Zhishan Chen, Shaoan Zhang, Zhenzhang Li, Huacong Ye, Haoran Yan, Jialong Xu, Ling Gao, Yang Li, Shizhen Zhang
{"title":"Thermally Stable NIR Broad Emission of Cr3+ Doping Phosphor With a High NIR Output Power","authors":"Zhishan Chen, Shaoan Zhang, Zhenzhang Li, Huacong Ye, Haoran Yan, Jialong Xu, Ling Gao, Yang Li, Shizhen Zhang","doi":"10.1039/d4qi01728e","DOIUrl":"https://doi.org/10.1039/d4qi01728e","url":null,"abstract":"The development of high-performance near-infrared (NIR) luminescent materials remains a significant challenge, particularly in enhancing thermal stability. Herein, we observed an anti-thermal quenching effect in the YGa<small><sub>1.5</sub></small>Al<small><sub>1.5</sub></small>(BO<small><sub>3</sub></small>)<small><sub>4</sub></small>:Cr<small><sup>3+</sup></small> phosphor, with its emission intensity reaching 104% at 423 K and 101% at 483 K compared to room temperature. This anti-thermal quenching is mainly attributed to thermal-induced emission compensation resulting from excited electrons trapped at crystal defects, as confirmed by density functional theory computation. Additionally, YGa<small><sub>1.5</sub></small>Al<small><sub>1.5</sub></small>(BO<small><sub>3</sub></small>)<small><sub>4</sub></small>:Cr<small><sup>3+</sup></small> exhibits a broad NIR emission peaking at 750 nm with a full width at half maximum of 135 nm and a high photoluminescence quantum yield (86%). As a proof-of-concept, we fabricated an NIR phosphor-converted light-emitting diode device that achieves an NIR output power of 59.67 mW with an input working current of 150 mA, demonstrating a photoelectric conversion efficiency of 13.6%. The utilization of this high-power NIR light-emitting diode device as a lighting source enables a penetration depth of up to 15 mm, demonstrating the potential applications of Cr<small><sup>3+</sup></small>-doped YGa<small><sub>1.5</sub></small>Al<small><sub>1.5</sub></small>(BO<small><sub>3</sub></small>)<small><sub>4</sub></small>:Cr<small><sup>3+</sup></small> phosphors for non-invasive detection of biological tissue.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142022059","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 Bis-Aromatic MOF System Constructed by a Copper Iodine Cluster and Porphyrinic Ligand for Enhancing Near-Infrared Photothermal Conversion","authors":"Man Cao, Qian-You Wang, Run-Meng Li, Fangfang Dai, Shan Wang, Peng Luo, Jia-Hua Hu, Xi-Yan Dong, Ren-Wu Huang","doi":"10.1039/d4qi01543f","DOIUrl":"https://doi.org/10.1039/d4qi01543f","url":null,"abstract":"Near-infrared (NIR) photothermal materials efficiently convert low-energy near-infrared light into heat and have a significant role across various domains. Herein, a copper iodine cluster node (Cu14I14) featuring inorganic aromaticity was assembled with porphyrinic ligands characterized by classical π-aromaticity to create a dual-aromatic crystalline MOF (denoted as Cu14I14-CuTPyP). Cu14I14-CuTPyP with extensive electron delocalization exhibited a broad NIR absorption and achieved a high NIR photothermal conversion efficiency of 63.77% under 1064 nm laser irradiation; this efficiency surpassed those of most reported porphyrin assembly materials. By combining in situ Raman spectroscopy, transient absorption spectroscopy, and control experiments, we revealed that the cooperation between aromatic Cu14I14 and porphyrin led to an active electron transfer pathway in Cu14I14-CuTPyP, which consumed a considerable portion of excited-state molecules (71.4%) through ultrafast nonradiative relaxation channels (2.1 ps). In this study, our thorough investigation of the photothermal properties of bis-aromatic MOFs could aid in the creation of set a new standard for material design.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142042596","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}
Tian-Shu Tang, Li Mao, Chun-Hua Huang, Chuan-Fang Zhao, Zhi-Sheng Liu, Jing Chen and Ben-Zhan Zhu
