Pub Date : 2024-07-05DOI: 10.1021/acs.analchem.4c00319
Ivana Pennisi, Matthew L Cavuto, Luca Miglietta, Kenny Malpartida-Cardenas, Oliver W Stringer, Katerina-Theresa Mantikas, Ruth Reid, Rebecca Frise, Nicolas Moser, Paul Randell, Frances Davies, Frances Bolt, Wendy Barclay, Alison Holmes, Pantelis Georgiou, Jesus Rodriguez-Manzano
The COVID-19 pandemic has highlighted the need for rapid and reliable diagnostics that are accessible in resource-limited settings. To address this pressing issue, we have developed a rapid, portable, and electricity-free method for extracting nucleic acids from respiratory swabs (i.e. nasal, nasopharyngeal and buccal swabs), successfully demonstrating its effectiveness for the detection of SARS-CoV-2 in residual clinical specimens. Unlike traditional approaches, our solution eliminates the need for micropipettes or electrical equipment, making it user-friendly and requiring little to no training. Our method builds upon the principles of magnetic bead extraction and revolves around a low-cost plastic magnetic lid, called SmartLid, in combination with a simple disposable kit containing all required reagents conveniently prealiquoted. Here, we clinically validated the SmartLid sample preparation method in comparison to the gold standard QIAamp Viral RNA Mini Kit from QIAGEN, using 406 clinical isolates, including 161 SARS-CoV-2 positives, using the SARS-CoV-2 RT-qPCR assays developed by the US Centers for Disease Control and Prevention (CDC). The SmartLid method showed an overall sensitivity of 95.03% (95% CI: 90.44-97.83%) and a specificity of 99.59% (95% CI: 97.76-99.99%), with a positive agreement of 97.79% (95% CI: 95.84-98.98%) when compared to QIAGEN's column-based extraction method. There are clear benefits to using the SmartLid sample preparation kit: it enables swift extraction of viral nucleic acids, taking less than 5 min, without sacrificing significant accuracy when compared to more expensive and time-consuming alternatives currently available on the market. Moreover, its simplicity makes it particularly well-suited for the point-of-care where rapid results and portability are crucial. By providing an efficient and accessible means of nucleic acid extraction, our approach aims to introduce a step-change in diagnostic capabilities for resource-limited settings.
{"title":"Rapid, Portable, and Electricity-free Sample Extraction Method for Enhanced Molecular Diagnostics in Resource-Limited Settings.","authors":"Ivana Pennisi, Matthew L Cavuto, Luca Miglietta, Kenny Malpartida-Cardenas, Oliver W Stringer, Katerina-Theresa Mantikas, Ruth Reid, Rebecca Frise, Nicolas Moser, Paul Randell, Frances Davies, Frances Bolt, Wendy Barclay, Alison Holmes, Pantelis Georgiou, Jesus Rodriguez-Manzano","doi":"10.1021/acs.analchem.4c00319","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c00319","url":null,"abstract":"<p><p>The COVID-19 pandemic has highlighted the need for rapid and reliable diagnostics that are accessible in resource-limited settings. To address this pressing issue, we have developed a rapid, portable, and electricity-free method for extracting nucleic acids from respiratory swabs (i.e. nasal, nasopharyngeal and buccal swabs), successfully demonstrating its effectiveness for the detection of SARS-CoV-2 in residual clinical specimens. Unlike traditional approaches, our solution eliminates the need for micropipettes or electrical equipment, making it user-friendly and requiring little to no training. Our method builds upon the principles of magnetic bead extraction and revolves around a low-cost plastic magnetic lid, called SmartLid, in combination with a simple disposable kit containing all required reagents conveniently prealiquoted. Here, we clinically validated the SmartLid sample preparation method in comparison to the gold standard QIAamp Viral RNA Mini Kit from QIAGEN, using 406 clinical isolates, including 161 SARS-CoV-2 positives, using the SARS-CoV-2 RT-qPCR assays developed by the US Centers for Disease Control and Prevention (CDC). The SmartLid method showed an overall sensitivity of 95.03% (95% CI: 90.44-97.83%) and a specificity of 99.59% (95% CI: 97.76-99.99%), with a positive agreement of 97.79% (95% CI: 95.84-98.98%) when compared to QIAGEN's column-based extraction method. There are clear benefits to using the SmartLid sample preparation kit: it enables swift extraction of viral nucleic acids, taking less than 5 min, without sacrificing significant accuracy when compared to more expensive and time-consuming alternatives currently available on the market. Moreover, its simplicity makes it particularly well-suited for the point-of-care where rapid results and portability are crucial. By providing an efficient and accessible means of nucleic acid extraction, our approach aims to introduce a step-change in diagnostic capabilities for resource-limited settings.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532874","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}
