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Synthesis and characterization of bis-germylenes stabilized by bis(β-diketiminate) ligands 双(β-双酮酸酯)配体稳定双-两性烯的合成与表征
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-12-01 DOI: 10.1016/j.ica.2025.123010
Yanling Zhu , Yufen Yang , Yi Han, Bin Li
Dinuclear germylenes 1 and 2 bearing bis(β-diketiminate) ligands with 1,3-phenylene and 1,2-cyclohexylene linkers, respectively, have been synthesized. The structure flexibility was verified by the variable-temperature NMR analysis. Further salt metathesis with AgOTf led to bis-germylene 3 with OTf substituent. The reaction of 1 with LiAl[OCH(CF3)2]4, aiming to get the dinuclear dication, resulted in the formation of alkoxyl substituted bis-germylene with the elimination of Al[OCH(CF3)2]3. All compounds have been characterized by nuclear magnetic resonance (NMR) and single-crystal X-ray diffraction (SC-XRD).
合成了以1,3-苯基和1,2-环己烯为连接体的双(β-二酮酸酯)配体的双核germylene 1和2。通过变温核磁共振分析验证了结构的柔性。与AgOTf进一步的盐复分解得到具有OTf取代基的双二甲苯3。1与LiAl[OCH(CF3)2]4反应,目的是得到双核构型,生成烷氧基取代双germylene, Al[OCH(CF3)2]3被消去。所有化合物都通过核磁共振(NMR)和单晶x射线衍射(SC-XRD)进行了表征。
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引用次数: 0
Editorial: Pharmacologically active metallodrugs: From design to mode of action studies 社论:药理活性金属药物:从设计到作用模式的研究
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-12-01 DOI: 10.1016/j.ica.2025.123012
Iogann Tolbatov , Tiziano Marzo
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引用次数: 0
Factors influencing imine activation in M(II) complexes to afford ligated N,O-aminal and hemiacetal groups: XRD, 1H NMR, and computational studies 影响M(II)配合物中亚胺活化以提供连接的N, o -动物和半缩醛基团的因素:XRD, 1H NMR和计算研究
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-30 DOI: 10.1016/j.ica.2025.123007
Daniel L. Singer , Jason G. Marmorstein , Joseph M. Tanski , Timothy J. Barnum , Laurie A. Tyler
The reactivity of ligated imines with alcohol-type nucleophiles has been investigated. Four Cu (II) complexes containing a N,N′-bis (2-pyridinylmethylene)-1,2-ethanediamine ((Py)2en) type ligand are reported, along with the hydrolysis or addition of solvent methanol across the imine CN bond. The products of this reactivity include the formation of ligated N,O-aminal or hemiacetal moieties as confirmed through single crystal X-ray crystallography. The observed product distribution is supported with ab initio and density functional theory calculations. A comprehensive 1H NMR study was performed with further derivatized ligand frames and diamagnetic Zn (II) species to explore the scope of the observed reactivity. These studies indicate that the ligand substituent strongly impacts the degree of imine activation toward reaction with solvent methanol and/or water (i.e. formation of mono N,O-aminal, bis N,O-aminal, hemiacetal or no reaction). The identity of the counterion in the hydrated zinc salt was also found to play a role, albeit to a lesser extent. The implications of the identity of the alcohol solvent on the CN reactivity was also investigated. Alcohols with decreased steric hindrance and increased nucleophilicity show the greatest propensity for addition.
研究了连接亚胺与醇型亲核试剂的反应性。报道了四种含有N,N ' -二(2-吡啶基亚甲基)-1,2-乙二胺((Py)2en)型配体的Cu (II)配合物,并在亚胺CN键上水解或加成溶剂甲醇。这种反应的产物包括通过单晶x射线晶体学证实的连接的N, o -动物或半缩醛部分的形成。观察到的产品分布得到从头算和密度泛函理论计算的支持。对进一步衍生化配体框架和抗磁性Zn (II)进行了全面的1H NMR研究,以探索观察到的反应性范围。这些研究表明,配体取代基强烈影响亚胺与溶剂甲醇和/或水反应的活化程度(即形成单N, o -氨基,双N, o -氨基,半缩醛或不反应)。水合锌盐中反离子的特性也被发现起作用,尽管程度较小。研究了醇溶剂的性质对CN反应性的影响。空间位阻降低和亲核性增加的醇表现出最大的加成倾向。
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引用次数: 0
A water-soluble Schiff base ligand and its Al(III) complex: optical properties, computational studies and photocatalytic performance 水溶性席夫碱配体及其Al(III)配合物:光学性质、计算研究和光催化性能
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-30 DOI: 10.1016/j.ica.2025.123014
Hajer Bouznif , Licínia L.G. Justino , Telma Costa , Maria I.L. Soares , M. Luísa Ramos , Teresa M.V.D. Pinho e Melo , Nabil Zouari , Rui Fausto