{"title":"Unusual singlet oxygen-dependent hydroxyl radical production by a unique ruthenium-polypyridyl-hydroxamate complex under visible light irradiation†","authors":"Tian-Shu Tang, Li Mao, Chun-Hua Huang, Chuan-Fang Zhao, Zhi-Sheng Liu, Jing Chen and Ben-Zhan Zhu","doi":"10.1039/D4QI00853G","DOIUrl":"10.1039/D4QI00853G","url":null,"abstract":"<p >Ruthenium polypyridyl complexes have been widely used in photodynamic therapy, during which singlet oxygen (<small><sup>1</sup></small>O<small><sub>2</sub></small>) plays a crucial role. Here, we synthesized a unique Ru complex Ru(bpy)<small><sub>2</sub></small>PhenHA (bpy – bipyridine, Phen – 1,10-phenanthroline, HA – hydroxamic acid) and unexpectedly found that not only <small><sup>1</sup></small>O<small><sub>2</sub></small>, but also reactive hydroxyl radical (˙OH) could be produced under visible-light irradiation of Ru(bpy)<small><sub>2</sub></small>PhenHA in the presence of a classic spin trapping agent, 5,5-dimethyl-1-pyrroline <em>N</em>-oxide (DMPO). Analogous ˙OH production was also observed with 3,3,5,5-tetramethyl-1-pyrroline-<em>N</em>-oxide (TMPO), but not with other spin trapping agents. In contrast, much less ˙OH was produced when substituting Ru(bpy)<small><sub>2</sub></small>PhenHA with Ru(bpy)<small><sub>2</sub></small>Phen lacking the HA group. However, when <em>N</em>-methyl-benzohydroxamic acid (a typical HA with reducing properties) was added into the DMPO/Ru(bpy)<small><sub>2</sub></small>Phen/VIS system, not only ˙OH, but also the corresponding secondary nitroxide radical was clearly detected. Similar results were also observed with other structurally-different reducing agents. Further studies with other known spin trapping agents suggest that the [DMPO–OOH]˙ intermediate might be transiently produced and then rapidly decomposed to produce ˙OH. Taken together, the molecular mechanism for the unusual ˙OH production was proposed: visible-light irradiation of Ru(bpy)<small><sub>2</sub></small>PhenHA produced <small><sup>1</sup></small>O<small><sub>2</sub></small>, which electrophilically added on DMPO, forming a peroxide intermediate, which then quickly decomposed to a biradical [DMPO–OO]˙˙. Then, H-abstraction took place between [DMPO–OO]˙˙ and the reducing hydroxamic acid, forming the unstable [DMPO–OOH]˙, which decomposed homolytically to produce ˙OH. These findings revealed a novel ˙OH-generating system mediated by Ru complexes, which were not only dependent on DMPO, but also on <small><sup>1</sup></small>O<small><sub>2</sub></small> and the presence of H-donating agents. These findings may have broad chemical and biomedical implications.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":6.1,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142022056","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}
Jiu-Yang Liu, Ming Zhu, Feng-Wen Zhang, Hao-Fei Ni, Zhi-Long Li, Bo Zhuang, Kun Ding, Da-Wei Fu, Hai-Feng Lu and Meng-Meng Lun
{"title":"Halogen regulation of multifunctional hybrid materials with photoluminescence and dielectric response†","authors":"Jiu-Yang Liu, Ming Zhu, Feng-Wen Zhang, Hao-Fei Ni, Zhi-Long Li, Bo Zhuang, Kun Ding, Da-Wei Fu, Hai-Feng Lu and Meng-Meng Lun","doi":"10.1039/D4QI01774A","DOIUrl":"10.1039/D4QI01774A","url":null,"abstract":"<p >Organic–inorganic hybrid switching materials are extensively employed as stimulus-responsive materials in sensors, intelligent switches, optoelectronic devices, <em>etc</em>. However, the design of organic–inorganic hybrid materials (OIHMs) that integrate the dielectric switching response and superior photoluminescence (PL) continues to encounter challenges. Here, we synthesized three zero-dimensional (0D) organic–inorganic hybrid PL compounds using a halogen regulation strategy, (2,5-FBTA)<small><sub>2</sub></small>MnX<small><sub>4</sub></small> (2,5-FBTA = 2,5-difluorobenzyltrimethylammonium, X = Br, Cl, I), which are FBTAM-Br, FBTAM-Cl, and FBTAM-I. With the halogen atom transitioning from I to Br, the phase transition temperature (<em>T</em><small><sub>p</sub></small>) gradually increases due to the enhanced intermolecular interaction force, with the <em>T</em><small><sub>p</sub></small> of FBTAM-I, FBTAM-Cl, and FBTAM-Br being 419, 425, and 438 K, respectively. In addition, the three compounds show excellent PL properties, and as the halogen atom transitions from I to Br, the PL quantum yields (PLQY) of FBTAM-I, FBTAM-Cl, and FBTAM-Br are 54.59%, 63.81% and 78.98%, respectively. Through a halogen regulation strategy, multifunctional OIHMs with dielectric and PL properties have been successfully synthesized. This not only enhances comprehension of the correlation between structures and properties but also introduces novel and innovative perspectives for the development of multifunctional OIHMs.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":6.1,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142022055","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}