Pub Date : 2024-07-05DOI: 10.1021/acssensors.4c00745
Zhuo Liu, He Lv, Yuchi Zhang, Jian Wang He, Le Han, Shuang Li, Lin Yang, Yan Xu
Limited by insufficient active sites and restricted mechanical strength, designing reliable and wearable gas sensors with high activity and ductility remains a challenge for detecting hazardous gases. In this work, a thermally induced and solvent-assisted oxyanion etching strategy was implemented for selective pore opening in a rigid microporous Cu-based metal-organic framework (referred to as CuM). A conductive CuM/MXene aerogel was then self-assembled through cooperative hydrogen bonding interactions between the carbonyl oxygen atom in PVP grafted on the surface of defect-rich Cu-BTC and the surface functional hydroxyl group on MXene. A flexible NO2 sensing performance using the CuM/MXene aerogel hybridized sodium alginate hydrogel is finally achieved, demonstrating extraordinary sensitivity (S = 52.47 toward 50 ppm of NO2), good selectivity, and rapid response/recovery time (0.9/4.5 s) at room temperature. Compared with commercial sensors, the relative error is less than 7.7%, thereby exhibiting significant potential for application in monitoring toxic and harmful gases. This work not only provides insights for guiding rational synthesis of ideal structure models from MOF composites but also inspires the development of high-performance flexible gas sensors for potential multiscenario applications.
{"title":"Synergistic Etching and Hydrogen Bonding-Induced Self-Assembly of MXene/MOF Hybrid Aerogel for Flexible Room-Temperature Gas Sensing.","authors":"Zhuo Liu, He Lv, Yuchi Zhang, Jian Wang He, Le Han, Shuang Li, Lin Yang, Yan Xu","doi":"10.1021/acssensors.4c00745","DOIUrl":"https://doi.org/10.1021/acssensors.4c00745","url":null,"abstract":"<p><p>Limited by insufficient active sites and restricted mechanical strength, designing reliable and wearable gas sensors with high activity and ductility remains a challenge for detecting hazardous gases. In this work, a thermally induced and solvent-assisted oxyanion etching strategy was implemented for selective pore opening in a rigid microporous Cu-based metal-organic framework (referred to as CuM). A conductive CuM/MXene aerogel was then self-assembled through cooperative hydrogen bonding interactions between the carbonyl oxygen atom in PVP grafted on the surface of defect-rich Cu-BTC and the surface functional hydroxyl group on MXene. A flexible NO<sub>2</sub> sensing performance using the CuM/MXene aerogel hybridized sodium alginate hydrogel is finally achieved, demonstrating extraordinary sensitivity (<i>S</i> = 52.47 toward 50 ppm of NO<sub>2</sub>), good selectivity, and rapid response/recovery time (0.9/4.5 s) at room temperature. Compared with commercial sensors, the relative error is less than 7.7%, thereby exhibiting significant potential for application in monitoring toxic and harmful gases. This work not only provides insights for guiding rational synthesis of ideal structure models from MOF composites but also inspires the development of high-performance flexible gas sensors for potential multiscenario applications.</p>","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":null,"pages":null},"PeriodicalIF":8.2,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532848","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}
Pub Date : 2024-07-05DOI: 10.1021/acsbiomaterials.4c00445
Hakan Berk Aydin, Altug Ozcelikkale, Ahmet Acar
Drug resistance is arguably one of the biggest challenges facing cancer research today. Understanding the underlying mechanisms of drug resistance in tumor progression and metastasis are essential in developing better treatment modalities. Given the matrix stiffness affecting the mechanotransduction capabilities of cancer cells, characterization of the related signal transduction pathways can provide a better understanding for developing novel therapeutic strategies. In this review, we aimed to summarize the recent advancements in tumor matrix biology in parallel to therapeutic approaches targeting matrix stiffness and its consequences in cellular processes in tumor progression and metastasis. The cellular processes governed by signal transduction pathways and their aberrant activation may result in activating the epithelial-to-mesenchymal transition, cancer stemness, and autophagy, which can be attributed to drug resistance. Developing therapeutic strategies to target these cellular processes in cancer biology will offer novel therapeutic approaches to tailor better personalized treatment modalities for clinical studies.
