Jiamin Guo, Na Feng, Yuanzhu Liu, Liyan Liu, Yawen Zhang, Xinjian Yang, Enjun Wang
{"title":"Multifunctional Gold Super-Nanoparticle-Based Nanosystem for SERS-Guided Oxygen-Independent Phototherapy.","authors":"Jiamin Guo, Na Feng, Yuanzhu Liu, Liyan Liu, Yawen Zhang, Xinjian Yang, Enjun Wang","doi":"10.1002/chem.202500537","DOIUrl":"https://doi.org/10.1002/chem.202500537","url":null,"abstract":"<p><p>Cancer treatment remains a formidable challenge due to the complex and hypoxic microenvironment of tumors, which often compromises therapeutic efficacy. To address this issue, a multifunctional gold super-nanoparticle-based nanosystem (GSPs1,4-BDT@PDA-AIPH-cRGD) was developed for surface-enhanced Raman scattering (SERS)-guided oxygen-independent phototherapy. This nanosystem integrates diagnostic and therapeutic functionalities through a gold superlattice-nanoparticle (GSP) core self-assembled from 5.8 nm gold nanoparticles (GNPs), functionalized with 1,4-benzenedithiol (1,4-BDT) as a Raman reporter. The GSPs are encapsulated with a polydopamine (PDA) shell for enhancing their structural stability, Raman signal amplification, and serving as a photothermal agent. The PDA coating is further loaded with 2,2'-azobis[2-(2-imidazolin-2-yl) propane] dihydrochloride (AIPH), a oxygen independent photosensitizer that releases cytotoxic free radicals, and cyclic arginine-glycine-aspartic acid (cRGD) peptide for tumor targeting. Under near-infrared (NIR) light irradiation, the nanosystem generates hyperthermia and releases free radicals, achieving oxygen-independent tumor ablation. Real-time SERS imaging ensures precise tumor monitoring, addressing key challenges in cancer management. This novel approach combines the benefits of highly sensitive SERS imaging, targeted drug delivery, and oxygen independent phototherapy, providing a robust platform for synergistic cancer diagnosis and treatment with significant therapeutic potential.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500537"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143770734","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}
Yun Li, Meng Su, Yu Hou, Yajun Zheng, Zhiping Zhang
{"title":"Integrating Electrochemical Electrodes into Mass Spectrometry Ionization Sources for Detection of Transient Intermediates.","authors":"Yun Li, Meng Su, Yu Hou, Yajun Zheng, Zhiping Zhang","doi":"10.1002/chem.202404646","DOIUrl":"https://doi.org/10.1002/chem.202404646","url":null,"abstract":"<p><p>Identifying short-lived transient intermediates is challenging due to their brief lifetimes (as short as nanoseconds, and even picoseconds) and therefore low concentrations in many chemical processes. Conducting electrochemical reactions within mass spectrometry ion sources (i.e., insource or in situ EC-MS) offers the advantage of minimizing the distance between the electrodes and the mass spectrometer, thereby improving the detection of transient intermediates. However, a key challenge for in-source EC-MS is the effective integration of the electrodes into the MS ion sources. This mini-review highlights three main integration strategies: exploiting inherent electrochemical properties, incorporating a two- or three-electrode system, and implementing bipolar electrodes, focusing on the underlying mechanisms, experimental setups, and applications of these approaches. Future perspectives emphasize the directions of designing and modifying ionization sources, integrating electrocatalysis, enhancing transfer efficiency, developing automated screening platforms, as well as expanding practical applications.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404646"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143770703","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}
Magdalena Malgorzata Lozinska, Ruxandra Georgiana Chitac, Elliott Bruce, Malavika Manoj, Yuanyuan Du, Daniel Dawson, Sharon Ashbrook, Paul Cox, Paul Anthony Wright
