Applied Organometallic Chemistry最新文献

{"title":"Efficient Capture of Pb (II) Ions From Aqueous Solutions Using Metal Organic Frameworks@Covalent Organic Framework Composites With Abundant Carboxyl Groups","authors":"Shaopeng Zhang,&nbsp;Jie Ding,&nbsp;Dayong Tian,&nbsp;Ruiqin Kang,&nbsp;Xiaolong Wang,&nbsp;Haoyang He,&nbsp;Minghua Lu","doi":"10.1002/aoc.7995","DOIUrl":"https://doi.org/10.1002/aoc.7995","url":null,"abstract":"<div>\u0000 \u0000 <p>The development of efficient adsorbents with high selectivity is essential for mitigating environmental pollution. This study introduces a novel adsorbent comprising a metal–organic framework (i.e., MIL-101(Fe)-NH₂) and a covalent organic framework (COF) enriched with carboxyl groups, which is designated MIL-101(Fe)-NH₂/COF-COOH. The adsorbent is synthesized through a Schiff base reaction followed by carboxymethylation and is subsequently employed for Pb (II) adsorption. The structure of MIL-101(Fe)-NH₂/COF-COOH is confirmed using various characterization techniques, including Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, and Brunauer, Emmett, and Teller surface area analysis. The adsorption capacity (q_e) value of MIL-101(Fe)-NH₂/COF-COOH is estimated through batch adsorption experiments^. The effects of several factors, including pH, adsorbent dosage, contact time, Pb (II) concentration, solution ionic strength, and temperature, on the adsorption process are systematically assessed. MIL-101(Fe)-NH₂/COF-COOH achieves the highest adsorption of 184 mg/g at pH 6. The adsorption kinetics, isotherms, and thermodynamics indicate that the adsorption process occur through a spontaneous monolayer chemical process. Moreover, MIL-101(Fe)-NH₂/COF-COOH displays remarkable anti-interference capability, and its q_e decreases by only 10% after 10 cycles. Based on the characterization results, the Pb (II) adsorption mechanism is determined to be primarily electrostatic and chelation interactions between Pb (II) and O- and N-containing functional groups. Thus, this highly efficient and recyclable adsorbent exhibits considerable potential for removing Pb (II) from aquatic ecosystems.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 2","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143114373","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":"Coordination Bond-Based Nanosystems for Manipulating Niche Framework in Biomedical Applications","authors":"Bhagyashree V. Salvi,&nbsp;Pravin Shende","doi":"10.1002/aoc.7978","DOIUrl":"https://doi.org/10.1002/aoc.7978","url":null,"abstract":"<div>\u0000 \u0000 <p>The extensive connectivity between organic ligands and inorganic metal ions enables precise design and physicochemical modification of metal–organic frameworks (MOFs) for various applications. The metal-based counterparts, nanoscale metal–organic frameworks (nMOFs), are among advanced classes of hybrid nanoparticles, with the fundamental characteristics of pristine MOFs and nanoscale dimensions that enhance their potential for clinical applications. The distinct structure, pore size tunability, easy surface functionalization, large surface area, and porosity enable loading of various therapeutic and imaging agents. In addition, nMOFs demonstrate biocompatibility, multifunctionality, and the relatively labile metal–ligand bonds impart biodegradability. Owing to such excellent properties, nMOFs exhibits biomedically relevant applications as therapeutic cargoes, bioimaging, biosensing and biocatalysts agents. This article elucidates the advantages of nMOFs over other existing nanocarriers (e.g., organic and inorganic) and focuses on new insights of synthesis, design strategies with surface modification techniques for hybrid material development. The biomedical applications with futuristic approach are discussed with relevant examples in detail to inspire further exploration of nMOFs as biomedically relevant agents with great market potential in biomedical sciences.