated progesterone, an endogenous steroid, placed in the gas phase by laser ablation and characterized in a supersonic expansion by Fourier transform microwave techniques. Guided by quantum-chemical calculations, we assigned the rotational spectrum of the most stable structure. The internal rotation of the acetyl methyl group led to the observation of A-E doublets in the spectrum, which were analyzed, resulting in a V3 barrier of 2.4425 ± 0.0025 kJ mol-1. By fitting over 250 transitions, we determined accurate rotational constants that enabled us to compare the gas phase geometrical parameters with those of crystalline forms and complexes with progesterone receptors. Our results indicate that the A ring of progesterone that contains the ketone group is surprisingly flexible, despite its rigid appearance. This finding is particularly significant, since this ring is an active biological site that is involved in strong intermolecular interactions. Notably, progesterone C21H30O2 is the largest molecule investigated using laser ablation rotational spectroscopy.

{"title":"Determining the Molecular Shape of Progesterone: Insights from Laser Ablation Rotational Spectroscopy.","authors":"Aran Insausti, Elena R Alonso, Sofía Municio, Iker León, Lucie Kolesniková, Santiago Mata","doi":"10.1021/acs.jpclett.4c03618","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03618","url":null,"abstract":"<p><p>Herein, we present the first experimental observation of isolated progesterone, an endogenous steroid, placed in the gas phase by laser ablation and characterized in a supersonic expansion by Fourier transform microwave techniques. Guided by quantum-chemical calculations, we assigned the rotational spectrum of the most stable structure. The internal rotation of the acetyl methyl group led to the observation of A-E doublets in the spectrum, which were analyzed, resulting in a V<sub>3</sub> barrier of 2.4425 ± 0.0025 kJ mol<sup>-1</sup>. By fitting over 250 transitions, we determined accurate rotational constants that enabled us to compare the gas phase geometrical parameters with those of crystalline forms and complexes with progesterone receptors. Our results indicate that the A ring of progesterone that contains the ketone group is surprisingly flexible, despite its rigid appearance. This finding is particularly significant, since this ring is an active biological site that is involved in strong intermolecular interactions. Notably, progesterone C<sub>21</sub>H<sub>30</sub>O<sub>2</sub> is the largest molecule investigated using laser ablation rotational spectroscopy.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"2425-2432"},"PeriodicalIF":4.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143514105","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Solid-State Alder-Ene Reaction of 1-Hexene under High Pressure.
IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-27 DOI: 10.1021/acs.jpclett.4c03696
Jingqin Xu, Puyi Lang, Shijie Liang, Jie Zhang, Yunfan Fei, Yajie Wang, Dexiang Gao, Takanori Hattori, Jun Abe, Xiao Dong, Haiyan Zheng, Kuo Li

The Alder-ene reaction is a chemical reaction between an alkene with an allylic hydrogen, and it provides an efficient method to construct the C-C bond. Traditionally, this reaction requires catalysts, high temperatures, or photocatalysis. In this study, we reported a high-pressure-induced solid-state Alder-ene reaction of 1-hexene at room temperature without a catalyst. 1-Hexene crystallizes at 4.3 GPa and polymerizes at 18 GPa, forming olefins. By exploring gas chromatography-mass spectrometry, we discovered that 1-hexene generates dimeric products through the Alder-ene reaction under high pressures. The in situ neutron diffraction shows that the reaction process did not obey the topochemical rule. A six-membered ring transition state including one C-H σ bond and two alkene π bonds was evidenced by the theoretical calculation, whose energy obviously decreased when compressed to 20 GPa. Our work offers a novel and promising method to realize the Alder-ene reaction at room temperature without a catalyst, expanding the application of this important reaction.