{"title":"In Situ Generation by Cyclisation of an Organic Structure Directing Agent for the Synthesis of High Silica Zeolite ERS-7.","authors":"Magdalena Malgorzata Lozinska, Ruxandra Georgiana Chitac, Elliott Bruce, Malavika Manoj, Yuanyuan Du, Daniel Dawson, Sharon Ashbrook, Paul Cox, Paul Anthony Wright","doi":"10.1002/chem.202500327","DOIUrl":"https://doi.org/10.1002/chem.202500327","url":null,"abstract":"<p><p>Zeolites with high framework Si/Al ratios are of interest for industrial applications due to their hydrothermal stability. They are usually synthesised in the presence of pre-prepared organic structure directing agents (OSDAs). The high silica ERS-7 zeolite (topology type ESV) can be crystallised using N,N'-dimethylpyrrolidinium (dmpyrr) that is formed in situ via cyclisation of N,N,N',N'-tetramethyldiaminobutane (tmdab) when a cationic polymer is also present. The in situ generation of dmpyrr is demonstrated by solid-state 13C NMR spectroscopy and supported by both chemical analyses and comparative syntheses using pre-prepared dmpyrr. The cationic polymer inhibits the crystallisation of mordenite, which is otherwise observed to be the favoured product. The ERS-7 prepared via in situ dmpyrr synthesis (Si/Al = 14) is characterised by PXRD and solid-state NMR spectroscopy. The CO2 adsorption seen for the H- and Na-forms indicate interactions with accessible Na+ cations. The synthetic studies indicate the potential for in situ generation of OSDAs to reduce the need for extended OSDA syntheses.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500327"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143770779","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}
{"title":"Making and Breaking Supramolecular Synthons for Modular Protein Frameworks.","authors":"Niamh Mockler, Colin Raston, Peter B Crowley","doi":"10.1002/chem.202500732","DOIUrl":"https://doi.org/10.1002/chem.202500732","url":null,"abstract":"<p><p>Anionic calixarenes are useful mediators of protein assembly. In some cases, protein - calixarene cocrystallization yields multiple polymorphs. Ralstonia solanacearum lectin (RSL) cocrystallizes with p-sulfonato-calix[8]arene (sclx8) in at least four distinct pH-dependent arrangements. One of these polymorphs, occurring at pH ≤4, is a cubic framework in which RSL nodes are connected by sclx8 dimers. These dimers are supramolecular synthons, occurring in distinct crystal structures. Now, we show that the discus-shaped dimer of p-phosphonato-calix[6]arene (pclx6), can replace the sclx8 dimer yielding a new assembly of RSL. Remarkably, just one type of RSL - pclx6 cocrystal was formed, irrespective of pH or crystallization condition. These results with pclx6 contrast starkly with sclx8 and suggest that the calixarene type (e.g. phosphonate versus sulfonate) dictates the synthon durability, which in turn exerts control over protein assembly and polymorph selection. Breaking the pclx6 dimer required a mutant of RSL with an affinity tag for macrocycle binding. This highly accessible, dicationic site resulted in a significantly altered and porous framework with pclx6 (but not with sclx8). Experiments with ternary mixtures of RSL, pclx6 and sclx8 provide evidence of pH-driven self-sorting. Thus, the 'mix-and-match' of protein and supramolecular synthons is a promising approach to protein crystal engineering.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500732"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143770730","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}
Fátima Lucio-Martínez, Balázs Szilágyi, Rocío Uzal-Varela, Paulo Pérez-Lourido, David Esteban-Gómez, Nicolas Lepareur, Gyula Tircsó, C Platas-Iglesias
{"title":"[natY/90Y]Yttrium and [natLu/177Lu]Lutetium Complexation by Rigid H4OCTAPA Derivatives. Effect of Ligand Topology.","authors":"Fátima Lucio-Martínez, Balázs Szilágyi, Rocío Uzal-Varela, Paulo Pérez-Lourido, David Esteban-Gómez, Nicolas Lepareur, Gyula Tircsó, C Platas-Iglesias","doi":"10.1002/chem.202500799","DOIUrl":"https://doi.org/10.1002/chem.202500799","url":null,"abstract":"<p><p>We present a detailed investigation on the coordination chemistry of [nat/90Y]Y3+ and [nat/177Lu]Lu3+ with the new acyclic chelator H4CHXOITAPA. This octadentate chelator forms nine-coordinated Y3+ and Lu3+ complexes thanks to the coordination of a water molecule, as demonstrated by the X-ray structure of [Y(HCHXOITAPA)(H2O)] and 1H, 13C and 89Y NMR studies in solution. These complexes display slightly higher thermodynamic stabilities compared with