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 2","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143114417","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":"Design, Preparation, Characterization, Density Functional Theory, and HOMO-LUMO Perspective of Fe3O4@SiO2-Pr-NH-IC as a New Nanomagnetic Chemosensor","authors":"Fatemeh Zamiran,&nbsp;Ghodsi Mohammadi Ziarani,&nbsp;Mehran Feizi-Dehnayebi,&nbsp;Marziesadat Mirhosseyni,&nbsp;Alireza Badiei,&nbsp;Ahmed M. Abu-Dief","doi":"10.1002/aoc.7998","DOIUrl":"https://doi.org/10.1002/aoc.7998","url":null,"abstract":"<div>\u0000 \u0000 <p>In this research, the Fe₃O₄@SiO₂-Pr-NH-IC magnetic nanoparticles (MNPs) were synthesized based on Fe₃O₄ nanoparticles. Initially, Fe₃O₄ was coated with tetraethylorthosilicate (TEOS) to produce Fe₃O₄@SiO₂, which was functionalized by the reaction with 3-aminopropyl three-methoxy silane (APTMS) to yield Fe₃O₄@SiO₂-Pr-NH₂, followed by the treatment with indole-3-carbaldehyde (IC) to obtain Fe₃O₄@SiO₂-Pr-NH-IC as target hybrid organic and inorganic material. The Fe₃O₄@SiO₂-Pr-NH-IC was analyzed using photoluminescence spectroscopy. It was shown that this compound can selectively detect Al³⁺ ions in aqueous media among various cations, with a limit of detection (LOD) of 2.47 × 10⁻⁶ M. Comprehensive DFT calculations were carried out utilizing the B3LYP functional in conjunction with the 6-311g (d,p) and LANL2DZ basis sets to analyze the ground state of the system. To elucidate the interaction mechanism, the MEP map was generated, and a full geometry optimization was performed. Additionally, the electronic properties and chemical reactivity were examined through a HOMO-LUMO analysis at the same computational level. The findings revealed that the incorporation of the Al³⁺ ion significantly enhances the reactivity of the Pr-NH-IC + Al³⁺ complex in comparison to the free Pr-NH-IC structure. These findings suggest that Fe₃O₄@SiO₂-Pr-NH-IC has significant potential for the development of advanced sensor systems for the selective detection of Al³⁺ ions in aqueous environments. Future research could focus on the modification of the nanostructure to enhance its sensitivity and selectivity toward other environmentally and biologically relevant metal ions. Additionally, the integration of this material into portable sensing devices or the development of a real-time detection system could pave the way for practical applications in environmental monitoring and water quality assessment.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 2","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143114374","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":"Synthesis and Structural Characterization of Four Bidentate Ortho-Hydroxy Schiff Bases and Their Copper (II) Complexes: Evaluation of Biological Activities, Antioxidant Power, and Molecular Docking Studies","authors":"Sadia Boukreris,&nbsp;Narimane Kheddam,&nbsp;Mohammed Hadj Youcef,&nbsp;Nisserine Hamini-Kadar,&nbsp;Tayeb Benabdallah","doi":"10.1002/aoc.7954","DOIUrl":"https://doi.org/10.1002/aoc.7954","url":null,"abstract":"<div>\u0000 \u0000 <p>Four ortho-hydroxy aromatic bidentate Schiff bases were synthesized along with the corresponding copper (II) complexes and characterized by various analytical methods. The spatial configurations of the metal complexes were suggested in light of the analytical results obtained. Antibacterial evaluations revealed that the ligands were more active than their Cu(II) complexes. The study of antifungal activity showed that the fungus <i>Candida albicans</i> was more inhibited by the ligands (HL₃ and HL₄) and their Cu(II) complexes (IZ = 25 mm). According to the evaluation of antioxidant potency by the DPPH method, only ligand HL₄ demonstrated a comparatively low ability to scavenge free radicals compared to the ascorbic acid reference. Using the AutoDock 4.2 program, molecular docking investigations were conducted with the aim of predicting the structure–activity relationship for antibacterial qualities. Using the active sites of receptor proteins, the synthesized ligands were evaluated by molecular docking assays. A good correlation was found between the results of experimental antibacterial activity and the molecular docking data.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 2","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143114376","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":"Synthesis, Antioxidant, and Antidiabetic Potential of Ferrocenylmethylnucleobase Compounds: In Vitro, In Silico Molecular Docking, DFT Calculation, and Molecular Dynamic Simulations","authors":"Aicha Adaika,&nbsp;Yahia Bekkar,&nbsp;Souhir Youmbai,&nbsp;Lotfi Bourougaa,&nbsp;Elhafnaoui Lanez,&nbsp;Mohammed Larbi Ben Amor,&nbsp;Kaouther Nesba,&nbsp;Touhami Lanez,&nbsp;Lazhar Bechki","doi":"10.1002/aoc.7988","DOIUrl":"https://doi.org/10.1002/aoc.7988","url":null,"abstract":"<div>\u0000 \u0000 <p>This study presents the synthesis and characterization of a novel series of ferrocenylmethylnucleobase compounds, namely, FcMeAd, FcMeCy, FcMeTh, and (FcMe)₂Ad with promising antioxidant and antidiabetic properties. Spectroscopic techniques confirmed their sandwich-like geometry, with the nucleobase