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A Nanoscale Cobalt Functionalized Strandberg-Type Phosphomolybdate with β-Sheet Conformation Modulation Ability in Anti-Amyloid Protein Misfolding 具有β片构象调制能力的纳米级钴官能化斯特兰堡型磷钼酸盐在抗淀粉样蛋白折叠中的作用
IF 2.9 4区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2023-11-18 DOI: 10.3390/inorganics11110442
M. Wang, J. Hua, Pei Zheng, Yuanzhi Tian, Shaodan Kang, Junjun Chen, Yifan Duan, Xiang Ma
For decades, amyloid β-peptide (Aβ) misfolding aggregates with β-sheet structures have been linked to the occurrence and advancement of Alzheimer’s disease (AD) development and progression. As a result, modulating the misfolding mode of Aβ has been regarded as an important anti-amyloid protein misfolding strategy. A polyoxometalate based on {Co(H2O)4}2+ complex and [P2Mo5O23]6− fragments, K8{[Co(H2O)4][HP2Mo5O23]2}·8H2O (abbreviated as CoPM), has been synthesized and structurally characterized using elemental analysis, single-crystal X-ray diffraction (SXRD), IR, UV spectra, bond valence sums (Σs) calculation, and powder XRD (PXRD). CoPM’s primary component, as revealed by structural analysis, is a nanoscale polyoxoanion made of [Co(H2O)4]2+ sandwiched between two [P2Mo5O23]6− pieces. Notably, it is demonstrated that CoPM efficiently modulates Aβ aggregates’ β-sheet-rich conformation.
几十年来,具有β片状结构的淀粉样β肽(Aβ)错误折叠聚集体一直与阿尔茨海默病(AD)的发生和发展有关。因此,调节 Aβ 的错误折叠模式被认为是一种重要的抗淀粉样蛋白错误折叠策略。一种基于{Co(H2O)4}2+复合物和[P2Mo5O23]6-片段的多氧金属盐 K8{[Co(H2O)4][HP2Mo5O23]2}-8H2O(缩写为 CoPM)被合成出来,并构建了其结构、的合成,并利用元素分析、单晶 X 射线衍射 (SXRD)、红外光谱、紫外光谱、键价和 (Σs)计算以及粉末 X 射线衍射 (PXRD) 对其结构进行了表征。结构分析表明,CoPM 的主要成分是由夹在两片 [P2Mo5O23]6- 之间的 [Co(H2O)4]2+ 组成的纳米级多氧阴离子。值得注意的是,研究表明 CoPM 能有效调节 Aβ 聚集体的 β-片状富构象。
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引用次数: 0
Spin Canting and Weak Ferromagnetism in a New 2D Coordination Polymer with the Co(II) Chain Bridged by a Single End-to-End Azide 一种新型二维配位聚合物中的自旋弯曲和弱铁磁性--Co(II)链由一个端对端叠氮化物桥接
IF 2.9 4区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2023-11-18 DOI: 10.3390/inorganics11110444
Y. Kuo, Hsin-Kuan Liu, Chen-I Yang
By employing semi-flexible multi-N donor auxiliary ligands, namely 1,4-bis(5-pyrimidyl)benzene (bpmb) in conjunction with azide, novel Co(II) 2D coordination polymers have been successfully synthesized and structurally characterized, along with magnetic analysis. The resulting compound, {Co(N3)(bpmb)(H2O)2·H2O}n (1), exhibits a unique 2D structure comprised of interconnected Co(II) chains bridged by single end-to-end (EE) azide moieties. These chains are further linked by twisted trans-μ2-N,N′-bpmb auxiliary ligands, forming a grid-like network. Additionally, the layers are held together in a 3D arrangement through hydrogen bonding interactions between the coordination water and the N atom of the bpmb ligands. Importantly, magnetic investigations reveal that compound 1 displays weak ferromagnetism attributed to spin canting, with a critical temperature (Tc) of 12 K.