those of the known H4CHXOCTAPA and H4OCTAPA chelators, reaching log KYL and log KLuL values of 21.24(5) and 21.96(1), respectively. Kinetic studies indicate that these complexes dissociate mainly through the spontaneous and proton-assisted pathways at pH 7.4. The chelator can be readily radiolabeled with [90Y]Y3+ and [177Lu]Lu3+ at room temperature in 10 min. The radio-complexes are stable in human serum at 37 ºC, in contrast with the analogues of the known H4CHXOCTAPA and H4OCTAPA chelators, which experience significant dissociation under these conditions. Thus, the H4CHXOITAPA chelator represents the most promising candidate among the H4OCTAPA family for the development of 90Y- and 177Lu-based radiopharmaceuticals.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500799"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143771006","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}
Eric Thomas Sletten, Jakob B Wolf, José Danglad-Flores, Peter H Seeberger
{"title":"Carbohydrate Synthesis is Entering the Data-Driven Digital Era.","authors":"Eric Thomas Sletten, Jakob B Wolf, José Danglad-Flores, Peter H Seeberger","doi":"10.1002/chem.202500289","DOIUrl":"https://doi.org/10.1002/chem.202500289","url":null,"abstract":"<p><p>Glycans are vital in biological processes, but their non-templated, heterogeneous structures complicate structure-function analyses. Glycosylation, the key reaction in synthetic glycochemistry, remains not entirely predictable due to its complex mechanism and the need for protecting groups that impact reaction outcomes. This Concept highlights recent advancements in glycochemistry and emphasizes the integration of digital tools, including automation, computational modelling, and data management, to improve carbohydrate synthesis and support further progress in the field.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500289"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143771013","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}
{"title":"Hierarchical Assemblies of Unsymmetric Pt Complexes with Ag ions: Two Types of Assembly Modes Depending on the Remote Ancillary Groups in the Bridging Ligands.","authors":"Yiming Yang, Shinnosuke Horiuchi, Kenichiro Omoto, Eri Sakuda, Yasuhiro Arikawa, Keisuke Umakoshi","doi":"10.1002/chem.202500948","DOIUrl":"https://doi.org/10.1002/chem.202500948","url":null,"abstract":"<p><p>Self-assembly via noncovalent interactions can amplify small structural differences in small molecular units, producing large supramolecular architectures with structure-dependent complexities and characteristics. In this paper, the unique self-assembly behaviors of mononuclear Pt(II) complex units accommodating Ag(I) ions are reported. The Pt complex with the N^C chelating ligand and two different kinds of pyrazole ligands gave two regioisomers, whose structural difference was only the position of the N and C donor atoms in the N^C chelating ligands. This small structural difference influences the assembled structures with Ag ions, producing two different types of heteropolynuclear complexes with different clustering motifs. This was further amplified via a hierarchical assembly process incorporating additional Ag ions to afford two different types of Pt-Ag cluster-of-cluster complexes. This study proves that the self-assembly of unsymmetrical fragments can endow significant complexity and perturbation in the molecular system, enabling the observation of unique molecular behaviors.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500948"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143770776","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}
Yang Wu, Jingbo Xu, Xiufen Yan, Mengdi Zhao, Zeyu Liu, Tian Lu