Mengxiang Ye, Huaimeng Li, Xi Wu, Guofeng Zhang, Yunxia Zhang
{"title":"Cobalt and lithium recovery from spent LiCoO2 using a free-standing potassium zinc hexacyanoferrate/carbon cloth composite electrode","authors":"Mengxiang Ye, Huaimeng Li, Xi Wu, Guofeng Zhang, Yunxia Zhang","doi":"10.1039/d4qi01752h","DOIUrl":"https://doi.org/10.1039/d4qi01752h","url":null,"abstract":"Rapid rejuvenation and extensive utilization of mobile electronic devices lead to the excessive accumulation of waste lithium-ion batteries (LIBs), especially represented by spent LiCoO2 cathode materials. Considering the shortage of metals resources and the surging price of raw materials in the battery industry, it is in urgent demand to exploit an efficient strategy for selectively extract valuable metals from spent LiCoO2. Herein, the nanocube-like potassium zinc hexacyanoferrate (denoted as KZHCF) has been successfully fabricated on carbon cloth (CC) substrate for selective Co2+ adsorption from spent LiCoO2 cathode via the combination of simple electrodeposition and hydrothermal treatment. Under the optimal operational conditions, 98.6% of Co2+ is effectively extracted within 120 min at a constant potential of −0.4 V (vs. Ag/AgCl) with CC/KZHCF composite as working electrode, accompanied by a Co2+ electrosorption capacity of 130.9 mg∙g−1. Further, lithium ions in the electrolyte are separated and recovered in the form of Li2CO3 via simple chemical precipitation, highlighting the feasibility of the developed electrochemical system toward cobalt and lithium recovery. Significantly, the CC/KZHCF electrode materials can be regenerated through simple potential inversion; while the adsorbed Co2+ ions are facilely desorbed from the electrode surface and recovered as Co(OH)2. This work will provide a meaningful guidance for the separation and recovery of various metals from waste LIBs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142022054","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":"Air promotes efficient and selective CO2 photoreduction with a molecule/semiconductor hybrid photocatalyst: the significant role of simultaneous photodegradation of organic pollutants†","authors":"Xinyue Hong, Yuru Zhu and Duobin Chao","doi":"10.1039/D4QI01739K","DOIUrl":"10.1039/D4QI01739K","url":null,"abstract":"<p >The photoreduction of CO<small><sub>2</sub></small> with atmospheric air represents a promising avenue toward the sustainable utilization of CO<small><sub>2</sub></small>. Herein, a noble-metal free molecule/semiconductor hybrid photocatalyst has been employed for the first time for converting CO<small><sub>2</sub></small> to CO with 100% selectivity in water and simultaneous photodegradation of tetracycline in the presence of air. The hybrid photocatalyst consists of carbon nitride and a molecular Ni(<small>II</small>)–terpyridine complex, which shows an order of magnitude improvement in CO yield when exposed to a mixed CO<small><sub>2</sub></small>/air atmosphere compared to high-purity CO<small><sub>2</sub></small> conditions. The CO yield is up to 623.3 μmol g<small><sup>−1</sup></small>, among the highest for CO<small><sub>2</sub></small> photoreduction in the presence of air. Our findings reveal that the simultaneous photodegradation of tetracycline is vital for the enhanced yield of CO in the presence of air. The photodegradation process consumes more photogenerated holes, aided by reactive oxygen species, which further optimizes the separation of photogenerated electron–hole pairs. Consequently, photogenerated electrons in the conduction band migrate more efficiently to the linked Ni(<small>II</small>)–terpyridine moiety, leading to improved CO<small><sub>2</sub></small> photoreduction efficiency. Notably, the presence of air does not inhibit but actually promotes the photoreduction of CO<small><sub>2</sub></small>. This study provides a unique strategy in which photocatalytic removal of organic pollutants is integrated with high-performance CO<small><sub>2</sub></small> photoreduction with the aid of air.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":6.1,"publicationDate":"2024-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142007630","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}