Although the field of inorganic photophysics and photochemistry has traditionally been dominated by complexes of precious and rare metals, increasing concerns regarding their scarcity and cost have led to a growing interest in earth-abundant metal-based compounds as more sustainable and economically viable alternatives. In this study, we investigated the photophysical properties of two water-soluble compounds: the di-Schiff base N,N′-bis(3-methoxy-5-sulfonatosalicylidene)-1,2-ethylenediamine disodium salt (MSS) and its corresponding Al(III) complex. To better understand the enol-imine (O-H···N) vs. keto-enamine (O···H-N) tautomeric behavior of MSS, we also considered its non-methoxy analogue (SS) as a reference compound. Using UV–vis absorption and diffuse reflectance spectroscopy, we examined the tautomeric preferences of MSS and SS in both the solid state and various solvents. The spectral features of MSS exhibited a noticeable bathochromic shift relative to SS in all media. In protic solvents (H2O, MeOH) and in the solid state, MSS is found predominantly in the keto-enamine form, while in aprotic polar solvents (DMSO, DMF), a mixture of keto and enol forms coexist. In contrast, SS shows a dynamic coexistence of both tautomeric forms in protic solvents, while the SS enol form becomes dominant in DMSO and DMF; in the solid-state SS predominantly adopts the keto-enamine form. These differences were rationalized in terms of electronic effects. The direct band gap energies were determined to be 2.75 eV for SS, 2.61 eV for MSS and 3.03 eV for the Al(III)/MSS complex, revealing their wide-band-gap-semiconductor character. These values were supported by DFT calculations, which were found to be able to reproduce the experimental trends and were also used to provide insight into the electronic structure of the studied compounds. Photoluminescence analysis revealed that MSS emits in the green region, while the Al(III)/MSS complex exhibits a blue-white emission, making both compounds promising candidates for application in single-layer white OLEDs. Additionally, the Al(III)/MSS complex displayed photocatalytic activity toward the degradation of methylene blue (MB), with a rate constant of 0.032 min−1, indicating its potential as a multifunctional material for both optoelectronic and environmental applications.
尽管无机光物理和光化学领域传统上以贵金属和稀有金属的配合物为主,但对其稀缺性和成本的日益关注导致人们对地球上丰富的金属基化合物越来越感兴趣,认为它们是更可持续和经济上可行的替代品。在这项研究中,我们研究了两种水溶性化合物:二希夫碱N,N ' -双(3-甲氧基-5-磺酰基水杨基)-1,2-乙二胺二钠盐(MSS)及其相应的Al(III)配合物的光物理性质。为了更好地了解烯醇-亚胺(O- h··N)与酮-烯胺(O··h·N)互变异构体的行为,我们还考虑了其非甲氧基类似物(SS)作为参考化合物。利用紫外-可见吸收和漫反射光谱,研究了MSS和SS在固态和各种溶剂中的互变异构偏好。在所有介质中,MSS的光谱特征都表现出明显的色移。在质子溶剂(H2O, MeOH)和固态中,MSS主要以酮-烯胺形式存在,而在非质子极性溶剂(DMSO, DMF)中,酮和烯醇形式的混合物共存。相反,SS在质子溶剂中表现出两种互变异构形式的动态共存,而SS烯醇形式在DMSO和DMF中占主导地位;在固态SS中主要采用酮-烯胺形式。根据电子效应,这些差异是合理的。结果表明,Al(III)/MSS配合物的直接带隙能为2.75 eV, MSS为2.61 eV, Al(III)/MSS配合物为3.03 eV。这些值得到了DFT计算的支持,DFT计算被发现能够重现实验趋势,并且还用于深入了解所研究化合物的电子结构。光致发光分析表明,MSS在绿色区域发射,而Al(III)/MSS配合物则呈现蓝白色发射,这使得这两种化合物都有希望应用于单层白色oled。此外,Al(III)/MSS配合物对亚甲基蓝(MB)的降解表现出光催化活性,速率常数为0.032 min−1,表明其具有作为光电和环境多功能材料的潜力。
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引用次数: 0
Carboxylated benzo and pyrazine annulated PV corrolazines. I. Synthesis, spectral-luminescence and acid-base properties of octaethyl esters 羧基苯并吡嗪环吡啶。一、辛乙酯的合成、光谱发光及酸碱性质
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-29 DOI: 10.1016/j.ica.2025.123000
Dmitriy A. Lazovskiy , Ekaterina S. Gnedina , Ivan A. Nikitin , Hailong Wang , Pavel A. Stuzhin
Ethyl octaesters of phthalocyanine bearing eight carboxy-groups, [EstPcH2] (3), and its pyrazine fused analogue [EstTPyzPAH]2 (4) were synthesized by melting of corresponding dicarbonitriles in presence of sodium hydroxide or ethoxide. Reaction of these macrocycles with PBr3 in pyridine leads to contraction of the porphyrazine macrocycle and formation of the corresponding PV corrolazines, isolated as oxophosphorus(V) and dihydroxidophosphorus(V) complexes, [EstTBzCAP=O] (5) and [EstTPyzCAP(OH)2] (6). Fusion of electron-withdrawing pyrazine rings increases the NH acidity of the porphyrazine macrocycle leading to easy deprotonation of 4 and decreases the basicity of meso‑nitrogens – all of them can be protonated in 5 and only one in 6. Combination of electron-deficient pyrazine rings and electron-withdrawing COOEt groups leads to enhanced singlet oxygen generating ability not only by corrolazine 6, but also by dianionic form of porphyrazine 4Δ = 0.58 and 0.32, respectively). The obtained octaethyl esters can be considered as precursors for water-soluble octacarboxylated derivatives and building blocks for design of organic frameworks.
