{"title":"Determination of Methyl Group Positions in Long-Chain Aliphatic Methyl Ethers and Alcohols by Gas Chromatography/Orbitrap Mass Spectrometry.","authors":"Tatsuya Kiuchi,Moritz Gerbaulet,Anton Möllerke,Tim Harig,Axel Dinter,Till Beuerle,Stefan Schulz","doi":"10.1021/acs.analchem.5c03083","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03083","url":null,"abstract":"Methylated long-chain aliphatic compounds such as terminal methyl ethers are a common compound type found on the epicuticular layer of arthropods, e.g., spiders. Because complex mixtures are encountered in small amounts when analyzing these mixtures, GC/MS is the method of choice for characterizing the individual constituents. However, the methyl branch location cannot be deduced from the original spectra due to the easy loss of methanol, resulting in nonspecific spectra, and a complex derivatization scheme has been employed to address this issue. We noted that although mass spectra obtained by EI-quadrupol and EI-Orbitrap ionization are superficially quite similar, a +2.0 V C-trap offset of the latter leads to reduced fragmentation. The high-resolution Orbitrap spectra contain enough information to allow for methyl group localization in the chain. However, the spectra of the methyl ethers contain many ions, making individual analysis quite time-consuming. Therefore, scripts using Excel and R were developed with the help of ChatGPT 4.0, resulting in ion series spectra (ISS) that contained only ions of a specific ion series. The analysis of 11 synthetic methyl ethers showed that especially the ion series CnH2n+1O (ISS45) and CnH2n-2 (ISS40) are of high diagnostic value, together with some methoxy group-induced fragmentation. The approach was successfully tested with lipids from the spider Tetragnatha versicolor, which had been previously analyzed by derivatization, and with web extracts of Erigone atra, revealing 1-methoxy-2,16-dimethylhenicosane as a male-specific component─the first spider methyl ether in a volatility range that would allow detection via the gas phase. This approach can also be applied to structurally related primary alcohols, although the diagnostic ions are of lower intensity.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"132 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719903","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Efficient Entropy-Driven Cross-Double-Loop Reaction Cascade Asymmetric CRISPR/Cas12a Cleavage for Ultrasensitive Electrochemical Biosensing.","authors":"Xudong Zhou,Rui Zhang,Luguang Cai,Hang Fu,Ding Wang,Ruo Yuan,Yali Yuan","doi":"10.1021/acs.analchem.5c02014","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c02014","url":null,"abstract":"The limited signal amplification efficiency of the conventional CRISPR/Cas12a-cleavage system was primarily due to the structural constraints of crRNA and single-trigger activation. Herein, an efficient target-induced entropy-driven cross-double-loop strand displacement reaction (SDR) cascade asymmetric CRISPR/Cas12a cleavage was developed to construct an ultrasensitive and reliable signal-off electrochemical biosensor. The desirable entropy-driven modulation could spontaneously undergo a cross-double-loop reaction that possessed self-accelerating ability, effectively improving the rate of chain replacement and avoiding the usage of extra fuel chains with generation of two abundant distinct DNA outputs, significantly improving target conversion efficiency. More importantly, all the targets and two distinct DNA outputs could simultaneously act as activators in the asymmetric CRISPR/Cas12a system, which cooperatively bound to both split and full-sized crRNAs to accomplish the highly efficient discharge of ferrocene-labeled single-stranded DNA (Fc-reporter) on the electrode, thereby markedly improving the detection sensitivity and reliably compared to that of traditional ones. The experimental results suggested that the proposed biosensor had a wide linear range spanning from 1 fM to1 nM with a detection limit as low as 0.23 fM. By integrating entropy-driven amplification with CRISPR-enhanced signal transduction, this work established a versatile and robust analytical tool for early cancer diagnosis and precision biomolecular detection.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"111 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719977","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"A General Strategy for Triggerable Donors and Analyte-Replacement Fluorescent Probes of Hydrogen Selenide.","authors":"Wenfang Liang,Yalun Dong,Long Yi","doi":"10.1021/acs.analchem.5c03272","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03272","url":null,"abstract":"Hydrogen selenide (H2Se) is the precursor for biosynthesis of Se-containing biomolecules and a potential nitric oxide (NO)-like gasotransmitter. Chemical tools for H2Se delivery and detection are crucial for exploring selenium (Se) biology and medicine. Nevertheless, general platforms for triggerable release of H2Se remain lacking, and H2Se fluorescent probes that do not irreversibly consume H2Se have not yet been reported. Herein, we report a general platform of the fast intramolecular arylthiol-activated arylselenoamides (general FITA) for H2Se donation and detection. We utilized self-immolative processes to controllable deprotection of an arylthiol for the tandem FITA and developed the first examples of nitroreductase-triggered and reactive oxygen species-triggered H2Se donors. We leveraged the general FITA motif to construct the first H2Se analyte-replacement probe which, upon reaction with a H2Se, generates a fluorescence response and releases a H2Se, thus underscoring the analyte homeostasis during detection of the H2Se donation. We anticipate that these well-defined chemistries will promote the development of advanced H2Se tools with therapeutic potential.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"1 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719978","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Au@Pt DNA Nanomachine Coupled with Photonic Crystal Microchip Enables High-Fidelity and Portable miRNA Detection.","authors":"Jing Li,Ruirui Chang,Wei Zhang,Yiting Lan,Dengxue Qiu,Chuanli Ren,Jin Huang,Qin Xu","doi":"10.1021/acs.analchem.5c02942","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c02942","url":null,"abstract":"Although great headway has been made in 3D DNA nanomachines, built from DNA-functionalized gold nanoparticles (Au NPs), for sensitive miRNA detection in complex media, their stability, accessibility, and portability still need to be improved. To surmount these hurdles, we are the first to develop a new way to integrate a Au@Pt (Pt-coated Au NPs) DNA nanomachine with a photonic crystal (PC) microchip for accurate and portable miRNA detection. Leveraging Au@Pt, characterized by ultraslow ligand exchange rate, as the core of 3D DNA nanomachines endows Au@Pt DNA nanomachine superior stability and signal fidelity. Meanwhile, a PC microchip capable of fluorescence enhancement capability acts as a solid-phase sensor chip, enabling on-site and portable miRNA-21 detection by interfacing with a miniaturized UV lamp device and a smartphone equipped with color recognition software. This newly developed sensor exhibits a swift response to miRNA, remarkable stability, and robust resistance to biothiols, as well as a high sensitivity (LOD as low as 0.144 pM). Clinical validation demonstrates its excellent diagnostic accuracy (AUC = 1) in the detection of miRNA-21 in patient serum, providing a paradigm for on-site and portable miRNA detection in areas with limited resources and equipment.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"50 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144720369","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}