Chemical Science最新文献

Photo-triggered NO release of nitrosyl complexes bearing first-row transition metals and therapeutic applications 含第一排过渡金属的亚硝基复合物的光触发 NO 释放及治疗应用

IF 8.4 1区化学

Chemical Science Pub Date : 2024-11-07 DOI: 10.1039/d4sc06820c

Seungwon Sun, Jisu Choe, Jaeheung Cho

{"title":"Photo-triggered NO release of nitrosyl complexes bearing first-row transition metals and therapeutic applications","authors":"Seungwon Sun, Jisu Choe, Jaeheung Cho","doi":"10.1039/d4sc06820c","DOIUrl":"https://doi.org/10.1039/d4sc06820c","url":null,"abstract":"In biological systems, nitric oxide (NO) is a crucial signaling molecule that regulates a wide range of physiological and pathological processes. Given the significance of NO, there has been considerable interest in delivering NO exogenously, particularly through light as a non-invasive therapeutic approach. However, due to the high reactivity and instability of NO under physiological conditions, directly delivering NO to targeted sites remains challenging. In recent decades, photo-responsive transition metal–nitrosyl complexes, especially based on first-row transition metals such as Mn, Fe, and Co, have emerged as efficient NO donors, offering higher delivery efficiency and quantum yields than heavy metal–nitrosyl complexes under light exposure. This review provides a comprehensive overview of current knowledge and recent developments in the field of photolabile first-row transition metal–nitrosyl complexes, focusing on the structural and electronic properties, photoreactivity, photodissociation mechanisms, and potential therapeutic applications. By consolidating the key features of photoactive nitrosyl complexes, the review offers deeper insights and highlights the potential of first-row transition metal–nitrosyl complexes as versatile tools for photo-triggered NO delivery.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589164","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}

引用次数: 0

Insights into the photoinduced anion translocation of the Donor-π-Acceptor+(ion)- molecules 光诱导阴离子在供体-π-受体+（离子）-分子中转移的启示

IF 8.4 1区化学

Chemical Science Pub Date : 2024-11-07 DOI: 10.1039/d4sc04738a

Hao-Ting Qu, Iida Partanen, Kai-Hsin Chang, Yan-Ding Lin, Igor O Koshevoy, Andrey Belyaev, Pi-Tai Chou

{"title":"Insights into the photoinduced anion translocation of the Donor-π-Acceptor+(ion)- molecules","authors":"Hao-Ting Qu, Iida Partanen, Kai-Hsin Chang, Yan-Ding Lin, Igor O Koshevoy, Andrey Belyaev, Pi-Tai Chou","doi":"10.1039/d4sc04738a","DOIUrl":"https://doi.org/10.1039/d4sc04738a","url":null,"abstract":"By strategic design and synthesis of a new series of phosphonium salts (compounds 1–7[OTf]), where [OTf]- stands for the trifluoromethanesulfonate anion, we performed comprehensive spectroscopic and dynamic studies on the photoinduced anion migration in toluene. Our aim is to probe if the anion migration is associated with an intrinsic barrier or is barrier free. After the occurrence of excited-state intramolecular charge transfer (ESICT) in 1–7, the charge redistribution of the cation triggers the translocation of the counter anion [OTf]–, resulting in emission spectral temporal evolution. As a result, we describe the photoinduced anion migration by introducing spectral response function C(t), a concept adopted from the solvent diffusional relaxation. The experimental results indicate that the anion migration lacks intrinsic barrier, i.e., the relaxation dynamics can be described by a biased Brownian motion along the charge transfer direction. The experimental findings are also qualitatively supported by theoretical calculations including restrained electrostatic potential (RESP) and hole-electron distribution analyses.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589174","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}

引用次数: 0

Probing water adsorption and stability under steam flow of Zr-based metal-organic frameworks using 91Zr solid-state NMR spectroscopy 利用 91Zr 固态 NMR 光谱探测 Zr 基金属有机框架在蒸汽流动下的水吸附性和稳定性

IF 8.4 1区化学

Chemical Science Pub Date : 2024-11-07 DOI: 10.1039/d4sc04589k

Athulya Nadol, Florian Venel, Raynald Giovine, Maeva Leloire, Christophe Volkringer, Thierry Loiseau, Christel Gervais, Caroline Mellot-Draznieks, Bertrand Doumert, Julien Trébosc, Olivier Lafon, Frédérique Pourpoint