通过在氢氧化钠或乙氧基存在下将相应的二腈熔化,合成了含有8个羧基的酞菁八酯[EstPcH2](3)及其吡嗪融合类似物[EstTPyzPAH]2(4)。这些大环与PBr3在吡啶中的反应导致卟啉大环收缩并形成相应的PV腐蚀嗪,分离为氧磷(V)和二羟基磷(V)配合物,[EstTBzCAP=O](5)和[EstTPyzCAP(OH)2](6)。吸电子吡嗪环的融合增加了卟啉大环的NH酸度,导致4容易去质子化,并降低了中位氮的碱度——所有中位氮都能在5中质子化,而在6中只有一个。缺乏电子的吡嗪环与吸电子的COOEt基团结合,不仅可以增强腐蚀嗪6的单线态产氧能力,还可以增强重阴离子形式的卟啉嗪4的单线态产氧能力(ФΔ = 0.58和0.32)。所得到的辛乙酯可以被认为是水溶性八羧基化衍生物的前体和设计有机框架的构建块。
{"title":"Carboxylated benzo and pyrazine annulated PV corrolazines. I. Synthesis, spectral-luminescence and acid-base properties of octaethyl esters","authors":"Dmitriy A. Lazovskiy ,&nbsp;Ekaterina S. Gnedina ,&nbsp;Ivan A. Nikitin ,&nbsp;Hailong Wang ,&nbsp;Pavel A. Stuzhin","doi":"10.1016/j.ica.2025.123000","DOIUrl":"10.1016/j.ica.2025.123000","url":null,"abstract":"<div><div>Ethyl octaesters of phthalocyanine bearing eight carboxy-groups, [<sup>Est</sup><em>Pc</em>H<sub>2</sub>] (<strong>3</strong>), and its pyrazine fused analogue [<sup>Est</sup><em>TPyzPA</em>H]<sub>2</sub> (<strong>4</strong>) were synthesized by melting of corresponding dicarbonitriles in presence of sodium hydroxide or ethoxide. Reaction of these macrocycles with PBr<sub>3</sub> in pyridine leads to contraction of the porphyrazine macrocycle and formation of the corresponding P<sup>V</sup> corrolazines, isolated as oxophosphorus(V) and dihydroxidophosphorus(V) complexes, [<sup>Est</sup><em>TBzCA</em>P=O] (<strong>5</strong>) and [<sup>Est</sup><em>TPyzCA</em>P(OH)<sub>2</sub>] (<strong>6</strong>). Fusion of electron-withdrawing pyrazine rings increases the NH acidity of the porphyrazine macrocycle leading to easy deprotonation of <strong>4</strong> and decreases the basicity of <em>meso</em>‑nitrogens – all of them can be protonated in <strong>5</strong> and only one in <strong>6</strong>. Combination of electron-deficient pyrazine rings and electron-withdrawing COOEt groups leads to enhanced singlet oxygen generating ability not only by corrolazine <strong>6</strong>, but also by dianionic form of porphyrazine <strong>4</strong> (Ф<sub>Δ</sub> = 0.58 and 0.32, respectively). The obtained octaethyl esters can be considered as precursors for water-soluble octacarboxylated derivatives and building blocks for design of organic frameworks.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123000"},"PeriodicalIF":3.2,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145683083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Unveiling the structural and electronic features of a hexamethylenetetramine complex of zinc 3-hydroxybenzoate: crystal structure, hirshfeld surface, DFT, and molecular docking studies 揭示3-羟基苯甲酸锌六亚甲基四胺配合物的结构和电子特征:晶体结构、hirshfeld表面、DFT和分子对接研究
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-29 DOI: 10.1016/j.ica.2025.123013
Giray Buğra Akbaba , Füreya Elif Öztürkkan , Elaheh Teymouri , Tuncer Hökelek , Hacali Necefoğlu
A novel dinuclear Zn(II) complex, [Zn₂(3HBA)₄(HMTA)₂]·2H₂O (3HBA: 3-hydroxybenzoate and HMTA: hexamethylenetetramine), has been synthesized and fully characterized by single-crystal X-ray diffraction, FT-IR, NMR, UV–Vis, and DFT studies. The crystal structure reveals a centrosymmetric dimeric framework where each Zn(II) ion adopts a slightly distorted square-pyramidal geometry, coordinated by four bridging 3-hydroxybenzoate anions and one nitrogen atom from a monodentate hexamethylenetetramine (HMTA) ligand. The crystal packing is stabilized through an extensive network of O–H···O, O–H···N, C–H···O, and C–H···N hydrogen bonds, as confirmed by Hirshfeld surface analysis, in which H···H (47.5 %) and H···O/O···H (16.3 %) contacts dominate the intermolecular interactions. The void analysis revealed a low porosity (5.81 %), suggesting a densely packed and mechanically stable lattice. Spectroscopic data corroborate coordination through both carboxylate oxygen and HMTA nitrogen donors, while DFT calculations (B3LYP/LANL2DZ) indicate a large HOMO–LUMO gap (ΔE = 4.28 eV), consistent with high kinetic stability and moderate electrophilicity (ω = 2.99 eV). The molecular electrostatic potential (MEP) map highlights electron-rich carboxylate oxygen atoms as probable electrophilic sites. Molecular docking simulations against DNA gyrase B (PDB: 4URM) and New Delhi metallo-β-lactamase-1 (NDM-1, PDB: 4HL2) revealed strong binding affinities (−8.1 and − 10.2 kcal/mol, respectively), involving multiple hydrogen bonds and π-interactions with key active-site residues. Overall, the combined experimental and theoretical findings confirm the robust structural integrity, electronic stability, and notable antibacterial binding potential of the complex, particularly against β-lactamase-type bacterial enzymes.