{"title":"Solid-State Alder-Ene Reaction of 1-Hexene under High Pressure.","authors":"Jingqin Xu, Puyi Lang, Shijie Liang, Jie Zhang, Yunfan Fei, Yajie Wang, Dexiang Gao, Takanori Hattori, Jun Abe, Xiao Dong, Haiyan Zheng, Kuo Li","doi":"10.1021/acs.jpclett.4c03696","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03696","url":null,"abstract":"<p><p>The Alder-ene reaction is a chemical reaction between an alkene with an allylic hydrogen, and it provides an efficient method to construct the C-C bond. Traditionally, this reaction requires catalysts, high temperatures, or photocatalysis. In this study, we reported a high-pressure-induced solid-state Alder-ene reaction of 1-hexene at room temperature without a catalyst. 1-Hexene crystallizes at 4.3 GPa and polymerizes at 18 GPa, forming olefins. By exploring gas chromatography-mass spectrometry, we discovered that 1-hexene generates dimeric products through the Alder-ene reaction under high pressures. The <i>in situ</i> neutron diffraction shows that the reaction process did not obey the topochemical rule. A six-membered ring transition state including one C-H σ bond and two alkene π bonds was evidenced by the theoretical calculation, whose energy obviously decreased when compressed to 20 GPa. Our work offers a novel and promising method to realize the Alder-ene reaction at room temperature without a catalyst, expanding the application of this important reaction.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"2445-2451"},"PeriodicalIF":4.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143514201","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Realizing Ultrafine Color Tuning of Organic Electronics Materials by Electronic State Informatics.
IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-27 DOI: 10.1021/acs.jpclett.4c03519
Daisuke Goto, Yusuke Kanebako, Kengo Takashima, Nahoko Kuroki, Hirotoshi Mori

Organic electrochromic (EC) materials enabling energy-efficient smart windows, human-friendly displays, and highly transparent medical lenses are key for a future society. However, developing organic EC molecules that change from transparent to pure magenta, one of the three primary colors, had been impossible through simple quantum chemical calculations and experiments alone, as it requires sophisticated spectral optimization involving multiple electronic transitions in neutral and radical states. In this study, we successfully identified structures exhibiting colorless-to-pure-magenta switching from 1.2 million triphenylamine derivatives using electronic state descriptors easily obtained from semiempirical molecular orbital calculations with qualitative accuracy. Subsequent organic synthesis and spectroelectrochemical experiments proved that the identified candidate molecules achieve the desired functionality.

{"title":"Realizing Ultrafine Color Tuning of Organic Electronics Materials by Electronic State Informatics.","authors":"Daisuke Goto, Yusuke Kanebako, Kengo Takashima, Nahoko Kuroki, Hirotoshi Mori","doi":"10.1021/acs.jpclett.4c03519","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03519","url":null,"abstract":"<p><p>Organic electrochromic (EC) materials enabling energy-efficient smart windows, human-friendly displays, and highly transparent medical lenses are key for a future society. However, developing organic EC molecules that change from transparent to pure magenta, one of the three primary colors, had been impossible through simple quantum chemical calculations and experiments alone, as it requires sophisticated spectral optimization involving multiple electronic transitions in neutral and radical states. In this study, we successfully identified structures exhibiting colorless-to-pure-magenta switching from 1.2 million triphenylamine derivatives using electronic state descriptors easily obtained from semiempirical molecular orbital calculations with qualitative accuracy. Subsequent organic synthesis and spectroelectrochemical experiments proved that the identified candidate molecules achieve the desired functionality.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"2419-2424"},"PeriodicalIF":4.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143514198","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Correction to "Probing the Stability of a β-Hairpin Scaffold after Desolvation".
IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-27 DOI: 10.1021/acs.jpclett.4c03626
Lukas R Benzenberg, Paul Katzberger, Ri Wu, Jonas B Metternich, Sereina Riniker, Renato Zenobi
{"title":"Correction to \"Probing the Stability of a β-Hairpin Scaffold after Desolvation\".","authors":"Lukas R Benzenberg, Paul Katzberger, Ri Wu, Jonas B Metternich, Sereina Riniker, Renato Zenobi","doi":"10.1021/acs.jpclett.4c03626","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03626","url":null,"abstract":"","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"2409"},"PeriodicalIF":4.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143514082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Accelerated Screening of Covalent Organic Frameworks for Ethylene Glycol/1,2-Butanediol Separation by Interpretable Machine Learning.
IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-27 Epub Date: 2025-02-13 DOI: 10.1021/acs.jpclett.4c03333
Yuying Sun, Mengqian Xu, Yunjie Lang, Jing Liu, Dong Zhai, Lei Sun, Weiqiao Deng, Yamin Li, Li Yang