通过采用半柔性多 N 供体辅助配体,即 1,4-双(5-嘧啶基)苯(bpmb)和叠氮化物,成功合成了新型 Co(II) 二维配位聚合物,并对其进行了结构表征和磁性分析。由此产生的化合物{Co(N3)(bpmb)(H2O)2-H2O}n (1)呈现出独特的二维结构,由相互连接的 Co(II) 链和单个端对端 (EE) 叠氮化物桥接而成。这些链通过扭曲的反式-μ2-N,N′-bpmb 辅助配体进一步连接,形成网格状网络。此外,通过配位水和 bpmb 配体的 N 原子之间的氢键相互作用,各层以三维排列方式固定在一起。重要的是,磁性研究表明,化合物 1 显示出了归因于自旋悬臂的弱铁磁性,临界温度 (Tc) 为 12 K。
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引用次数: 0
Naphthalimide-Modified Tridentate Platinum(II) Complexes: Synthesis, Characterization, and Application in Singlet Oxygen Generation 萘二甲酰亚胺修饰的三叉铂(II)配合物:合成、表征及在单线态氧生成中的应用
IF 2.9 4区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2023-11-17 DOI: 10.3390/inorganics11110438
Zhongliang Gong, Qing-Jun Pan, Dian-Xue Ma, Yu‐Wu Zhong
Singlet oxygen (1O2), representing an important reactive oxygen species, has promising applications in biomedical, material, and environmental sciences. Photosensitized production of 1O2 using organic dyes is highly desirable and the exploration of highly efficient photosensitizers has received considerable attention. Herein, two tridentate Pt(II) complexes, i.e., cationic 1(PF6) and neutral 2, modified with the ethynylnaphthalimide chromophore, were designed and prepared for the application in 1O2 generation. Spectroscopic studies and computational results suggest that 1(PF6) and 2 display the lowest-energy absorption bands centered at 435–465 nm with the molar extinction coefficients of 0.6–3.2 × 104 M−1 cm−1, originating from the singlet ligand-to-ligand charge transfer (1LLCT) and a mixture of 1LLCT and singlet ligand-centered (LC) transitions, respectively. Moreover, they show similar phosphorescence at 620–640 nm assigned to the Pt-perturbed triplet LC emission of the ethynylnaphthalimide moiety. Thanks to the relatively long phosphorescence lifetimes, these complexes exhibit O2-dependent phosphorescence intensities with good reversibility and stability. They are able to behave as efficient triplet photosensitizers to promote the 1O2 generation with high quantum yields (84–89%). This work indicates that the combination of an organic chromophore with Pt(II) complexes provides an effective method to obtain photosensitizers for 1O2 generation.
单线态氧(1O2)是一种重要的活性氧,在生物医学、材料和环境科学领域有着广阔的应用前景。利用有机染料光敏生成 1O2 是非常理想的,而对高效光敏剂的探索也受到了广泛关注。本文设计并制备了两种三叉铂(II)配合物,即阳离子 1(PF6) 和中性 2,并用乙炔基萘二甲酰亚胺发色团修饰,以应用于生成 1O2。光谱研究和计算结果表明,1(PF6) 和 2 显示出以 435-465 nm 为中心的最低能量吸收带,摩尔消光系数为 0.6-3.2 × 104 M-1 cm-1,分别源于单质配体到配体的电荷转移(1LLCT)以及 1LLCT 和单质配体为中心的混合转变(LC)。此外,它们还在 620-640 纳米波长处显示出类似的磷光,这归因于乙炔基萘酰亚胺分子的铂扰动三重低电平发射。由于磷光寿命相对较长,这些复合物的磷光强度与氧气有关,具有良好的可逆性和稳定性。它们能够作为高效的三重光敏剂,以高量子产率(84-89%)促进 1O2 的生成。这项工作表明,有机发色团与 Pt(II) 复合物的结合为获得生成 1O2 的光敏剂提供了一种有效的方法。
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引用次数: 0
Effect of the Annealing Temperature of Lithiophilic Ag–Cu Co-Deposition on the Cycling Performance of Li-Metal Anodes 亲锂银铜共沉积的退火温度对锂金属阳极循环性能的影响
IF 2.9 4区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2023-11-17 DOI: 10.3390/inorganics11110440
Dae Hyun Kim, Seul Gi Kang, Bo Jung Kim, Heegyoun Lee, Jinmo Kim, Chang-Bun Yoon