合成了一种新型的双核Zn(II)配合物[Zn₂(3HBA)₄(HMTA)₂]·2H₂O (3HBA: 3-羟基苯甲酸盐和HMTA:六亚甲基四胺),并通过单晶x射线衍射、FT-IR、NMR、UV-Vis和DFT研究对其进行了充分的表征。晶体结构显示出中心对称的二聚体框架,其中每个Zn(II)离子采用略微扭曲的方锥体几何形状,由四个桥接的3-羟基苯甲酸阴离子和一个来自单齿六亚甲基四胺(HMTA)配体的氮原子配位。Hirshfeld表面分析证实,O - H·O、O - H·N、C-H·O和C-H·N氢键组成的广泛网络稳定了晶体填充,其中H·H(47.5%)和H·O/O·H(16.3%)接触主导了分子间相互作用。孔洞分析显示其孔隙率低(5.81%),表明其晶格密集且机械稳定。光谱数据证实了羧酸氧和HMTA氮给体的配位,而DFT计算(B3LYP/LANL2DZ)表明HOMO-LUMO间隙很大(ΔE = 4.28 eV),具有高的动力学稳定性和中等的亲电性(ω = 2.99 eV)。分子静电势(MEP)图突出了富电子羧酸氧原子作为可能的亲电位点。与DNA旋切酶B (PDB: 4URM)和新德里金属β-内酰胺酶1 (NDM-1, PDB: 4HL2)的分子对接模拟显示,它们具有很强的结合亲和力(分别为−8.1和−10.2 kcal/mol),涉及多个氢键和与关键活性位点残基的π相互作用。总的来说,实验和理论结果证实了该复合物具有强大的结构完整性、电子稳定性和显著的抗菌结合潜力,特别是针对β-内酰胺酶型细菌酶。
{"title":"Unveiling the structural and electronic features of a hexamethylenetetramine complex of zinc 3-hydroxybenzoate: crystal structure, hirshfeld surface, DFT, and molecular docking studies","authors":"Giray Buğra Akbaba ,&nbsp;Füreya Elif Öztürkkan ,&nbsp;Elaheh Teymouri ,&nbsp;Tuncer Hökelek ,&nbsp;Hacali Necefoğlu","doi":"10.1016/j.ica.2025.123013","DOIUrl":"10.1016/j.ica.2025.123013","url":null,"abstract":"<div><div>A novel dinuclear Zn(II) complex, [Zn₂(3HBA)₄(HMTA)₂]·2H₂O (3HBA: 3-hydroxybenzoate and HMTA: hexamethylenetetramine), has been synthesized and fully characterized by single-crystal X-ray diffraction, FT-IR, NMR, UV–Vis, and DFT studies. The crystal structure reveals a centrosymmetric dimeric framework where each Zn(II) ion adopts a slightly distorted square-pyramidal geometry, coordinated by four bridging 3-hydroxybenzoate anions and one nitrogen atom from a monodentate hexamethylenetetramine (HMTA) ligand. The crystal packing is stabilized through an extensive network of O–H···O, O–H···N, C–H···O, and C–H···N hydrogen bonds, as confirmed by Hirshfeld surface analysis, in which H···H (47.5 %) and H···O/O···H (16.3 %) contacts dominate the intermolecular interactions. The void analysis revealed a low porosity (5.81 %), suggesting a densely packed and mechanically stable lattice. Spectroscopic data corroborate coordination through both carboxylate oxygen and HMTA nitrogen donors, while DFT calculations (B3LYP/LANL2DZ) indicate a large HOMO–LUMO gap (ΔE = 4.28 eV), consistent with high kinetic stability and moderate electrophilicity (ω = 2.99 eV). The molecular electrostatic potential (MEP) map highlights electron-rich carboxylate oxygen atoms as probable electrophilic sites. Molecular docking simulations against DNA gyrase B (PDB: <span><span>4URM</span><svg><path></path></svg></span>) and New Delhi metallo-β-lactamase-1 (NDM-1, PDB: <span><span>4HL2</span><svg><path></path></svg></span>) revealed strong binding affinities (−8.1 and − 10.2 kcal/mol, respectively), involving multiple hydrogen bonds and π-interactions with key active-site residues. Overall, the combined experimental and theoretical findings confirm the robust structural integrity, electronic stability, and notable antibacterial binding potential of the complex, particularly against β-lactamase-type bacterial enzymes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"591 ","pages":"Article 123013"},"PeriodicalIF":3.2,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145690758","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Coordination compounds of lithium, sodium, and potassium with 2-nitrophenol: Single-crystal X-ray diffraction and FT-IR spectroscopic study 锂、钠、钾与2-硝基苯酚的配位化合物:单晶x射线衍射和红外光谱研究
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-27 DOI: 10.1016/j.ica.2025.123006
