Marwan El Chazli, Juan Francisco Bada Juarez, Louis W. Perrin, Jiajie Gao, Chan Cao
{"title":"Enhanced Analytes Capture by Engineering Electrostatics at the Entry of Aerolysin Nanopore","authors":"Marwan El Chazli, Juan Francisco Bada Juarez, Louis W. Perrin, Jiajie Gao, Chan Cao","doi":"10.1002/hlca.202400180","DOIUrl":"https://doi.org/10.1002/hlca.202400180","url":null,"abstract":"<p>Nanopore technology is a powerful single-molecule platform for detecting and sequencing a wide range of biomolecules. Among nanopores, aerolysin has emerged as a particularly promising candidate for peptide sensing. However, its ability to capture long biopolymers is limited due to its lack of a vestibule structure. In this study, we engineered electrostatics at the entry of the aerolysin pore and observed an increase in event frequency – up to 2 times higher for DNA and for the peptide compared to wild-type aerolysin. Importantly, this modification did not affect the pore's current-voltage characteristics. When tested with DNA and α-synuclein peptides, the engineered pore (D209R) exhibited comparable dwell times and current blockages to the wild-type pore, while ion selectivity and electroosmotic flux show an increase. These findings highlight that fine-tuning the electrostatic properties at the pore entry can significantly enhance event frequency without compromising key transport properties such as current blockage or dwell time. This improvement expands the utility of aerolysin nanopores for sensing and sequencing applications and paves the way for more effective diagnostic tools and analytical methods in the field of proteomics and biomarker discovery.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"108 6","pages":""},"PeriodicalIF":1.5,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144292274","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Introduction for the Special Collection of Papers in the Honor of the President of the 57th Bürgenstock Conference, Erick M. Carreira","authors":"","doi":"10.1002/hlca.202500069","DOIUrl":"https://doi.org/10.1002/hlca.202500069","url":null,"abstract":"<p>\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"108 6","pages":""},"PeriodicalIF":1.5,"publicationDate":"2025-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500069","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144291790","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Efficient Polymer Functionalization by Means of Extreme Ultraviolet","authors":"Di Qu, Minglei Wang, Léonard Bezinge, Celine Hensky, Filippo Longo, Claudia Masucci, Mirushe Suloska, Jing Wang, Davide Bleiner","doi":"10.1002/hlca.202400100","DOIUrl":"https://doi.org/10.1002/hlca.202400100","url":null,"abstract":"<p>Extreme ultraviolet (XUV) radiation is highly efficient for functionalization of solid materials by means of pronounced radical formation. To prevent collective effects, and study single photon effects, a low-fluence XUV source with 200 μJ/cm<sup>2</sup> was used to irradiate polymers such as poly-methyl methacrylate (PMMA) and poly-tetrafluoroethylene (PTFE). The unexposed and XUV-exposed sample domains were analyzed with time-of-flight secondary ion mass spectrometry (TOF-SIMS), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). The findings show that XUV photons drive photochemical modification of the surface, fragmentation, and ionization of the desorbed products. Besides a theoretical analysis, the XUV-induced surface modification of PTFE is discussed a new application for surface functionalization.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"108 5","pages":""},"PeriodicalIF":1.5,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144074724","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kirill M. Kuznetsov, Kallol Purkait, Pierre Mesdom, Philippe Arnoux, Céline Frochot, Kevin Cariou, Gilles Gasser
{"title":"Synthesis, Characterization, and Biological Evaluation of Red Light-Activatable BODIPY-Caged Ceritinib Compounds","authors":"Kirill M. Kuznetsov, Kallol Purkait, Pierre Mesdom, Philippe Arnoux, Céline Frochot, Kevin Cariou, Gilles Gasser","doi":"10.1002/hlca.202500023","DOIUrl":"https://doi.org/10.1002/hlca.202500023","url":null,"abstract":"<p>In this work, we aimed at photocaging the well-known anticancer agents dasatinib, ceritinib, gemcitabine, and combretastatin A4 with red-light activatable 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-based cages using a carbonate/carbamate linking strategy. Due to the synthetic challenges discussed in this article, we only obtained two target compounds, namely two caged ceritinib compounds. The latter were characterized in-depth by nuclear magnetic resonance spectroscopy (NMR, <sup>1</sup>H, COSY, <sup>13</sup>C), high-resolution mass spectrometry (HRMS), infrared (IR) spectroscopy, and their purity was evaluated by elemental analysis. Their photophysical characteristics were also measured including absorption and emission spectra, quantum yields, and lifetimes. Analysis of the products after irradiation of the compounds allowed us to make assumptions about the possible mechanism of the phototransformations. Moreover, we conducted biological studies to determine the phototoxicity indexes of A549 cancer cells. While the two compounds were found to be non-toxic, the BODIPY precursors themselves were found to be highly toxic upon irradiation with phototoxicity indexes up to 1400.