{"title":"Interesting Aromaticity of Franck-Condon Excited States of Cyclo[16]carbon.","authors":"Yang Wu, Jingbo Xu, Xiufen Yan, Mengdi Zhao, Zeyu Liu, Tian Lu","doi":"10.1002/chem.202404138","DOIUrl":"https://doi.org/10.1002/chem.202404138","url":null,"abstract":"<p><p>Inspired by the realization of cyclo[16]carbon (C16) and driven by curiosity about its properties in excited states, a comprehensive theoretical study was conducted on the aromatic characteristics in the Franck-Condon states of C16. This work demonstrates that at the ground-state (S0 state) geometry, C16 exhibits aromaticity not only in the triplet states (T1(in→out), T2(out→out), and T3(in→in)), but also more prominently in the quintet state (Q1 state), and different electronic transition modes result in different essential sources of aromaticity for each excited state. Quantitatively, C16 is about three times more aromatic in the quintet state than in the triplet states. These conclusions are supported by multiple robust indicators such as atomic force, induced current, and magnetic shielding, from qualitative, quantitative, and graphical perspectives.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404138"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143770707","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}
Junfei Xue, Qi Yu, Jiyang Yu, Tarek Trabelsi, Joseph S Francisco, Xiaoqing Zeng
{"title":"Chlorosulfenic Acid: An Important Linker in the Coupled Sulfur and Chlorine Chemistry in the Venusian Atmosphere.","authors":"Junfei Xue, Qi Yu, Jiyang Yu, Tarek Trabelsi, Joseph S Francisco, Xiaoqing Zeng","doi":"10.1002/chem.202500174","DOIUrl":"https://doi.org/10.1002/chem.202500174","url":null,"abstract":"<p><p>The coupled sulfur and chlorine chemistry plays an important role in the chemical cycle of the Venusian atmosphere. However, the reactivity of the abundant sulfur monoxide (SO) toward hydrochloric acid (HCl) in the Venusian atmosphere remains hitherto unknown. In this work, we report the generation, spectroscopic characterization, and photochemistry of chlorosulfenic acid (HOSCl), a simple molecule that acts not only as a potential candidate for the near-UV absorber but also as an important linker in the coupled sulfur and chlorine chemistry in the Venusian atmosphere. This molecule has bright absorption from 330 to 440 nm. The photochemistry of HOSCl at 365 nm yields SO and HCl as a novel hydrogen-bonded molecular complex in a cryogenic Ar-matrix at 10 K, and the subsequent irradiation at 193 nm leads to recombination of the two fragments by reformation of HOSCl. The photochemistry of HOSCl underscores its importance in the photochemical models of the sulfur and chlorine species in Venusian atmosphere.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500174"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143770771","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}
{"title":"FeOHSO4@C Cathode with Low Strain and High Pseudocapacitance for Advanced Potassium-ion Batteries.","authors":"Dai-Huo Liu, Cheng Yun, Bao Li, Dongmei Dai, Fang Xu, Yunli Li, Ao Wang, Chunyan Xu, Zhenjiang Li, Mengqin Song, Zhuangzhuang Zhang, Junpo Guo","doi":"10.1002/chem.202500280","DOIUrl":"https://doi.org/10.1002/chem.202500280","url":null,"abstract":"<p><p>Iron-based polyanionic cathode materials in potassium-ion batteries (KIBs) have appealed to an increasing number of interest due to these advantages of low cost, environmental friendliness and excellent structural stability. However, these inherent drawbacks of inferior electronic conductivity and terrible nanostructural stability hinder its practical application. Here we report a novel low-strain iron-based polyanion-type cathode material FeOHSO4@C for KIBs. In this work, the surface of FeOHSO4 nanoparticles are well carbon encapsulated, carbon coating layer with large surface area and excellent electrical conductivity is ~2.5 nm in thick, which can not only inhibits the aggregation and growth between FeOHSO4@C nanoparticles during charging and discharging, but also provides a three-dimensional (3D) electronic conductive framework that activates electrochemical reactivity. As a result, the FeOHSO4@C cathode exhibits outstanding potassium storage capacity (capacity retention of 80.95% over 200 cycles at 20 mA g-1) attributed to a low-strain mechanism for K+ uptake/removal, high pseudocapacitance, as well as 3D electronic conductive framework. Operando XRD and ex situ XPS analyses revealed a single phase reaction route of orthorhombic FeOHSO4@C during cycling.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500280"},"PeriodicalIF":3.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143770774","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}