A.A. Bezdomnikov , F.M. Dolgushin , L.I. Demina , V.E. Sharov , E.A. Kurenkova , V.E. Baulin , A.Yu. Tsivadze
Alkyl derivatives of 2-nitrophenol are promising extractants for the selective recovery of lithium in the presence of large excesses of sodium and potassium ions. To probe the structural factors underpinning lithium selectivity, we synthesized coordination compounds of lithium, sodium and potassium with 2-nitrophenol and established their composition and structures by elemental analysis, single-crystal X-ray diffraction (SCXRD) and FT-IR spectroscopy. General regularities in the binding of 2-nitrophenol with Li+, Na+ and K+ were identified. The ability of 2-nitrophenol to form six-membered chelate metallacycles with alkali-metal cations has been confirmed. Notably, the geometry of lithium metallacycles, even within the same compound, varies from nearly planar to boat and envelope conformations.
2-硝基酚的烷基衍生物是一种很有前途的萃取剂,用于在钠离子和钾离子大量过量的情况下选择性回收锂。为了探究影响锂选择性的结构因素,我们与2-硝基苯酚合成了锂、钠和钾的配位化合物,并通过元素分析、单晶x射线衍射(SCXRD)和傅里叶红外光谱(FT-IR)确定了它们的组成和结构。鉴定了2-硝基苯酚与Li+、Na+和K+结合的一般规律。2-硝基苯酚与碱金属阳离子形成六元螯合金属环的能力已得到证实。值得注意的是,即使在同一化合物中,锂金属循环的几何形状也从接近平面到船形和包膜构象。
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引用次数: 0
Investigation of vibrational properties of rare-earth ruddlesden-popper nickelates Ln₂NiO₄ (Ln = La, Pr, Nd, Eu, Gd) 稀土杂铜镍酸盐Ln₂NiO₄(Ln = La, Pr, Nd, Eu, Gd)的振动性能研究
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-27 DOI: 10.1016/j.ica.2025.123005
Neenu Saini , Ruby Jindal , Archana Tripathi , Uma Shekhawat , Reechu Saini , Naveen Kumar
The Raman and Infrared (IR) phonon analysis of monolayer Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd) rare-earth Ruddlesden-Popper (RP) Nickelates in the tetragonal phase, which have potential applications as electrocatalysts for solid oxide cells, has been carried out using normal coordinates. The Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd) Ruddlesden-Popper compounds possess D174h Point Group Symmetry, fall under the space group 139, and crystallize in the phase I4/mmm with a formula unit number Z = 2. The Layered Perovskite Oxides Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd) represent the initial members of the Ruddlesden-Popper Nickelates Series, which are structurally defined by the general stoichiometry Lnn+1NinO3n+1 (Ln = La, Pr, Nd, Eu, Gd) with n = 1. The theoretical analysis of the optical phonon modes in Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd) Ruddlesden-Popper Nickelates crystallizing in the I4/mmm structural phase employs a set of nine Short-Range Force Constants (SRFCs). Wilson's GF-Matrix Method has characterized and assigned the optical vibrational modes in rare-earth Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd) Ruddlesden-Popper Nickelates. The study further investigates the impact of the A-site Lanthanide cation-Ln (Ln = La, Pr, Nd, Eu, Gd) substitution on the lattice dynamics of the isostructural compounds Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd) within the framework of monolayered tetragonal structures. To elucidate the effects of cation-Ln substitution, a comparative analysis of the frequencies at the zone centre, bond lengths, and force constants is conducted. The vibrational frequencies primarily governed by the Ln-atoms (Ln = La, Pr, Nd, Eu, Gd) display unique features that change with atomic number, highlighting the significant influence of Ln-ion size on the phonon dynamics of Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd) rare-earth Nickel Oxides. Furthermore, for each normal mode in the Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd) rare-earth Ruddlesden-Popper Nickelates, the study of Potential Energy Distribution (PED) emphasizes the considerable role played by Short-Range Force Constants in shaping the wavenumbers, thereby offering a deeper insight into the lattice dynamics and interatomic interactions. Layered Perovskite Oxides Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd) exhibit key LnO and NiO phonon modes that govern oxygen ion transport, defect chemistry, and SOFC efficiency.