{"title":"Probing water adsorption and stability under steam flow of Zr-based metal-organic frameworks using 91Zr solid-state NMR spectroscopy","authors":"Athulya Nadol, Florian Venel, Raynald Giovine, Maeva Leloire, Christophe Volkringer, Thierry Loiseau, Christel Gervais, Caroline Mellot-Draznieks, Bertrand Doumert, Julien Trébosc, Olivier Lafon, Frédérique Pourpoint","doi":"10.1039/d4sc04589k","DOIUrl":"https://doi.org/10.1039/d4sc04589k","url":null,"abstract":"The stability of metal-organic frameworks (MOFs) in the presence of water is crucial for a wide range of applications, including the production of freshwater, desiccation, humidity control, heat pumps/chillers and capture and separation of gas. In particular, their stability under steam flow is essential since most industrial streams contain water vapor. Nevertheless, to the best of our knowledge, the stability under steam flow of Zr-based MOFs, which are among the most widely studied MOFs, has not been investigated so far. We explore it herein for three UiO-like Zr-based MOFs built from the same Zr cluster but distinct organic linkers at temperature ranging from 80 to 200 °C. We demonstrate the possibility to acquire their 91Zr NMR spectra using high magnetic field (18.8 T) and low temperature (140 K) and to interpret them by comparing experimental data with NMR parameters calculated by DFT. NMR observation of this challenging isotope combined with more conventional techniques, such as N2 adsorption, X-ray diffraction, IR, 1H and 13C solid-state NMR spectroscopies, provides information on the possible collapse of the MOF framework but also on the adsorption of molecules into the pores. We notably show that UiO-66(Zr) and UiO-66-Fum(Zr) built from terephthalate and fumarate linkers, respectively, are stable over 24 h (and even over 7 days for UiO-66(Zr)) under steam flow at all investigated temperatures, whereas UiO-67-NH2 containing 2-amino-[1,1’-biphenyl]-4,4’-dicarboxylate linker degrades under steam flow at temperature ranging from 80 to 150 °C but is preserved at 200 °C. The lower stability of UiO-67-NH2 stems from its larger pores and its weaker Zr−O coordination bonds, whereas its preservation at 200 °C results from a more limited condensation of water in the pores.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594196","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}

引用次数: 0

Pd(II)-Catalyzed Enantioselective C-H Olefination and Photoregulation of Sterically-Hindered Diarylethenes Pd(II)催化的对映体选择性 C-H 烯化反应和静态受阻二元酚的光调节作用

IF 8.4 1区化学

Chemical Science Pub Date : 2024-11-07 DOI: 10.1039/d4sc05375c

Guanlun Zhang, Xu Wu, Shiyu Mao, Mengqi Li, Honglong Hu, Bing-Feng Shi, Weihong Zhu

{"title":"Pd(II)-Catalyzed Enantioselective C-H Olefination and Photoregulation of Sterically-Hindered Diarylethenes","authors":"Guanlun Zhang, Xu Wu, Shiyu Mao, Mengqi Li, Honglong Hu, Bing-Feng Shi, Weihong Zhu","doi":"10.1039/d4sc05375c","DOIUrl":"https://doi.org/10.1039/d4sc05375c","url":null,"abstract":"Sterically-hindered diarylethenes with intrinsic chirality have shown great potential in chiral signal regulation, light-controlled liquid crystals (LCs), etc. Their unique enantiospecific phototransformation between axial chirality of ring-open isomer and central chirality of ring-closed isomer can break through the bottleneck of the interference between multiple chiral centers in traditional chiral diarylethenes. However, these intrinsic chiral diarylethenes require necessary chiral resolution through preparative chiral HPLC, typically resulting in limited separation efficiency and production scale. Here, we present an enantioselective olefination strategy to directly construct intrinsic chiral diarylethenes from a prochiral sterically-hindered diarylethene, achieving high yields and enantioselectivity. The resulting isomers can be further decorated by incorporating mesogenic units, and the derivatives enable the successful reversible photoregulation of blue, green, and red reflection colors of LC with excellent thermal stability, fatigue resistance, and little texture disorderliness, demonstrating the practical application potential of direct enantioselective olefination in photoregulation with intrinsic chiral diarylethenes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589163","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}

引用次数: 0

Cationic Al oxo-hydroxide clusters: syntheses, molecular structures, and functional applications 阳离子氧化铝-氢氧化物团簇：合成、分子结构和功能应用

IF 8.4 1区化学

Chemical Science Pub Date : 2024-11-07 DOI: 10.1039/d4sc05707d

Naoki Ogiwara, Wei Zhou, Sayaka Uchida

引用次数: 0

Mechanism of Action and Evaluation of Ratiometric Probes for Uric Acid Using Lanthanide Complexes with Tetraazatriphenylene Sensitisers 使用镧系元素络合物与四氮杂三亚苯基敏化剂的尿酸比率探针的作用机制与评估