moiety coordinated to the ferrocene unit. Density functional theory (DFT) optimization revealed alignment with existing crystallographic data and indicated low frontier molecular orbital (FMO) energy gaps, suggesting facile intramolecular charge transfer and potential biological activity. The antidiabetic activity was evaluated in vitro through inhibition assays targeting α-glucosidase and α-amylase enzymes, which was supported by in silico molecular docking studies. Among the compounds, FcMeTh exhibited the highest antidiabetic and antioxidant properties due to the presence of carbonyl and amide functionalities, along with an electron-donating methyl group. Molecular dynamics (MD) simulations confirmed high binding affinity and structural stability of the docked compounds, with strong interactions with the target enzymes, further validating the potential of these compounds as effective inhibitors. Pharmacokinetic and ADMET evaluations indicated their nontoxic, noncarcinogenic nature and suitability for oral administration. The combined in vitro and in silico findings, including the critical insights from MD simulations, suggest that these ferrocenylmethylnucleobase compounds, especially FcMeTh, possess enhanced antioxidant and antidiabetic properties. This highlights their potential as promising therapeutic agents for managing oxidative stress and Type 2 diabetes.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 2","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143114589","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":"Anthracene-Based Schiff Base Allied Triazolyl Silatranes: A Comparison of Stability and Biological Activity With Open Analog Silane","authors":"Gurjaspreet Singh,&nbsp; Pawan,&nbsp;Manickam Selvaraj,&nbsp;Harshbir Kaur,&nbsp;Brij Mohan,&nbsp;Amarjit Kaur,&nbsp; Sanchita","doi":"10.1002/aoc.7972","DOIUrl":"https://doi.org/10.1002/aoc.7972","url":null,"abstract":"<div>\u0000 \u0000 <p>In this article, we have synthesized a series of anthracene-based triazolyl silatranes (ABSiT 1–7) using their open analogs, that is, anthracene-based triazolyl tri-ethoxysilanes via transesterification reaction. All synthesized compounds have been characterized using FTIR, NMR (¹H and ¹³C), DFT techniques, and TGA/DSC analysis to identify the stability and melting temperatures. The prepared silatranes were subsequently subjected to hydrolysis to compare their stability with their open-chain counterparts and explore their behavior under hydrolytic conditions. The data demonstrate that silatranes are about three times less prone to attack by water than organo-triethoxysilane and are hydrolytically more stable. Moreover, the thermal stability and pH stability were checked, and it was found that silatranes are stable up to a temperature range of 400°C and at pH 9.4, thus indicating that silatranes are more stable than their corresponding silanes at higher temperatures and large pH range. Moreover, all synthesized silatranes were tested for antioxidant and cytotoxicity activities, and the results disclosed their efficacy. A molecular docking study showed interactions of silatranes with Mutant p53 antitumor protein with binding affinity in the range −8.0 to −9.0 kcal/mol and identified as potent inhibitors.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 2","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143113730","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":"Pseudoagostic Interaction Based Zirconium Sensing Using 1,2,3-Triazole and Its Anticarcinogenic Potential Evaluation Through In Vitro and In Silico Approach","authors":"Gurjaspreet Singh,&nbsp; Heena,&nbsp;Sumesh Khurana,&nbsp; Mithun,&nbsp;Baljinder Singh Gill,&nbsp;Deepanjali Baliyan,&nbsp; Vikas,&nbsp;Necmi Dege,&nbsp;Erdoğan Tarcan","doi":"10.1002/aoc.7983","DOIUrl":"https://doi.org/10.1002/aoc.7983","url":null,"abstract":"<div>\u0000 \u0000 <p>With excellent yield, high selectivity, and sensitivity new 1,4-disubstituted 1,2,3-triazoles (<b>8a</b>) and (<b>8b</b>) were synthesized via Cu(I) catalyzed click reaction stitching the hydrazone tethered azide moiety with two different alkyne probes. They were subsequently characterized by ¹H NMR, ¹³C NMR, mass spectrometry, and FT-IR spectroscopy. In addition, X-ray crystallography offered the full structural elucidation of compounds (<b>4</b>), (<b>5</b>), and (<b>8a</b>). The optical properties of the designed chemosensor (<b>8a</b>) towards Zr(IV) have been assessed through UV–visible and fluorescence spectroscopy. The LOD values obtained from absorption and emission spectroscopy are 50 and 0.90 nM, respectively. The pseudoagostic interaction between (<b>8a</b>) and Zr(IV) was established using ¹H NMR, mass spectrometry, and FT-IR spectroscopy. (<b>8a</b>) and (<b>8b</b>) exhibited good antioxidant properties with 0.7135 and 0.856 μM IC₅₀ values and also revealed anticarcinogenic action in both in vitro and docking examinations, it may be anticipated that both probes have the potential to act as antitumor drugs.