利用正坐标法,对具有固体氧化物电池电催化剂潜力的四相稀土Ruddlesden-Popper (RP)镍酸盐单层(Ln = La, Pr, Nd, Eu, Gd)进行了拉曼和红外声子分析。Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd) Ruddlesden-Popper化合物具有D174h点群对称性,属于139空间群,在I4/mmm相中结晶,公式单位数为Z = 2。层状钙钛矿氧化物Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd)是Ruddlesden-Popper镍酸盐系列的初始成员,其结构由n = 1的一般化学计量Lnn+1NinO3n+1 (Ln = La, Pr, Nd, Eu, Gd)定义。采用9个短程力常数(SRFCs)对在I4/mmm结构相中结晶的Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd) Ruddlesden-Popper镍酸盐的光学声子模式进行了理论分析。Wilson的gf矩阵方法表征和分配了稀土Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd) Ruddlesden-Popper镍酸盐的光学振动模式。本研究进一步探讨了a位镧系阳离子-Ln (Ln = La, Pr, Nd, Eu, Gd)取代对单层四方结构框架内同构化合物Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd)晶格动力学的影响。为了阐明阳离子- ln取代的影响,对区中心的频率、键长和力常数进行了比较分析。主要由Ln原子(Ln = La, Pr, Nd, Eu, Gd)控制的振动频率显示出随原子序数变化的独特特征,突出了Ln离子尺寸对Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd)稀土镍氧化物声子动力学的显著影响。此外,对于Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd)稀土Ruddlesden-Popper镍酸盐中的每个正态模式,势能分布(PED)的研究强调了近距离力常数在形成波数方面的重要作用,从而对晶格动力学和原子间相互作用提供了更深入的了解。层状钙钛矿氧化物Ln2NiO4 (Ln = La, Pr, Nd, Eu, Gd)表现出控制氧离子传输、缺陷化学和SOFC效率的关键LnO和NiO声子模式。
{"title":"Investigation of vibrational properties of rare-earth ruddlesden-popper nickelates Ln₂NiO₄ (Ln = La, Pr, Nd, Eu, Gd)","authors":"Neenu Saini ,&nbsp;Ruby Jindal ,&nbsp;Archana Tripathi ,&nbsp;Uma Shekhawat ,&nbsp;Reechu Saini ,&nbsp;Naveen Kumar","doi":"10.1016/j.ica.2025.123005","DOIUrl":"10.1016/j.ica.2025.123005","url":null,"abstract":"<div><div>The Raman and Infrared (IR) phonon analysis of monolayer Ln<sub>2</sub>NiO<sub>4</sub> (Ln = La, Pr, Nd, Eu, Gd) rare-earth Ruddlesden-Popper (RP) Nickelates in the tetragonal phase, which have potential applications as electrocatalysts for solid oxide cells, has been carried out using normal coordinates. The Ln<sub>2</sub>NiO<sub>4</sub> (Ln = La, Pr, Nd, Eu, Gd) Ruddlesden-Popper compounds possess <span><math><msubsup><mi>D</mi><mn>17</mn><mrow><mn>4</mn><mi>h</mi></mrow></msubsup></math></span> Point Group Symmetry, fall under the space group 139, and crystallize in the phase I4/mmm with a formula unit number Z = 2. The Layered Perovskite Oxides Ln<sub>2</sub>NiO<sub>4</sub> (Ln = La, Pr, Nd, Eu, Gd) represent the initial members of the Ruddlesden-Popper Nickelates Series, which are structurally defined by the general stoichiometry Ln<sub>n+1</sub>Ni<sub>n</sub>O<sub>3n+1</sub> (Ln = La, Pr, Nd, Eu, Gd) with <em>n</em> = 1. The theoretical analysis of the optical phonon modes in Ln<sub>2</sub>NiO<sub>4</sub> (Ln = La, Pr, Nd, Eu, Gd) Ruddlesden-Popper Nickelates crystallizing in the I4/mmm structural phase employs a set of nine Short-Range Force Constants (SRFCs). Wilson's GF-Matrix Method has characterized and assigned the optical vibrational modes in rare-earth Ln<sub>2</sub>NiO<sub>4</sub> (Ln = La, Pr, Nd, Eu, Gd) Ruddlesden-Popper Nickelates. The study further investigates the impact of the A-site Lanthanide cation-Ln (Ln = La, Pr, Nd, Eu, Gd) substitution on the lattice dynamics of the isostructural compounds Ln<sub>2</sub>NiO<sub>4</sub> (Ln = La, Pr, Nd, Eu, Gd) within the framework of monolayered tetragonal structures. To elucidate the effects of cation-Ln substitution, a comparative analysis of the frequencies at the zone centre, bond lengths, and force constants is conducted. The vibrational frequencies primarily governed by the Ln-atoms (Ln = La, Pr, Nd, Eu, Gd) display unique features that change with atomic number, highlighting the significant influence of Ln-ion size on the phonon dynamics of Ln<sub>2</sub>NiO<sub>4</sub> (Ln = La, Pr, Nd, Eu, Gd) rare-earth Nickel Oxides. Furthermore, for each normal mode in the Ln<sub>2</sub>NiO<sub>4</sub> (Ln = La, Pr, Nd, Eu, Gd) rare-earth Ruddlesden-Popper Nickelates, the study of Potential Energy Distribution (PED) emphasizes the considerable role played by Short-Range Force Constants in shaping the wavenumbers, thereby offering a deeper insight into the lattice dynamics and interatomic interactions. Layered Perovskite Oxides Ln<sub>2</sub>NiO<sub>4</sub> (Ln = La, Pr, Nd, Eu, Gd) exhibit key Ln<img>O and Ni<img>O phonon modes that govern oxygen ion transport, defect chemistry, and SOFC efficiency.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123005"},"PeriodicalIF":3.2,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145645729","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Advancing anticancer chelation therapy: Insights from enhancing cytotoxic potency, targeted cellular delivery, metal-based immunomodulation, and combinatorial strategies 推进抗癌螯合治疗:从增强细胞毒性、靶向细胞递送、金属基免疫调节和组合策略的见解