Ting Feng, Le Zhang, Shang-Xiao Wu, Xiaochao Shi and Ying-Feng Han
{"title":"Applications of metal N-heterocyclic carbene complexes in olefin polymerizations","authors":"Ting Feng, Le Zhang, Shang-Xiao Wu, Xiaochao Shi and Ying-Feng Han","doi":"10.1039/D4QI01470G","DOIUrl":"10.1039/D4QI01470G","url":null,"abstract":"<p >Polyolefins play an important role in modern society and are applied as both commodity plastics and high-performance polymers. Nowadays, they are widely used in large-scale industrial production and considered one among the most important polymers in the world. Since the 1950s, the exploration of Ziegler–Natta catalysts has not just brought continuous breakthroughs in the industrialization of polyolefins, but has also promoted the development of research in organometallic chemistry. Obviously, a key and long-standing focus in the polyolefin industry is the investigation of new metal catalysts that possess customizable catalytic performances. Over the past few decades, metal complexes with N-heterocyclic carbene (NHC) ligands have achieved great improvements and found vast applications in diverse research fields, and definitely, they have been also demonstrated to show excellent catalytic performances in olefin polymerization. Numerous reviews have been published on the catalytic performances of NHC-chelated metal complexes; however, a comprehensive overview of them with the central metals across the periodic table in olefin polymerization is currently lacking. This review aims to bridge this gap by providing a comprehensive summary of NHC catalysts and their corresponding structure–activity relationships in the polymerization and copolymerization of different olefins.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":6.1,"publicationDate":"2024-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142013815","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 Review on Covalent Organic Frameworks: Exploration of Their Growing Potential as Porous Materials in Photocatalytic Applications","authors":"Kamal Prakash, Rakesh Deka, Shaikh M. Mobin","doi":"10.1039/d4qi01480d","DOIUrl":"https://doi.org/10.1039/d4qi01480d","url":null,"abstract":"Photocatalysis powered by unlimited solar energy is an effective strategy to resolve energy and environmental issues. To achieve an efficient photocatalytic system, photocatalysts need to be highly crystalline and porous with excellent photostability under extreme conditions. Covalent organic framework (COF) has shown immense potential for photocatalytic application due to its unique structure, electronic, and photophysical characteristics. COF possesses a crystalline porous network with light absorption capabilities and excellent stability. Functionalized COFs can be developed through organic unit variation to obtain broader absorption, narrow bandgap, effective charge separation, and transportation. Furthermore, high photocatalytic efficiency can be achieved by heterostructure formation through anchoring or post-synthetic modification. Our review is focused on the recent advancement of COF as photocatalysts for various photocatalytic applications. The exploration commences by emphasizing the topological design, linkage chemistry, and functionalization of COFs, underscoring principles and requirements for high photocatalytic efficiency. It provides a deep dive into COF capabilities in different photocatalytic applications, covering areas such as hydrogen and oxygen evolution, carbon dioxide reduction, organic transformation, and organic pollutant degradation. Finally, it summarizes the pivotal points that need demanding attention and outlines future avenues, to offer fresh perspectives and contribute to revolutionary innovations in this rapidly evolving field.