Practical applications of Li-metal anodes are limited by dendrite formation, Li loss, and poor reaction, resulting in a low Coulombic efficiency. In this study, we investigated the effects of island-shaped Ag atoms on the electrochemical behavior of Li-metal anodes. A Ag–Cu film was co-deposited through sputtering and subsequent annealing to anchor the Ag atoms with an island shape on a Cu substrate. The Ag target was co-sputtered with Cu with controlled atomic ratios in the Ag–Cu alloy. The sputtering thickness was set to 100 nm, and various annealing conditions were applied. The embedded island-shaped Ag atoms provided effective nucleation sites for Li deposition during the electrochemical nucleation of Li, increasing the nucleation density and spatial uniformity while decreasing the nucleation size and potential. Compact dendrite-free high-density Li deposition was achieved by annealing the Ag–Cu current collector (CC) at 600 °C. Under repetitive Li plating and stripping for 110 cycles at a current density of 0.5 mAcm−2 and capacity of 1 mAhcm−2, a high Coulombic efficiency of 98.5% was achieved. Conversely, the bare Cu CC had a life of up to 67 cycles under the same test conditions.
锂金属阳极的实际应用受到枝晶形成、锂损耗和反应不良的限制,导致库仑效率较低。在本研究中,我们研究了岛状银原子对锂金属阳极电化学行为的影响。通过溅射和随后的退火共同沉积了一层银-铜薄膜,从而在铜基底上锚定了岛状的银原子。在银铜合金中,以可控的原子比将银靶与铜共同溅射。溅射厚度设定为 100 nm,并采用了不同的退火条件。在锂的电化学成核过程中,嵌入的岛状银原子为锂沉积提供了有效的成核位点,提高了成核密度和空间均匀性,同时减小了成核尺寸和电位。通过将银铜集流器(CC)在 600 °C 下退火,实现了紧凑无树枝状晶粒的高密度锂沉积。在电流密度为 0.5 mAcm-2 和容量为 1 mAhcm-2 的条件下,重复锂电镀和剥离 110 个循环,库仑效率高达 98.5%。相反,在相同的测试条件下,裸铜 CC 的寿命最长为 67 个周期。
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引用次数: 0
Photocatalytic Degradation of Emerging Contaminants with N-Doped TiO2 Using Simulated Sunlight in Real Water Matrices 利用模拟阳光在真实水质中使用掺杂 N 的 TiO2 光催化降解新出现的污染物
IF 2.9 4区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2023-11-17 DOI: 10.3390/inorganics11110439
Elisa Gaggero, Arianna Giovagnoni, Alessia Zollo, Paola Calza, M. Paganini
In the present work, the photodegradation performances of N-doped TiO2 photocatalysts with enhanced absorption of visible light were exploited for the abatement of some representative contaminants of emerging concern (CECs). Pristine TiO2 and N-TiO2 were synthesized using hydrothermal (HT) and sol–gel (SG) routes, they were characterized using XRD and UV-Vis spectroscopy, and their band gaps were determined via analysis in diffuse reflectance. Their photodegradation efficiency was tested on a mixture of recalcitrant organic pollutants, namely, benzotriazole, diclofenac, sulfamethoxazole, and bisphenol A, using a solar simulator lamp with two different cut-off filters (λ > 340 nm and λ > 400 nm). The evaluation of the photocatalytic performances was initially carried out in spiked ultrapure water and subsequently in aqueous matrices of increasing complexity such as Po River water and water coming from an aquaculture plant. The exclusive utilization of visible light (λ > 400 nm) highlighted the advantage of introducing the dopant into the TiO2 photocatalyst since this modification allows for the material to be responsive to visible light, which is not sufficient in the case of pristine TiO2 and the higher efficiency of materials obtained via the sol–gel route. Thanks to the doping, improved performance was obtained in both ultrapure water and real water matrices, indicating the potential of the doped material for future applications in the field.