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-27 DOI: 10.1016/j.ica.2025.123004
Carmen Acosta , Oscar Claudio-Ares , Irfan Ullah , Laura Catalina Cruz , Adam C. Ducey, Adriana Vidal, Alejandro Escalante-Castaneda, Ambar R. Maldonado-Santos, Biao Liu, Cristina N. Villanueva, Diego A. Martínez-Sebastian, Jubilie Zeda-Rodríguez, Norian Ceballos-Plaza, Sofía V. González-Tossas, Stephanie K. Reyes-Vargas, Wilarye Trujillo-Rivera, Wentao Hou, Yailiz A. Velez-Pizarro, Yiomaris Rodríguez-Manzano, Arthur D. Tinoco
Chelation therapy has long been recognized for its success in treating heavy metal poisoning and iron overload disorders. Building on this foundation, drug repurposing of FDA-approved iron chelators for anticancer therapy has been extensively explored, alongside the development of novel agents such as the promising triapine. Current research increasingly targets the essential metals iron, copper, and zinc in oncology, with a focus on chelators that actively modulate the biochemical effects of these metals rather than functioning as ionophores. This review highlights recent advances in refining chelation strategies to enhance cytotoxic potency and tumor specificity, including approaches that tune metal redox activity, synergize with platinum(II)-based drugs, incorporate nanoparticulate delivery systems, leverage metal-driven immunostimulation, and combine with established or emerging therapies. By assessing the successes and limitations of recent studies and surveying relevant human clinical trials, we evaluate the feasibility of integrating chelation therapy into clinical oncology. Evidence suggests that chelation is most effective when combined with other treatment modalities, offering potential synergistic benefits in cancer management.
螯合疗法在治疗重金属中毒和铁超载疾病方面的成功早已得到认可。在此基础上,fda批准的铁螯合剂用于抗癌治疗的药物再利用已经得到了广泛的探索,同时也开发了新的药物,如有前途的曲平。目前的研究越来越多地针对肿瘤中的必需金属铁、铜和锌,并将重点放在积极调节这些金属的生化作用的螯合剂上,而不是作为离子载体。这篇综述强调了在改进螯合策略以提高细胞毒性效力和肿瘤特异性方面的最新进展,包括调整金属氧化还原活性、与铂(II)基药物协同、结合纳米颗粒递送系统、利用金属驱动的免疫刺激以及与现有或新兴疗法结合的方法。通过评估最近研究的成功和局限性以及调查相关的人体临床试验,我们评估了将螯合治疗纳入临床肿瘤学的可行性。有证据表明,当与其他治疗方式联合使用时,螯合治疗最有效,在癌症治疗中提供潜在的协同效益。
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引用次数: 0
Targeting and bioimaging of human lung cancer cells via Heteroleptic iridium complexes 异效铱复合物对人肺癌细胞的靶向和生物成像研究
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-26 DOI: 10.1016/j.ica.2025.123009
Özlem Altsoy , Özlem Biçen Ünlüer , Filiz Yilmaz , Sibel Emir Diltemiz , Deniz Hür , Arzu Ersöz , Ridvan Say
Two bis-cyclometalated iridium complexes [Ir(ppyCF3)2(MAA)] (ppyCF3: 2-(4-trifluoromethylphenyl)pyridine; MAA: methacryloylamino acid) have been synthesized and characterized by 1H NMR, 13C NMR, 19F NMR, UV–Vis and FT-IR spectroscopy. The potential of the synthesized Ir(III) complexes as bioimaging agents was examined through their interaction with transferrin receptors in cells. The iridium complexes were attached to the transferrin protein via electron transfer using the tyrosine or tryptophan groups in the MAA ligand. This interaction enhances intracellular targeting and imaging efficiency, thereby expanding the potential applications of Ir(III) complexes in biological systems. In our study, we obtained two different types of biomaterials by interacting Ir(III) complexes with transferrin. The first type is iridium-transferrin cross-linked conjugates (Ir-Tf), and the second type is nano-structured iridium-transferrin cross-linked polymers (nanoIr-Tf). Our findings demonstrate that [Ir(ppyCF3)2(MATyr)]-Tf and nano[Ir(ppyCF3)2(MATyr)]-Tf show promise as efficient bioimaging agents. When interacting with both cancerous and normal lung cells, these complexes displayed robust fluorescence emission, enabling precise imaging and visualization. Notably, the complexes selectively localized within the cytoplasm of cancer cells, highlighting their potential for targeted imaging.