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"108 6","pages":""},"PeriodicalIF":1.5,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500023","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144292275","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Blue Fluorescent Chlorophyll Catabolites from Banana Leaves Hypermodified with Terpenoidic Groups Related to Abscisic Acid","authors":"Clemens Vergeiner, Bernhard Kräutler","doi":"10.1002/hlca.202500042","DOIUrl":"https://doi.org/10.1002/hlca.202500042","url":null,"abstract":"<p>In senescent leaves of banana (<i>Musa acuminata</i>) hypermodified fluorescent chlorophyll (Chl) catabolites (<i>hm</i>FCCs) accumulate and give these leaves an easily observable blue fluorescence. Non-fluorescent Chl-catabolites (NCCs) are not detected, the typical colourless Chl-catabolites that accumulate in most de-greened plant leaves. Here, we report the isolation and spectroscopic structural characterization of two very lipophilic <i>hm</i>FCCs, named <i>Ma</i>-FCC-78 and <i>Ma</i>-FCC-79. These two novel <i>Ma</i>-FCCs are hypermodified with megastigmane (Megs) residues, terpenoids related to the plant hormone abscisic acid (ABA). Thus, these hypermodified <i>Ma</i>-FCCs from senescent banana leaves may possibly play novel physiological roles, on the one hand, in the regulation of stress response, a fundamental role of ABA, on the other hand, by providing some of the cytotoxic, antibacterial and antioxidant activities of Megs.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"108 6","pages":""},"PeriodicalIF":1.5,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500042","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144292428","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Giulia Coffetti, Giorgio Facchetti, Alessandro Ajò, Isabella Rimoldi, Luisa De Cola
{"title":"Breakable Nanomaterials to Allow Hair Coloring with Natural Dyes","authors":"Giulia Coffetti, Giorgio Facchetti, Alessandro Ajò, Isabella Rimoldi, Luisa De Cola","doi":"10.1002/hlca.202500007","DOIUrl":"https://doi.org/10.1002/hlca.202500007","url":null,"abstract":"<p>The use of melanin as a colorant has been significantly limited by its low solubility and the difficulty of penetrating the hair shaft or follicles. However, the proposed nanotechnological approach demonstrates that it is possible to encapsulate a melanin precursor, 5,6-dihydroxyindole (DHI), within breakable particles and trigger its oxidation into insoluble black melanin, which can be released upon the degradation of the carrier using UV light. This process can be monitored via UV spectroscopy and has also been successfully tested on hair. In fact, when applied to human white hair, the result was a brownish coloration, with melanin naturally formed and adsorbed by the hair. This mild and harmless method shows great promise for the development of nanoparticles capable of penetrating hair follicles, potentially enabling natural hair pigmentation at the roots.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"108 6","pages":""},"PeriodicalIF":1.5,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500007","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144292605","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Enhanced Photocatalytic Alkylation using Mg(SPh)2: The Role of Lewis Acidity in Catalyst Activity","authors":"Yasuhiro Yamashita, Tomoya Hisada, Yuki Sato, Shū Kobayashi","doi":"10.1002/hlca.202400207","DOIUrl":"https://doi.org/10.1002/hlca.202400207","url":null,"abstract":"<p>The role of Mg(SPh)<sub>2</sub> on photocatalytic alkylation of an active methylene with a nonactivated alkene was investigated. Kinetic studies indicate that one-electron oxidation of a Mg enolate is the rate-determining step. ESR experiments suggest an interaction between Lewis acidic metals and a radical anion species of 4CzIPN. These results suggest that the higher Lewis acidity of Mg(SPh)<sub>2</sub> stabilizes the 4CzIPN radical anion species to enhance its relative abundance and might influence both the one-electron oxidation step and the radical addition step in the catalytic cycle, leading to enhanced reaction efficiency.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"108 5","pages":""},"PeriodicalIF":1.5,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400207","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144074770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}