本研究利用掺杂 N 的二氧化钛光催化剂对可见光的吸收增强的光降解性能,来消除一些具有代表性的新关注污染物(CECs)。采用水热法(HT)和溶胶-凝胶法(SG)合成了纯净的二氧化钛(TiO2)和掺氮二氧化钛(N-TiO2),使用 XRD 和紫外-可见光谱对它们进行了表征,并通过漫反射分析确定了它们的带隙。使用带有两种不同截止滤光片(λ > 340 nm 和 λ > 400 nm)的太阳模拟灯测试了它们对苯并三唑、双氯芬酸、磺胺甲噁唑和双酚 A 等难降解有机污染物混合物的光降解效率。对光催化性能的评估最初是在加标超纯水中进行的,随后又在波河水和水产养殖厂水等复杂程度越来越高的水基质中进行。对可见光(λ > 400 nm)的专门利用凸显了在二氧化钛光催化剂中引入掺杂剂的优势,因为这种改性可使材料对可见光产生反应,而原始二氧化钛对可见光的反应是不够的,而且通过溶胶-凝胶路线获得的材料效率更高。由于进行了掺杂,在超纯水和真水基质中的性能都得到了提高,这表明掺杂材料未来在该领域的应用潜力巨大。
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引用次数: 0
Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(η5-Cp*)X2]− (X = Cl − I) 含单阴离子铁(II)半三明治络合物 [Fe(η5-Cp*)X2]- (X = Cl - I)的铵盐和鏻盐
IF 2.9 4区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2023-11-17 DOI: 10.3390/inorganics11110437
Julian Zinke, C. Bruhn, U. Siemeling
Half-sandwich iron(II) dihalido complexes of the type [Fe(η5-Cp’)X2]− (Cp’ = C5H5 or substituted cyclopentadienyl) which are thermally stable at room temperature are extremely scarce, being limited to congeners containing the bulky C5H2-1,2,4-tBu3 ligand. We extended this to homologues [Fe(η5-Cp*)X2]− (X = Cl, Br, I) containing the particularly popular C5Me5 (Cp*) ligand. Corresponding ionic compounds ER4[Fe(η5-Cp*)X2] are easily accessible from FeX2, MCp* (M = Li, K) and a suitable halide source R4EX (E = N, P) in THF. Despite their high sensitivity towards air and moisture, the new compounds NnPr4[Fe(η5-Cp*)X2] (X = Cl, Br), NnPr4[Fe(η5-Cp*)BrCl], and PPh4[Fe(η5-Cp*)X2] (X = Cl, Br, I) were structurally characterised using single-crystal X-ray diffraction. NnPr4[Fe(η5-Cp*)Cl2] reacts readily with CO to afford [Fe(η5-Cp*)Cl(CO)2], indicating the synthetic potential of ER4[Fe(η5-Cp*)X2] in FeCp* half-sandwich chemistry.