{"title":"Exploiting Matrix Stiffness to Overcome Drug Resistance.","authors":"Hakan Berk Aydin, Altug Ozcelikkale, Ahmet Acar","doi":"10.1021/acsbiomaterials.4c00445","DOIUrl":"https://doi.org/10.1021/acsbiomaterials.4c00445","url":null,"abstract":"<p><p>Drug resistance is arguably one of the biggest challenges facing cancer research today. Understanding the underlying mechanisms of drug resistance in tumor progression and metastasis are essential in developing better treatment modalities. Given the matrix stiffness affecting the mechanotransduction capabilities of cancer cells, characterization of the related signal transduction pathways can provide a better understanding for developing novel therapeutic strategies. In this review, we aimed to summarize the recent advancements in tumor matrix biology in parallel to therapeutic approaches targeting matrix stiffness and its consequences in cellular processes in tumor progression and metastasis. The cellular processes governed by signal transduction pathways and their aberrant activation may result in activating the epithelial-to-mesenchymal transition, cancer stemness, and autophagy, which can be attributed to drug resistance. Developing therapeutic strategies to target these cellular processes in cancer biology will offer novel therapeutic approaches to tailor better personalized treatment modalities for clinical studies.</p>","PeriodicalId":8,"journal":{"name":"ACS Biomaterials Science & Engineering","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532864","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-05DOI: 10.1021/acs.nanolett.4c01581
Ruixia Zhong, Zhongzheng Yang, Qi Wang, Fanbang Zheng, Wenhui Li, Juefei Wu, Chenhaoping Wen, Xi Chen, Yanpeng Qi, Shichao Yan
By using low-temperature scanning tunneling microscopy and spectroscopy (STM/STS), we observe in-gap states induced by Andreev tunneling through a single impurity state in a low carrier density superconductor (NaAlSi). The energy-symmetric in-gap states appear when the impurity state is located within the superconducting gap. In-gap states can cross the Fermi level, and they show X-shaped spatial variation. We interpret the in-gap states as a consequence of the Andreev tunneling through the impurity state, which involves the formation or breakup of a Cooper pair. Due to the low carrier density in NaAlSi, the in-gap state is tunable by controlling the STM tip-sample distance. Under strong external magnetic fields, the impurity state shows Zeeman splitting when it is located near the Fermi level. Our findings not only demonstrate the Andreev tunneling involving single electronic state but also provide new insights for understanding the spatially dependent in-gap states in low carrier density superconductors.
通过使用低温扫描隧道显微镜和光谱学(STM/STS),我们在低载流子密度超导体(NaAlSi)中观察到了安德烈耶夫隧道通过单一杂质态诱导的隙内态。当杂质态位于超导间隙内时,就会出现能量对称的内隙态。内隙态可以跨越费米级,并呈现出 X 型空间变化。我们将这些内隙态解释为安德烈耶夫隧穿杂质态的结果,其中涉及库珀对的形成或断裂。由于 NaAlSi 中的载流子密度较低,因此可通过控制 STM 尖端与样品的距离来调整内隙态。在强外部磁场作用下,杂质态位于费米级附近时会出现泽曼分裂。我们的发现不仅证明了涉及单电子态的安德烈耶夫隧道现象,而且为理解低载流子密度超导体中空间依赖性内隙态提供了新的见解。
{"title":"Spatially Dependent in-Gap States Induced by Andreev Tunneling through a Single Electronic State.","authors":"Ruixia Zhong, Zhongzheng Yang, Qi Wang, Fanbang Zheng, Wenhui Li, Juefei Wu, Chenhaoping Wen, Xi Chen, Yanpeng Qi, Shichao Yan","doi":"10.1021/acs.nanolett.4c01581","DOIUrl":"https://doi.org/10.1021/acs.nanolett.4c01581","url":null,"abstract":"<p><p>By using low-temperature scanning tunneling microscopy and spectroscopy (STM/STS), we observe in-gap states induced by Andreev tunneling through a single impurity state in a low carrier density superconductor (NaAlSi). The energy-symmetric in-gap states appear when the impurity state is located within the superconducting gap. In-gap states can cross the Fermi level, and they show X-shaped spatial variation. We interpret the in-gap states as a consequence of the Andreev tunneling through the impurity state, which involves the formation or breakup of a Cooper pair. Due to the low carrier density in NaAlSi, the in-gap state is tunable by controlling the STM tip-sample distance. Under strong external magnetic fields, the impurity state shows Zeeman splitting when it is located near the Fermi level. Our findings not only demonstrate the Andreev tunneling involving single electronic state but also provide new insights for understanding the spatially dependent in-gap states in low carrier density superconductors.