The separation of ethylene glycol (EG) and 1,2-butanediol (1,2-BDO) azeotrope in the synthesis process of EG via coal and biomass is becoming increasingly commercial and of environmental importance. Selective adsorption is deemed as the most promising method because of energy savings and environment favorability. In this study, we developed an interpretable decision tree (DT) model to facilitate high-throughput screening of covalent organic frameworks (COFs) as adsorbents for the separation of EG/1,2-BDO mixtures, achieving an R2 value of 0.96. The interpretable decision tree analysis has shown that using the difference in isosteric heat (ΔQst) between EG (Qst-EG) and 1,2-BDO (Qst-BDO), combined with the largest cavity diameter (LCD), is effective for selecting the optimal COFs for EG/1,2-BDO separation. COFs with ΔQst greater than 6.5 kcal/mol and an LCD ranging from 3.6 to 4.8 Å typically exhibit superior performance and can serve as preselection criteria to accelerate the screening process. Six COFs with high EG working capacity and exceptional adsorption selectivity for EG/1,2-BDO were selected using the selection principle. All the selected COFs containing strong electronegative groups. The electronegative groups can significantly amplify the disparity in adsorption strength between EG and 1,2-BDO, thereby boosting separation efficiency. The principles proposed in this work can be used to guide the design of COFs for effective separation of EG and 1,2-BDO.

在通过煤炭和生物质合成乙二醇(EG)的过程中,乙二醇(EG)和 1,2-丁二醇(1,2-BDO)共沸物的分离越来越具有商业和环保意义。选择性吸附被认为是最有前途的方法,因为它既节能又环保。在这项研究中,我们开发了一种可解释的决策树(DT)模型,以促进高通量筛选共价有机框架(COFs)作为分离 EG/1,2-BDO 混合物的吸附剂,其 R2 值达到 0.96。可解释的决策树分析表明,利用 EG(Qst-EG)和 1,2-BDO(Qst-BDO)之间的等位热量差(ΔQst),结合最大空腔直径(LCD),可以有效地选择用于 EG/1,2-BDO 分离的最佳 COF。ΔQst 大于 6.5 kcal/mol 且 LCD 在 3.6 至 4.8 Å 之间的 COF 通常表现出卓越的性能,可作为加速筛选过程的预选标准。根据这一筛选原则,我们选出了六种具有较高 EG 工作能力和对 EG/1,2-BDO 具有优异吸附选择性的 COF。所有入选的 COF 都含有强电负基团。电负性基团可显著放大 EG 和 1,2-BDO 之间的吸附强度差异,从而提高分离效率。本研究提出的原则可用于指导 COF 的设计,以有效分离 EG 和 1,2-BDO。
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引用次数: 0
High-Resolution Photoelectron Imaging of Cryogenically-Cooled B8- and CB7- Clusters: From Borozene to Carborozene.
IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-27 Epub Date: 2025-02-18 DOI: 10.1021/acs.jpclett.5c00208
Han-Wen Gao, Jie Hui, Lai-Sheng Wang

The closed-shell B73-, B82-, and B9- species are recognized recently to be electron-precise molecular wheels with three delocalized π-bonds reminiscent of benzene, giving rise to the concept of "borozene". The B82- borozene is especially stable because the B7 ring has the right size to host a central boron atom. Replacing a B atom by C yields a highly stable closed-shell CB7-, which is isoelectronic to B82-. Here we use high-resolution cryogenic photoelectron imaging to probe B8- and CB7-, revealing rich vibrational information about B8 and CB7 and the vibrational modes responsible for the structure changes from the anions to the neutrals. Surprisingly, a minor isomer is also observed for B8- and found to be due to Jahn-Teller splitting, analogous to the Jahn-Teller effect in the C6H6+ benzene cation. The transformation from the B82- borozene to the CB7- carborozene is similar to that from the B12H122- borane to the CB11H12- carborane.