在室温下具有热稳定性的[Fe(η5-Cp')X2]-(Cp'= C5H5 或取代的环戊二烯基)半夹心二卤化铁(II)配合物非常稀少,仅限于含有笨重的 C5H2-1,2,4-tBu3 配体的同系物。我们将其扩展到含有特别常用的 C5Me5(Cp*)配体的同系物[Fe(η5-Cp*)X2]-(X = Cl、Br、I)。相应的离子化合物 ER4[Fe(η5-Cp*)X2]很容易从四氢呋喃中的 FeX2、MCp*(M = Li、K)和合适的卤化物源 R4EX(E = N、P)中获得。尽管新化合物 NnPr4[Fe(η5-Cp*)X2](X = Cl、Br)、NnPr4[Fe(η5-Cp*)BrCl]和 PPh4[Fe(η5-Cp*)X2](X = Cl、Br、I)对空气和湿气的敏感性很高,但我们还是利用单晶 X 射线衍射对它们进行了结构表征。NnPr4[Fe(η5-Cp*)Cl2]很容易与 CO 反应,生成[Fe(η5-Cp*)Cl(CO)2],这表明 ER4[Fe(η5-Cp*)X2] 在 FeCp* 半三明治化学中具有合成潜力。
{"title":"Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(η5-Cp*)X2]− (X = Cl − I)","authors":"Julian Zinke, C. Bruhn, U. Siemeling","doi":"10.3390/inorganics11110437","DOIUrl":"https://doi.org/10.3390/inorganics11110437","url":null,"abstract":"Half-sandwich iron(II) dihalido complexes of the type [Fe(η5-Cp’)X2]− (Cp’ = C5H5 or substituted cyclopentadienyl) which are thermally stable at room temperature are extremely scarce, being limited to congeners containing the bulky C5H2-1,2,4-tBu3 ligand. We extended this to homologues [Fe(η5-Cp*)X2]− (X = Cl, Br, I) containing the particularly popular C5Me5 (Cp*) ligand. Corresponding ionic compounds ER4[Fe(η5-Cp*)X2] are easily accessible from FeX2, MCp* (M = Li, K) and a suitable halide source R4EX (E = N, P) in THF. Despite their high sensitivity towards air and moisture, the new compounds NnPr4[Fe(η5-Cp*)X2] (X = Cl, Br), NnPr4[Fe(η5-Cp*)BrCl], and PPh4[Fe(η5-Cp*)X2] (X = Cl, Br, I) were structurally characterised using single-crystal X-ray diffraction. NnPr4[Fe(η5-Cp*)Cl2] reacts readily with CO to afford [Fe(η5-Cp*)Cl(CO)2], indicating the synthetic potential of ER4[Fe(η5-Cp*)X2] in FeCp* half-sandwich chemistry.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"75 3","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139264739","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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
Dibromo- and Dichlorotriphenylphosphino N-Acyclic Carbene Complexes of Platinum(II)—Synthesis and Cytotoxicity 铂的二溴和二氯三苯基膦N-无环卡宾配合物(II)——合成及其细胞毒性
IF 2.9 4区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2023-09-08 DOI: 10.3390/inorganics11090365
Anna Farasat, L. Labella, M. D. Di Paolo, L. Dalla Via, S. Samaritani
Some new dichloro- and dibromotriphenylphosphino isonitrile and N-acyclic (NAC) carbene complexes of platinum(II) were synthesized, starting from suitable dinuclear precursors. The reaction of cyclohexylisonitrile with trans-[Pt(μ-X)X(PPh3)]2, followed by the addition of N,N-diethylamine afforded the corresponding N-acyclic carbene (NAC)derivatives cis-[PtX2(PPh3)(NAC)] in 61–64% isolated yield. The cis geometry was attributed based on the comparison with known structures. The stability of the complexes in pure DMSO, DMSO/H2O, and DMSO/NaClaq mixtures was evaluated. While pure DMSO, as well as DMSO/H2O, did not affect the nature of either dichloro- or dibromo-compounds, dibromo derivatives were not stable in the presence of chloride ions. Since a high concentration of chloride ions is essential to perform in vitro cell assays, only dichlorocomplexes were tested as cytotoxic agents against HepG2 and human tumor cells. Among the tested complexes, NAC derivatives showed a moderate effect on MSTO-211H.