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 2","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143113742","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":"Construction of Covalent Triazine Framework With D-A1-A2 Configuration via Post-Modification for Photocatalytic Hydrogen Evolution","authors":"Yong Yang,&nbsp;Wei He,&nbsp;Dengmeng Song,&nbsp;Fang Xie,&nbsp;Jiaying Li,&nbsp;Jun Li,&nbsp;Ning Wang","doi":"10.1002/aoc.7980","DOIUrl":"https://doi.org/10.1002/aoc.7980","url":null,"abstract":"<div>\u0000 \u0000 <p>A D-A₁-A₂ type covalent triazine framework (CTF) was prepared for the photocatalytic hydrogen evolution (HER). In the resulting CTF-CZ-Bpy²⁺, 9-ethyl-9<i>H</i>-carbazole (CZ) group is used as the donor, triazine ring as the first acceptor, and cyclic diquat (Bpy²⁺) moiety as the second acceptor. Both experimental and theoretical results show that the D-A₁-A₂ structure significantly enhances the efficiency of photogenerated charge separation and transfer. As a result, CTF-CZ-Bpy²⁺ demonstrated outstanding photocatalytic HER activity with a yield rate of 31.1 mmol g⁻¹ h⁻¹, which is 7.8 times higher than that of nonfunctionalized CTF-CZ-Bpy.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 2","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143113744","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":"Nitrilotriacetic Acid Assisted Preparation of NiCo Bimetallic Nitride/N-Doped Carbon for Supercapacitor Electrode","authors":"Maiyong Zhu,&nbsp;Xun Zhang,&nbsp;Yu Yang,&nbsp;Qiao Luo,&nbsp;Songjun Li","doi":"10.1002/aoc.7986","DOIUrl":"https://doi.org/10.1002/aoc.7986","url":null,"abstract":"<div>\u0000 \u0000 <p>Transition metal nitride has been proved to be an ideal supercapacitor electrode material, and how to synthesize high-performance transition metal nitride-based materials rapidly and stably becomes critical. Here, we complexed the polydentate organic small molecule nitrilotriacetic acid with the transition metals Ni²⁺ and Co²⁺ and nitrided them by pyrolysis of urea. Considering the influence of the structure and morphology of the material on its energy storage properties, we further added sodium citrate to the system to study its effect on the morphology and properties of the complex. The composite (Ni-Co-N/NC) prepared under the optimal sodium citrate addition has a high specific capacitance of 610 F g⁻¹ at a current density of 1 A g⁻¹, and the specific capacitance remains at 84.4% of the initial capacitance after 5000 cycles at 5 A g⁻¹, which shows excellent cycling stability. The maximum energy density of the hybrid capacitor (Ni-Co-N/NC//AC ASC) assembled with activated carbon was 21.1 Wh·kg⁻¹ at a power density of 250 W·kg⁻¹, which shows a promising application in the field of energy storage.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 2","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143113470","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":"Coating MOF Layer on Fe3O4 Nanoparticles Towards Enhancing Photocatalysis Activation of Peroxydisulfate via Layer Thickness Control","authors":"Xi Chen,&nbsp;Danni Li,&nbsp;Mengkun Xu,&nbsp;Ping Wang,&nbsp;Wenshuai Qiu,&nbsp;Jinge Lu,&nbsp;Xingchen Li,&nbsp;Shaoming Yang,&nbsp;Yongxin Liu,&nbsp;Jiali Zhang","doi":"10.1002/aoc.7994","DOIUrl":"https://doi.org/10.1002/aoc.7994","url":null,"abstract":"<div>\u0000 \u0000 <p>As the photocatalytic layer, metal organic frameworks (MOFs) with thickness control were coated on the surface of Fe₃O₄ nanoparticles to investigate the influence of photocatalysis on the activation of peroxydisulfate to degrade antibiotic pollutants. A suitable thickness of MOF layer can not only enhance the adsorption of the substrate molecules on the composite catalyst but also provide optimized electron transfer distance and path, which is conducive to improving the efficiency of electron–hole separation, thereby enhancing the activation of peroxydisulfate and the degradation efficiency of pollutants.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 2","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143113472","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}