{"title":"High-Resolution Photoelectron Imaging of Cryogenically-Cooled B<sub>8</sub><sup>-</sup> and CB<sub>7</sub><sup>-</sup> Clusters: From Borozene to Carborozene.","authors":"Han-Wen Gao, Jie Hui, Lai-Sheng Wang","doi":"10.1021/acs.jpclett.5c00208","DOIUrl":"10.1021/acs.jpclett.5c00208","url":null,"abstract":"<p><p>The closed-shell B<sub>7</sub><sup>3-</sup>, B<sub>8</sub><sup>2-</sup>, and B<sub>9</sub><sup>-</sup> species are recognized recently to be electron-precise molecular wheels with three delocalized π-bonds reminiscent of benzene, giving rise to the concept of \"borozene\". The B<sub>8</sub><sup>2-</sup> borozene is especially stable because the B<sub>7</sub> ring has the right size to host a central boron atom. Replacing a B atom by C yields a highly stable closed-shell CB<sub>7</sub><sup>-</sup>, which is isoelectronic to B<sub>8</sub><sup>2-</sup>. Here we use high-resolution cryogenic photoelectron imaging to probe B<sub>8</sub><sup>-</sup> and CB<sub>7</sub><sup>-</sup>, revealing rich vibrational information about B<sub>8</sub> and CB<sub>7</sub> and the vibrational modes responsible for the structure changes from the anions to the neutrals. Surprisingly, a minor isomer is also observed for B<sub>8</sub><sup>-</sup> and found to be due to Jahn-Teller splitting, analogous to the Jahn-Teller effect in the C<sub>6</sub>H<sub>6</sub><sup>+</sup> benzene cation. The transformation from the B<sub>8</sub><sup>2-</sup> borozene to the CB<sub>7</sub><sup>-</sup> carborozene is similar to that from the B<sub>12</sub>H<sub>12</sub><sup>2-</sup> borane to the CB<sub>11</sub>H<sub>12</sub><sup>-</sup> carborane.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"2039-2046"},"PeriodicalIF":4.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447519","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Large Guest Molecules Selectively Forming sII- or sH-Type Hydrates: Chameleon-Like Behavior
IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-27 DOI: 10.1021/acs.jpclett.4c0369210.1021/acs.jpclett.4c03692
Jiwoong Seol*, 

Over the past decades, extensive research on large guest molecules (LGMs) has shown that a given LGM exclusively forms only a single type of clathrate hydrate (sI, sII, or sH). This study challenges this prevailing understanding by revealing that certain LGMs can selectively form sII- or sH-type hydrates depending on the environment. This study presents various experimental evidence demonstrating that cyclohexylamine and cyclohexanol exhibit chameleon-like behavior, forming sII or sH hydrates when mixed with sII or sH formers, respectively. This intriguing structural modification induced by coguest inclusion is expected to broaden the scope of physicochemical investigations into hydrate materials. Furthermore, this study also suggests that shifting from the traditional approach, which has predominantly focused on single LGMs, could potentially drive breakthroughs in the development and application of sustainable hydrate-based technologies.

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引用次数: 0
Prediction on a Missing Ferroelectric Butterfly Phosphorus Allotrope and Its Energy-Favorable Low-Dimensional Forms.
IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-27 Epub Date: 2025-02-18 DOI: 10.1021/acs.jpclett.5c00257
Yu Han, Hao Gao, Shaobo Yu, Qiuhan Jia, Zhixin Liang, Yunlong Wang, Chi Ding, Junjie Wang, Jian Sun

Elemental phosphorus exhibits a remarkable diversity of allotropes, including black, white, and violet phosphorus, each with unique structural and electronic properties. Recently, phosphorus has experienced a renaissance in scientific interest for its potential applications across various fields. Among these, the red phosphorus (RP) possesses a considerable variety of stacking configurations. By analyzing the preference for the P21 building block in Type II, Type IV, and Type V RP allotropes, we proposed a novel butterfly connected structural scheme. This new structure's stability was well confirmed by ab initio calculations. It is characterized as a semiconductor with a band gap of 1.4 eV, exhibiting a red appearance. Additionally, this structure demonstrates ferroelectric behavior, making it an instance of single-element ferroelectric materials. Furthermore, our investigation of chain-type phosphorus structures within carbon nanotubes (CNTs) revealed that the butterfly type connection scheme represents the lowest energy configuration within specifically sized CNTs.