</p>","PeriodicalId":53,"journal":{"name":"Nano Letters","volume":null,"pages":null},"PeriodicalIF":9.6,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532789","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-05DOI: 10.1021/acs.orglett.4c02128
Álvaro Martínez-Pinel, Luis Lezama, Juan M Cuerva, Raquel Casares, Víctor Blanco, Carlos M Cruz, Alba Millán
We report the synthesis and study of the optoelectronic, magnetic, and chiroptical properties of a helically chiral diradicaloid based on dibenzoindeno[2,1-c]fluorene. The molecule shows a small HOMO-LUMO gap and a moderate singlet-triplet gap, which agrees with the results of DFT calculations. The helical structure of the compound, confirmed by X-ray diffraction, is configurationally stable, which allows the isolation of both enantiomers and the evaluation of the chiroptical properties (ECD).
我们报告了一种基于二苯并茚并[2,1-c]芴的螺旋手性二维类化合物的合成及其光电、磁性和气光性质研究。该分子显示出较小的 HOMO-LUMO 间隙和适度的单线-三线间隙,这与 DFT 计算的结果一致。经 X 射线衍射证实,该化合物的螺旋结构在构型上是稳定的,因此可以分离出两种对映体并评估其气光性质(ECD)。
{"title":"A Configurationally Stable Helical Indenofluorene.","authors":"Álvaro Martínez-Pinel, Luis Lezama, Juan M Cuerva, Raquel Casares, Víctor Blanco, Carlos M Cruz, Alba Millán","doi":"10.1021/acs.orglett.4c02128","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c02128","url":null,"abstract":"<p><p>We report the synthesis and study of the optoelectronic, magnetic, and chiroptical properties of a helically chiral diradicaloid based on dibenzoindeno[2,1-<i>c</i>]fluorene. The molecule shows a small HOMO-LUMO gap and a moderate singlet-triplet gap, which agrees with the results of DFT calculations. The helical structure of the compound, confirmed by X-ray diffraction, is configurationally stable, which allows the isolation of both enantiomers and the evaluation of the chiroptical properties (ECD).</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532791","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}
Pub Date : 2024-07-05DOI: 10.1021/acs.langmuir.4c01550
Yaning Liu, Yuhan Yang, Wei Cheng, Ziyao Ma, Nan Gao, Hongdong Li
The toxic gases emitted from industrial production have caused significant damage to the environment and human health, necessitating efficient gas sensors for their detection and removal. In this work, first-principles calculations are employed to investigate the potential application of diamanes for high-performance toxic gas sensors. The results show that nine gas molecules (CO, CO2, NO, NO2, NH3, SO2, N2, O2, and H2O) are physisorbed on pristine diamane by weak van der Waals interactions. After introducing H/F defects, diamane can effectively capture specific toxic gases (CO, NO, NO2, and SO2) in the presence of interfering gases (N2, O2, and H2O), suggesting excellent selectivity and anti-interference ability. Orbital hybridization and significant charge redistribution between gas molecules and defective diamane dominate the enhanced adsorbate-substrate interactions. More importantly, the high sensitivity and good reversibility of defective diamane for detecting CO, NO, and SO2 molecules enable its reuse as a superior resistance-type gas sensor. Our calculations provide valuable insights into the potential of defective diamane for detecting toxic gases and shed light on the practical application of novel carbon-based materials in the gas-sensing field.