IF 8.4 1区化学

Chemical Science Pub Date : 2024-11-07 DOI: 10.1039/d4sc05743k

Xinyi Wen, Huishan Li, Zhijie Ju, Renren Deng, David Parker

引用次数: 0

Bipolar Electrochemiluminescence at the Water/Organic Interface 水/有机物界面的双极电化学发光

IF 8.4 1区化学

Chemical Science Pub Date : 2024-11-06 DOI: 10.1039/d4sc06103a

Yuheng Fu, Bingbing Xie, Miaoxia Liu, Shaojuan Hou, Qunyan Zhu, Alexander Kuhn, Lin Zhang, Wensheng Yang, Neso Sojic

{"title":"Bipolar Electrochemiluminescence at the Water/Organic Interface","authors":"Yuheng Fu, Bingbing Xie, Miaoxia Liu, Shaojuan Hou, Qunyan Zhu, Alexander Kuhn, Lin Zhang, Wensheng Yang, Neso Sojic","doi":"10.1039/d4sc06103a","DOIUrl":"https://doi.org/10.1039/d4sc06103a","url":null,"abstract":"Electrochemiluminescence (ECL) has emerged as a valuable tool for understanding multiphasic and compartmentalized systems, which have crucial wide-ranging applications across diverse fields. However, ECL reactions are limited to the vicinity of the electrode surface due to spatial constraints of electron transfer and the short lifetime of radical species, making ECL emission in bulk multiphasic solution challenging. To address this limitation, we propose a novel bipolar electrochemistry (BPE) approach for wireless dual-color ECL emission at the water/oil (w/o) interface. Firstly, amphiphilic glass carbon (GC) microbeads with distinct hydrophilic and hydrophobic regions are prepared by bipolar electrografting of hydrophobic trifluoromethyl diazonium salt, then the resulting Janus beads are positioned at the w/o interface. Subsequently, two model ECL systems containing luminol and H2O2 in the aqueous phase, and [Ru(bpy)3]²⁺ and benzoyl peroxide (BPO) in the organic phase, are selected based on their solubility to confine light-emitting reactions to their respective phases. Upon application of an electric field perpendicular to the interface, the Janus microbeads get polarized, triggering simultaneous oxidative blue ECL (425 nm) and reductive red ECL (620 nm) in the aqueous and organic phases, respectively. Taking advantage of ECL imaging, the potential gradient distribution on the GC microbead at the w/o interface is revealed, indicating a \"pseudo-closed\" bipolar system due to limited ion transfer between phases. We also investigate the effect of changing the electric field direction parallel to the interface, which alters the ECL emission area from a hemisphere to a quarter of the microbead's surface. This bipolar ECL approach at the w/o interface not only offers opportunities for imaging the aqueous phase and organic phase simultaneously, but also enables ECL imaging and light generation in the bulk solution, thus overcoming the usual spatial limitation requiring proximity to the electrode surface.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580757","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}

引用次数: 0

The Effect of gem-Difluorination on the Conformation and Properties of a Model Macrocyclic System 宝石二氟化对模型大环系统构象和性质的影响

IF 8.4 1区化学

Chemical Science Pub Date : 2024-11-06 DOI: 10.1039/d4sc05424e

Laurent Knerr, Thomas Cogswell, Marie. Ahlqvist, Richard James Lewis, Anneli Nordqvist, Christian Sköld

{"title":"The Effect of gem-Difluorination on the Conformation and Properties of a Model Macrocyclic System","authors":"Laurent Knerr, Thomas Cogswell, Marie. Ahlqvist, Richard James Lewis, Anneli Nordqvist, Christian Sköld","doi":"10.1039/d4sc05424e","DOIUrl":"https://doi.org/10.1039/d4sc05424e","url":null,"abstract":"Conformational control of drug candidates to engineer improved potency and ADME properties is an ongoing area of research. Macrocyclic rings tend to offer a greater degree of rigidity than non-cyclised small molecules, and, as a result they are perfect platforms to instil conformational controls. In this study, the difluoroalkoxyphenyl moiety is examined as a tool to alter the conformation of macrocycles. A fluorinated and non-fluorinated macrocyclic matched pair is compared in terms of conformation preferences and related ADME properties. The synthesised macrocycles are found to give similar major conformations exhibiting a trans amide in the macrocyclic backbone. However, for the fluorinated macrocycle, the major trans amide conformation is in equilibrium with a cis amide minor conformation, seen by 1H NMR in a 4:1 ratio of trans/cis. The conformational fits for the minor fluorinated isomer demonstrate the out of plane preference of the difluoroalkoxy system encouraging the amide within the macrocycle backbone to adopt a cis conformation. A dramatic reduction in metabolic stability was found for the fluorinated macrocycle compared to the non-fluorinated and is postulated to be a result of the interconversion of trans amide to the cis amide, which may be more readily metabolised.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580753","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}