两种双环金属化铱配合物[Ir(ppyCF3)2(MAA)] (ppyCF3: 2-(4-三氟甲基苯基)吡啶;合成了甲基丙烯酰氨基酸(MAA: methacryloylamino acid),并用1H NMR、13C NMR、19F NMR、UV-Vis和FT-IR对其进行了表征。通过与细胞内转铁蛋白受体的相互作用,研究了合成的Ir(III)复合物作为生物显像剂的潜力。铱配合物利用MAA配体中的酪氨酸或色氨酸基团通过电子转移与转铁蛋白结合。这种相互作用增强了细胞内靶向和成像效率,从而扩大了Ir(III)复合物在生物系统中的潜在应用。在我们的研究中,我们通过Ir(III)配合物与转铁蛋白相互作用获得了两种不同类型的生物材料。第一类是铱-转铁蛋白交联缀合物(Ir-Tf),第二类是纳米结构的铱-转铁蛋白交联聚合物(nanoIr-Tf)。我们的研究结果表明,[Ir(ppyCF3)2(MATyr)]-Tf和纳米[Ir(ppyCF3)2(MATyr)]-Tf有望成为高效的生物显像剂。当与癌细胞和正常肺细胞相互作用时,这些复合物显示出强大的荧光发射,从而实现精确的成像和可视化。值得注意的是,这些复合物选择性地定位于癌细胞的细胞质中,突出了它们在靶向成像方面的潜力。
{"title":"Targeting and bioimaging of human lung cancer cells via Heteroleptic iridium complexes","authors":"Özlem Altsoy ,&nbsp;Özlem Biçen Ünlüer ,&nbsp;Filiz Yilmaz ,&nbsp;Sibel Emir Diltemiz ,&nbsp;Deniz Hür ,&nbsp;Arzu Ersöz ,&nbsp;Ridvan Say","doi":"10.1016/j.ica.2025.123009","DOIUrl":"10.1016/j.ica.2025.123009","url":null,"abstract":"<div><div>Two bis-cyclometalated iridium complexes [Ir(ppyCF<sub>3</sub>)<sub>2</sub>(MAA)] (ppyCF<sub>3</sub>: 2-(4-trifluoromethylphenyl)pyridine; MAA: methacryloylamino acid) have been synthesized and characterized by <sup>1</sup>H NMR, <sup>13</sup>C NMR, <sup>19</sup>F NMR, UV–Vis and FT-IR spectroscopy. The potential of the synthesized Ir(III) complexes as bioimaging agents was examined through their interaction with transferrin receptors in cells. The iridium complexes were attached to the transferrin protein via electron transfer using the tyrosine or tryptophan groups in the MAA ligand. This interaction enhances intracellular targeting and imaging efficiency, thereby expanding the potential applications of Ir(III) complexes in biological systems. In our study, we obtained two different types of biomaterials by interacting Ir(III) complexes with transferrin. The first type is iridium-transferrin cross-linked conjugates (Ir-Tf), and the second type is nano-structured iridium-transferrin cross-linked polymers (nanoIr-Tf). Our findings demonstrate that [Ir(ppyCF<sub>3</sub>)<sub>2</sub>(MATyr)]-Tf and nano[Ir(ppyCF<sub>3</sub>)<sub>2</sub>(MATyr)]-Tf show promise as efficient bioimaging agents. When interacting with both cancerous and normal lung cells, these complexes displayed robust fluorescence emission, enabling precise imaging and visualization. Notably, the complexes selectively localized within the cytoplasm of cancer cells, highlighting their potential for targeted imaging.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123009"},"PeriodicalIF":3.2,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145645727","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
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Inorganica Chimica Acta
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