{"title":"Prediction on a Missing Ferroelectric Butterfly Phosphorus Allotrope and Its Energy-Favorable Low-Dimensional Forms.","authors":"Yu Han, Hao Gao, Shaobo Yu, Qiuhan Jia, Zhixin Liang, Yunlong Wang, Chi Ding, Junjie Wang, Jian Sun","doi":"10.1021/acs.jpclett.5c00257","DOIUrl":"10.1021/acs.jpclett.5c00257","url":null,"abstract":"<p><p>Elemental phosphorus exhibits a remarkable diversity of allotropes, including black, white, and violet phosphorus, each with unique structural and electronic properties. Recently, phosphorus has experienced a renaissance in scientific interest for its potential applications across various fields. Among these, the red phosphorus (RP) possesses a considerable variety of stacking configurations. By analyzing the preference for the P<sub>21</sub> building block in Type II, Type IV, and Type V RP allotropes, we proposed a novel butterfly connected structural scheme. This new structure's stability was well confirmed by <i>ab initio</i> calculations. It is characterized as a semiconductor with a band gap of 1.4 eV, exhibiting a red appearance. Additionally, this structure demonstrates ferroelectric behavior, making it an instance of single-element ferroelectric materials. Furthermore, our investigation of chain-type phosphorus structures within carbon nanotubes (CNTs) revealed that the butterfly type connection scheme represents the lowest energy configuration within specifically sized CNTs.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"2029-2038"},"PeriodicalIF":4.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447523","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 Combined X-ray Absorption and UV-Vis Spectroscopic Study of the Iron-Catalyzed Belousov-Zhabotinsky Reaction.
IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-27 Epub Date: 2025-02-14 DOI: 10.1021/acs.jpclett.4c03490
Giorgio Capocasa, Marika Di Berto Mancini, Federico Frateloreto, Daniele Del Giudice, Osvaldo Lanzalunga, Stefano Di Stefano, Paola D'Angelo, Francesco Tavani

The iron-catalyzed Belousov-Zhabotinsky (BZ) oscillating reaction was investigated in an unstirred reactor by combining Br K-edge X-ray absorption and UV-vis spectroscopies. The experimental data were analyzed through an integrated approach based on principal component analysis, multivariate curve resolution, and ab initio theoretical X-ray absorption spectroscopy (XAS), providing quantitative insights into the properties of the key reaction bromine species while contextually tracking the Fe2+ to Fe3+ oscillatory transformation. The high-quality XAS experimental data supported by the multivariate and theoretical analyses provide clear-cut evidence of the conversion of bromate, initially predominant in the reaction mixture, to the brominated derivative of the employed allylmalonic acid substrate. The described interdisciplinary method was proven to be valuable to monitor the fate of the main BZ reaction brominated species, which are silent to conventional spectroscopic methods of detection, and the developed approach may support future mechanistic investigations of other oscillatory systems.