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142007597","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":"Fabrication of a multifunctional ionic covalent organic framework via the Menshutkin reaction and ion-exchange for dual-mode detection of organochlorine pesticides and design of a smartphone sensing platform†","authors":"Xiaoqin Shen and Bing Yan","doi":"10.1039/D4QI01698J","DOIUrl":"10.1039/D4QI01698J","url":null,"abstract":"<p >The synthesis of ionic covalent organic frameworks (iCOFs) is considerably limited due to the low solubility and challenging synthesis of the required monomers, making the ionic conversion of neutral COFs <em>via</em> post-synthetic modification (PSM) a viable alternative. Herein, we successfully converted a neutral COF (TfaTta) into a cationic COF (TfaTta–Br) through the Menshutkin reaction, utilizing benzyl bromide (BnBr) as the halogenated hydrocarbon, which subsequently underwent ion-exchange with the anionic compound methyl blue (MB) to generate a multifunctional material (TfaTta–MB) with dual emission. Studies demonstrated that TfaTta–MB is capable of ratiometric sensing of dicamba (DMA) and 2,6-dichloro-4-nitroaniline (DCN), two commonly used organochlorine pesticides, with limits of detection as low as 0.0241 μM and 0.128 μM, respectively. Density functional theory (DFT) calculations were performed for further research on the responsive mechanism. A hydrogel film (TfaTta–MB/AG) was prepared and affixed to a laboratory glove, creating a portable sensing device for detecting pesticide residues on the surface of vegetables. Notably, the obtained material enables colorimetric sensing of DMA and a smart sensing platform has been developed leveraging this functionality. In short, this work not only broadens the scope of ion transformation methods for neutral COFs, but also imposes great improvement in ratiometric sensing for organochlorine pesticide residues.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":6.1,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142007621","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 novel albumin-binding macrocyclic Gd-HPDO3A complex bearing a deoxycholic acid residue: the role of the hydration state, water exchange and local dynamics in the observed relaxivity†","authors":"Ferdeze Hasallari, Carla Carrera, Eleonora Cavallari, Eliana Gianolio and Silvio Aime","doi":"10.1039/D4QI00894D","DOIUrl":"10.1039/D4QI00894D","url":null,"abstract":"<p >Gd-HPDO3A (ProHance, Bracco) appears to be one of the MRI contrast agents with the lowest level of gadolinium retention in the body. Recently, we reported the synthesis and characterization of a Gd-HPDO3A derivative with good binding affinity to human serum albumin whose MR contrast efficiency was limited by the slow exchange rate of the coordinated water molecule and reduced hydration state of the albumin-bound complex. Here, we report the results on a strictly related analogue, Gd-HIBDO3A-DCA, which contains an additional methyl group on the hydroxyl arm. The minor structural modification resulted in the stabilization of the TSAP isomer (85%) (as clearly assessed by means of the <small><sup>1</sup></small>H-NMR spectroscopy of the europium complex). Gd-HIBDO3A-DCA displayed an enhanced water exchange rate (<em>τ</em><small><sub>M</sub></small> = 53 ns), by maintaining the stability of the parent Gd-HPDO3A complex. The expected high relaxivity of the supramolecular adduct with HSA is partly “quenched” by the flexibility of the spacer joining the Gd(<small>III</small>) chelate and the deoxycholic acid moiety. The high HSA binding capacity (three bound complexes) yields an excellent agent with good contrasting ability as shown in <em>in vivo</em> images acquired on a preclinical MRI scanner operating at 1T in a murine breast tumor model. Gd-HIBDO3A-DCA, administered at a half-dose (0.05 mmol kg<small><sup>−1</sup></small>) with respect to the conventional clinical dose, yielded more than two fold signal enhancement compared to ProHance in the tumor region. Moreover, the very high liver signal enhancement makes this complex a promising candidate for liver imaging in hepatic diseases.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":6.1,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/qi/d4qi00894d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142007602","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}