{"title":"Defective Diamane: A Superior Sensor for Toxic Gases Capture and Detection with Excellent Selectivity, Sensitivity, and Reversibility at Room Temperature.","authors":"Yaning Liu, Yuhan Yang, Wei Cheng, Ziyao Ma, Nan Gao, Hongdong Li","doi":"10.1021/acs.langmuir.4c01550","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01550","url":null,"abstract":"<p><p>The toxic gases emitted from industrial production have caused significant damage to the environment and human health, necessitating efficient gas sensors for their detection and removal. In this work, first-principles calculations are employed to investigate the potential application of diamanes for high-performance toxic gas sensors. The results show that nine gas molecules (CO, CO<sub>2</sub>, NO, NO<sub>2</sub>, NH<sub>3</sub>, SO<sub>2</sub>, N<sub>2</sub>, O<sub>2</sub>, and H<sub>2</sub>O) are physisorbed on pristine diamane by weak van der Waals interactions. After introducing H/F defects, diamane can effectively capture specific toxic gases (CO, NO, NO<sub>2</sub>, and SO<sub>2</sub>) in the presence of interfering gases (N<sub>2</sub>, O<sub>2</sub>, and H<sub>2</sub>O), suggesting excellent selectivity and anti-interference ability. Orbital hybridization and significant charge redistribution between gas molecules and defective diamane dominate the enhanced adsorbate-substrate interactions. More importantly, the high sensitivity and good reversibility of defective diamane for detecting CO, NO, and SO<sub>2</sub> molecules enable its reuse as a superior resistance-type gas sensor. Our calculations provide valuable insights into the potential of defective diamane for detecting toxic gases and shed light on the practical application of novel carbon-based materials in the gas-sensing field.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532832","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}
Donor-acceptor-based organic small molecules with an electronic push-pull effect can demonstrate intramolecular charge transfer to show interesting photoluminescence properties. This is an essential criterion for designing fluorogenic probes for cell imaging studies and the development of organic light-emitting diodes. Now, to design such optical materials sometimes it is necessary to tune the band gap by controlling the energies of the highest occupied molecular orbital and lowest unoccupied molecular orbital. Typically, the band gaps could be modulated by installing unsaturated handles between electron-rich donors and electron-deficient acceptors. However, these methods are often synthetically and economically challenging due to the involvement of expensive catalysts and difficult reaction setups. In our present study, we show a straightforward, cost-effective method for obtaining a series of donor-acceptor-type Vinylogous Cyano Aminoaryls (VinCAs) with diverse emission colors. Further studies reveal that these VinCAs can serve as effective cell imaging agents, showcasing potential use in chemical biology. Additionally, these molecules could be further used to generate white light emission (WLE), showing their potential utility in advanced lighting technologies.
具有电子推拉效应的供体-受体型有机小分子可以通过分子内电荷转移显示出有趣的光致发光特性。这是设计用于细胞成像研究的荧光探针和开发有机发光二极管的基本标准。现在,要设计此类光学材料,有时需要通过控制最高占位分子轨道和最低未占位分子轨道的能量来调整带隙。通常情况下,可以通过在富电子供体和缺电子受体之间安装不饱和手柄来调节带隙。然而,由于涉及昂贵的催化剂和困难的反应设置,这些方法往往在合成和经济上具有挑战性。在本研究中,我们展示了一种简单、经济高效的方法,可以获得一系列具有不同发射颜色的供体-受体型乙烯基氰基氨基芳基(Vinylogous Cyano Aminoaryls,VinCAs)。进一步的研究表明,这些 VinCAs 可作为有效的细胞成像剂,在化学生物学中具有潜在用途。此外,这些分子还可进一步用于产生白光发射(WLE),显示了它们在先进照明技术中的潜在用途。
{"title":"One-Pot Synthesis of Vinylogous Cyano Aminoaryls (VinCAs) as Benzenic Fluorophores: Tailoring Diverse Emission Colors for White Light Emitting Materials and Cell Imaging.","authors":"Saurajit Ghosh, Shubham Kumar, Swathi Suneesh, Himanshi Bhambri, Sanjay K Mandal, Sarbani Ghosh, Rajdeep Chowdhury, Partha Sarathi Addy","doi":"10.1021/acs.joc.4c00320","DOIUrl":"10.1021/acs.joc.4c00320","url":null,"abstract":"<p><p>Donor-acceptor-based organic small molecules with an electronic push-pull effect can demonstrate intramolecular charge transfer to show interesting photoluminescence properties. This is an essential criterion for designing fluorogenic probes for cell imaging studies and the development of organic light-emitting diodes. Now, to design such optical materials sometimes it is necessary to tune the band gap by controlling the energies of the highest occupied molecular orbital and lowest unoccupied molecular orbital. Typically, the band gaps could be modulated by installing unsaturated handles between electron-rich donors and electron-deficient acceptors. However, these methods are often synthetically and economically challenging due to the involvement of expensive catalysts and difficult reaction setups. In our present study, we show a straightforward, cost-effective method for obtaining a series of donor-acceptor-type Vinylogous Cyano Aminoaryls (VinCAs) with diverse emission colors. Further studies reveal that these VinCAs can serve as effective cell imaging agents, showcasing potential use in chemical biology. Additionally, these molecules could be further used to generate white light emission (WLE), showing their potential utility in advanced lighting technologies.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140943025","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}