{"title":"A Combined X-ray Absorption and UV-Vis Spectroscopic Study of the Iron-Catalyzed Belousov-Zhabotinsky Reaction.","authors":"Giorgio Capocasa, Marika Di Berto Mancini, Federico Frateloreto, Daniele Del Giudice, Osvaldo Lanzalunga, Stefano Di Stefano, Paola D'Angelo, Francesco Tavani","doi":"10.1021/acs.jpclett.4c03490","DOIUrl":"10.1021/acs.jpclett.4c03490","url":null,"abstract":"<p><p>The iron-catalyzed Belousov-Zhabotinsky (BZ) oscillating reaction was investigated in an unstirred reactor by combining Br K-edge X-ray absorption and UV-vis spectroscopies. The experimental data were analyzed through an integrated approach based on principal component analysis, multivariate curve resolution, and <i>ab initio</i> theoretical X-ray absorption spectroscopy (XAS), providing quantitative insights into the properties of the key reaction bromine species while contextually tracking the Fe<sup>2+</sup> to Fe<sup>3+</sup> oscillatory transformation. The high-quality XAS experimental data supported by the multivariate and theoretical analyses provide clear-cut evidence of the conversion of bromate, initially predominant in the reaction mixture, to the brominated derivative of the employed allylmalonic acid substrate. The described interdisciplinary method was proven to be valuable to monitor the fate of the main BZ reaction brominated species, which are silent to conventional spectroscopic methods of detection, and the developed approach may support future mechanistic investigations of other oscillatory systems.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"1840-1846"},"PeriodicalIF":4.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11873914/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143412421","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Determining the Molecular Shape of Progesterone: Insights from Laser Ablation Rotational Spectroscopy
IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-27 DOI: 10.1021/acs.jpclett.4c0361810.1021/acs.jpclett.4c03618
Aran Insausti, Elena R. Alonso*, Sofía Municio, Iker León, Lucie Kolesniková and Santiago Mata, 

Herein, we present the first experimental observation of isolated progesterone, an endogenous steroid, placed in the gas phase by laser ablation and characterized in a supersonic expansion by Fourier transform microwave techniques. Guided by quantum-chemical calculations, we assigned the rotational spectrum of the most stable structure. The internal rotation of the acetyl methyl group led to the observation of A-E doublets in the spectrum, which were analyzed, resulting in a V3 barrier of 2.4425 ± 0.0025 kJ mol–1. By fitting over 250 transitions, we determined accurate rotational constants that enabled us to compare the gas phase geometrical parameters with those of crystalline forms and complexes with progesterone receptors. Our results indicate that the A ring of progesterone that contains the ketone group is surprisingly flexible, despite its rigid appearance. This finding is particularly significant, since this ring is an active biological site that is involved in strong intermolecular interactions. Notably, progesterone C21H30O2 is the largest molecule investigated using laser ablation rotational spectroscopy.

{"title":"Determining the Molecular Shape of Progesterone: Insights from Laser Ablation Rotational Spectroscopy","authors":"Aran Insausti,&nbsp;Elena R. Alonso*,&nbsp;Sofía Municio,&nbsp;Iker León,&nbsp;Lucie Kolesniková and Santiago Mata,&nbsp;","doi":"10.1021/acs.jpclett.4c0361810.1021/acs.jpclett.4c03618","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03618https://doi.org/10.1021/acs.jpclett.4c03618","url":null,"abstract":"<p >Herein, we present the first experimental observation of isolated progesterone, an endogenous steroid, placed in the gas phase by laser ablation and characterized in a supersonic expansion by Fourier transform microwave techniques. Guided by quantum-chemical calculations, we assigned the rotational spectrum of the most stable structure. The internal rotation of the acetyl methyl group led to the observation of A-E doublets in the spectrum, which were analyzed, resulting in a V<sub>3</sub> barrier of 2.4425 ± 0.0025 kJ mol<sup>–1</sup>. By fitting over 250 transitions, we determined accurate rotational constants that enabled us to compare the gas phase geometrical parameters with those of crystalline forms and complexes with progesterone receptors. Our results indicate that the A ring of progesterone that contains the ketone group is surprisingly flexible, despite its rigid appearance. This finding is particularly significant, since this ring is an active biological site that is involved in strong intermolecular interactions. Notably, progesterone C<sub>21</sub>H<sub>30</sub>O<sub>2</sub> is the largest molecule investigated using laser ablation rotational spectroscopy.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 9","pages":"2425–2432 2425–2432"},"PeriodicalIF":4.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547701","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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The Journal of Physical Chemistry Letters
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