引用次数: 0

Direct synthesis of N-perfluoro-tert-butyl secondary amines from N-trifluoromethyl secondary amines 从 N-三氟甲基仲胺直接合成 N-全氟叔丁基仲胺

IF 8.4 1区化学

Chemical Science Pub Date : 2024-11-06 DOI: 10.1039/d4sc06335j

leibing Wang, Zhongyu Feng, Zhen Luo, Zihao Guo, Jieping Wang, WenBin Yi

{"title":"Direct synthesis of N-perfluoro-tert-butyl secondary amines from N-trifluoromethyl secondary amines","authors":"leibing Wang, Zhongyu Feng, Zhen Luo, Zihao Guo, Jieping Wang, WenBin Yi","doi":"10.1039/d4sc06335j","DOIUrl":"https://doi.org/10.1039/d4sc06335j","url":null,"abstract":"N-Perfluoro-tert-butyl (N-PFtB) secondary amines, harboring a unique 19F-reporting moiety linked directly to nitrogen, are highly attractive due to their diverse potential applications. However, their mild and facile synthesis remains a significant challenge. Herein, we present a safe and efficient strategy for the direct synthesis of N-perfluoro-tert-butyl secondary amines from readily available N-trifluoromethyl secondary amines. Experiments and theoretical calculations demonstrate that this novel protocol encompasses three main processes: the elimination of hydrogen fluoride from the N-trifluoromethyl precursor, consecutive addition-elimination conversion of difluoromethyl imine (R-N=CF2) to hexafluoropropyl imine (R-N=C(CF3)2), and final addition of R-N=C(CF3)2 with the in situ generated fluoroform (HCF3). Key advantages of this reaction include the utilization of a single trifluoromethyl source and the N-trifluoromethyl starting material itself as the hydrogen source. Notably, the elimination of hydrogen fluoride, facilitated by CsF, is critical for the success of this approach. This method is compatible with a broad range of functional groups, including heterocyclic compounds. 19F MRI experiments suggest promising prospects for PFtB-labeled secondary amines as 19F MRI contrast agents.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580760","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}

引用次数: 0

Dilute nanocomposites for capacitive energy storage: progress, challenges and prospects 用于电容式储能的稀释纳米复合材料：进展、挑战与前景

IF 8.4 1区化学

Chemical Science Pub Date : 2024-11-06 DOI: 10.1039/d4sc05437g

Li Li, Wenhan Xu, Guanchun Rui, Shixian Zhang, Qiming Zhang, Qing Wang

{"title":"Dilute nanocomposites for capacitive energy storage: progress, challenges and prospects","authors":"Li Li, Wenhan Xu, Guanchun Rui, Shixian Zhang, Qiming Zhang, Qing Wang","doi":"10.1039/d4sc05437g","DOIUrl":"https://doi.org/10.1039/d4sc05437g","url":null,"abstract":"Electrostatic capacitors (ECs) are critical components in advanced electronics and electric power systems due to their rapid charge-discharge rate and high power density. While polymers are ideal for ECs due to their high voltage tolerance and mechanical flexibility, their low dielectric constants (K) and limited energy density remain significant limitations. Traditional polymer nanocomposites, which incorporate high-K ceramic fillers, have shown promise in enhancing dielectric properties but often at the cost of electric breakdown strength and scalability. In this Perspective, we explore a pioneering approach that utilizes ultralow loadings of small-sized inorganic nanofillers to significantly improve dielectric constants without compromising other key properties. We delve into the unconventional effects observed in these polymer nanocomposites, including dielectric enhancements, charge trapping, mechanical reinforcements, and microstructural changes, and highlight the impressive energy storage performance achieved with minimal filler contents. We discuss innovative design strategies from viewpoints of polymer and filler structures and showcase recent advancements in nanoscale characterizations and theoretical modelling for understanding the crucial role of polymer-filler interfaces. Finally, we stress fundamental challenges and prospects, providing insights into the transformative potential of these nanocomposites for next-generation energy storage applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580755","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}

引用次数: 0