Detection of exhaled volatile organic compounds (VOCs) is promising for noninvasive screening of esophageal cancer (EC). Cellular VOC analysis can be used to investigate potential biomarkers. Considering the crucial role of methionine (Met) during cancer development, exploring associated abnormal metabolic phenotypes becomes imperative. In this work, we employed headspace solid-phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC-MS) to investigate the volatile metabolic profiles of EC cells (KYSE150) and normal esophageal epithelial cells (HEECs) under a Met regulation strategy. Using untargeted approaches, we analyzed the metabolic VOCs of the two cell types and explored the differential VOCs between them. Subsequently, we utilized targeted approaches to analyze the differential VOCs in both cell types under gradient Met culture conditions. The results revealed that there were five/six differential VOCs between cells under Met-containing/Met-free culture conditions. And the difference in levels of two characteristic VOCs (1-butanol and ethyl 2-methylbutyrate) between the two cell types intensified with the increase of the Met concentration. Notably, this is the first report on VOC analysis of EC cells and the first to consider the effect of Met on volatile metabolic profiles. The present work indicates that EC cells can be distinguished through VOCs induced by Met regulation, which holds promise for providing novel insights into diagnostic strategies.
检测呼出的挥发性有机化合物(VOC)有望用于食管癌(EC)的无创筛查。细胞挥发性有机化合物分析可用于研究潜在的生物标记物。考虑到蛋氨酸(Met)在癌症发展过程中的关键作用,探索相关的异常代谢表型势在必行。在这项研究中,我们采用顶空固相微萃取-气相色谱-质谱联用仪(HS-SPME-GC-MS)研究了Met调控策略下EC细胞(KYSE150)和正常食管上皮细胞(HEECs)的挥发性代谢谱。我们使用非靶向方法分析了两种细胞类型的代谢挥发性有机化合物,并探索了它们之间的挥发性有机化合物差异。随后,我们利用靶向方法分析了两种细胞在梯度 Met 培养条件下的不同 VOCs。结果表明,在含金属元素/不含金属元素的培养条件下,细胞间存在五种/六种不同的挥发性有机化合物。而随着 Met 浓度的增加,两种细胞间两种特征性挥发性有机化合物(1-丁醇和 2-甲基丁酸乙酯)的含量差异也在加剧。值得注意的是,这是第一份关于欧共体细胞挥发性有机化合物分析的报告,也是第一份考虑 Met 对挥发性代谢特征影响的报告。本研究结果表明,可以通过 Met 调节诱导的挥发性有机化合物来区分心肌细胞,这有望为诊断策略提供新的见解。
{"title":"Distinguish Esophageal Cancer Cells through VOCs Induced by Methionine Regulation.","authors":"Jijuan Zhou, Dianlong Ge, Yajing Chu, Yue Liu, Yan Lu, Yannan Chu","doi":"10.1021/acs.jproteome.4c00270","DOIUrl":"10.1021/acs.jproteome.4c00270","url":null,"abstract":"<p><p>Detection of exhaled volatile organic compounds (VOCs) is promising for noninvasive screening of esophageal cancer (EC). Cellular VOC analysis can be used to investigate potential biomarkers. Considering the crucial role of methionine (Met) during cancer development, exploring associated abnormal metabolic phenotypes becomes imperative. In this work, we employed headspace solid-phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC-MS) to investigate the volatile metabolic profiles of EC cells (KYSE150) and normal esophageal epithelial cells (HEECs) under a Met regulation strategy. Using untargeted approaches, we analyzed the metabolic VOCs of the two cell types and explored the differential VOCs between them. Subsequently, we utilized targeted approaches to analyze the differential VOCs in both cell types under gradient Met culture conditions. The results revealed that there were five/six differential VOCs between cells under Met-containing/Met-free culture conditions. And the difference in levels of two characteristic VOCs (1-butanol and ethyl 2-methylbutyrate) between the two cell types intensified with the increase of the Met concentration. Notably, this is the first report on VOC analysis of EC cells and the first to consider the effect of Met on volatile metabolic profiles. The present work indicates that EC cells can be distinguished through VOCs induced by Met regulation, which holds promise for providing novel insights into diagnostic strategies.</p>","PeriodicalId":48,"journal":{"name":"Journal of Proteome Research","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141304824","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Visible-light-promoted thiolation of benzyl chlorides with thiosulfonates is disclosed via an electron donor-acceptor complex strategy. In addition to efficiently delivering a series of arylbenzylsulfide compounds, versatile thioglycosides were also successfully constructed by applying the metal- and photocatalyst-free protocol. Preliminary mechanistic studies suggest that a radical-radical coupling process was involved in this transformation.
{"title":"Visible-Light-Promoted Thiolation of Benzyl Chlorides with Thiosulfonates via a Photoactive Electron Donor-Acceptor Complex.","authors":"Chao Gong, Jialun Huang, Liuyan Cai, Yilong Yuan, Tonglv Pu, Mingjie Huang, Si-Hai Wu, Lianhui Wang","doi":"10.1021/acs.joc.4c00748","DOIUrl":"10.1021/acs.joc.4c00748","url":null,"abstract":"<p><p>Visible-light-promoted thiolation of benzyl chlorides with thiosulfonates is disclosed via an electron donor-acceptor complex strategy. In addition to efficiently delivering a series of arylbenzylsulfide compounds, versatile thioglycosides were also successfully constructed by applying the metal- and photocatalyst-free protocol. Preliminary mechanistic studies suggest that a radical-radical coupling process was involved in this transformation.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141309642","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}
Pub Date : 2024-07-05Epub Date: 2024-06-20DOI: 10.1021/acs.joc.4c00234
Pallabi Halder, Krishanu Mondal, Arijit Jash, Parthasarathi Das
In this study, a ligand-free palladium-catalyzed carbonylation of phenols is conducted under ambient conditions, utilizing the "Chloroform-COware" chemistry. The developed methodology enables the conversion of diverse medicinally relevant phenols, encompassing both natural and synthetic derivatives, into their respective aryl ester counterparts. This transformation is achieved through the reaction with a broad spectrum of aryl and heteroaryl iodides. The protocol is characterized by its simplicity, generality, and wide substrate scope, delivering bioactive aryl ester derivatives in good to excellent yields. A direct comparison with the one-pot approach, resulting in poor yields of aryl esters, highlights the superior efficiency of the two-chamber setup (COware). Moreover, we successfully applied this two-chamber technique for gram-scale synthesis and postmodification of the synthesized ester to a pharmaceutically important benzocoumarin core.
{"title":"Exploiting Chloroform-COware Chemistry for Pd-Catalyzed Carbonylation of Naturally Occurring and Medicinally Relevant Phenols.","authors":"Pallabi Halder, Krishanu Mondal, Arijit Jash, Parthasarathi Das","doi":"10.1021/acs.joc.4c00234","DOIUrl":"10.1021/acs.joc.4c00234","url":null,"abstract":"<p><p>In this study, a ligand-free palladium-catalyzed carbonylation of phenols is conducted under ambient conditions, utilizing the \"Chloroform-COware\" chemistry. The developed methodology enables the conversion of diverse medicinally relevant phenols, encompassing both natural and synthetic derivatives, into their respective aryl ester counterparts. This transformation is achieved through the reaction with a broad spectrum of aryl and heteroaryl iodides. The protocol is characterized by its simplicity, generality, and wide substrate scope, delivering bioactive aryl ester derivatives in good to excellent yields. A direct comparison with the one-pot approach, resulting in poor yields of aryl esters, highlights the superior efficiency of the two-chamber setup (COware). Moreover, we successfully applied this two-chamber technique for gram-scale synthesis and postmodification of the synthesized ester to a pharmaceutically important benzocoumarin core.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141425709","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}