以合适的双核前体为原料,合成了一些新的铂(II)的二氯和二溴三苯基膦异腈和N-环(NAC)卡宾配合物。环己基单腈与反式-Pt(μ-X)X(PPh3)]2反应,然后加入N,N-二乙胺,以61–64%的分离产率得到相应的N-环状卡宾(NAC)衍生物顺式-PtX2。基于与已知结构的比较,对顺式几何结构进行了归属。评估了配合物在纯DMSO、DMSO/H2O和DMSO/NaCaq混合物中的稳定性。虽然纯DMSO以及DMSO/H2O不影响二氯或二溴化合物的性质,但二溴衍生物在氯离子存在下不稳定。由于高浓度的氯离子对于进行体外细胞测定是必不可少的,因此仅测试了二氯络合物作为针对HepG2和人类肿瘤细胞的细胞毒性剂。在测试的复合物中,NAC衍生物对MSTO-211H表现出中等的作用。
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引用次数: 0
Efficient Disposal of Basic Fuchsin Dye from Aqueous Media Using ZrO2/MgMn2O4/Mg(Mg0.333Mn1.333)O4 as a Novel and Facilely Synthesized Nanocomposite ZrO2/MgMn2O4/Mg(Mg0.333Mn1.333)O4作为一种新的、易于合成的纳米复合材料从水介质中有效处理碱性品红染料
IF 2.9 4区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2023-09-07 DOI: 10.3390/inorganics11090363
A. Al-Wasidi, Mohamed Khairy, B. Abdulkhair, Ehab A. Abdelrahman
In this work, amorphous and crystalline novel products based on Zr, Mg, and Mn were facilely fabricated through the Pechini sol–gel procedure using inexpensive chemicals and an uncomplicated apparatus. Also, these products showed high efficiency as novel adsorbents in getting rid of basic fuchsin dye from aqueous solutions. The adsorbent, which was fabricated before calcination, was abbreviated as KE. In addition, the adsorbents, which were created at 500 and 700 °C, were designated as KE500 and KE700, respectively. The created adsorbents were characterized using high-level transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), N2 adsorption/desorption analyzer, and field emission scanning electron microscope (FE-SEM). The XRD showed that the KE adsorbent is amorphous, whereas the KE500 and KE700 adsorbents are mixtures of ZrO2, MgMn2O4, and Mg(Mg0.333Mn1.333)O4 nanostructures. The HR-TEM exhibited that the KE adsorbent consists of very fine irregular shapes, whereas the KE500 adsorbent contains quasi-spherical particles with a mean diameter of 45.16 nm. Furthermore, the HR-TEM exhibited that the KE700 adsorbent consists of polyhedral shapes with a mean diameter of 76.28 nm. Furthermore, the BET surface area of the KE, KE500, and KE700 adsorbents is 67.85, 20.15, and 13.60 m2/g, respectively. Additionally, the elimination of basic fuchsin dye by the KE, KE500, and KE700 adsorbents is exothermic, physical in nature, and follows the pseudo-first-order as well as Langmuir equations. Further, the maximum uptake capabilities of the KE, KE500, and KE700 adsorbents toward basic fuchsin dye are 239.81, 174.83, and 93.19 mg/g, respectively.
在这项工作中,通过Pechini溶胶-凝胶程序,使用廉价的化学品和简单的设备,容易地制备了基于Zr、Mg和Mn的非晶和结晶新产品。此外,这些产物在从水溶液中去除碱性品红染料方面显示出作为新型吸附剂的高效性。在煅烧前制造的吸附剂缩写为KE。此外,在500和700°C下产生的吸附剂分别命名为KE500和KE700。使用高级透射电子显微镜(HR-TEM)、X射线衍射(XRD)、能量色散X射线光谱(EDS)、N2吸附/脱附分析仪和场发射扫描电子显微镜(FE-SEM)对所产生的吸附剂进行表征。XRD表明KE吸附剂是无定形的,而KE500和KE700吸附剂是ZrO2、MgMn2O4和Mg(Mg0.333Mn1.333)O4纳米结构的混合物。HR-TEM表明,KE吸附剂由非常精细的不规则形状组成,而KE500吸附剂包含平均直径为45.16nm的准球形颗粒。此外,HR-TEM显示KE700吸附剂由平均直径为76.28nm的多面体组成。此外,KE、KE500和KE700吸附剂的BET表面积分别为67.85、20.15和13.60m2/g。此外,KE、KE500和KE700吸附剂对碱性品红染料的消除是放热的,本质上是物理的,并且遵循伪一阶和Langmuir方程。此外,KE、KE500和KE700吸附剂对碱性品红染料的最大吸收能力分别为239.81、174.83和93.19mg/g。
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引用次数: 3
Isocyanide Cycloaddition and Coordination Processes at Trigonal Phosphinidene-Bridged MoRe and MoMn Complexes 异氰化物环加成和配位过程的三角膦烯桥接MoRe和MoMn配合物
IF 2.9 4区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2023-09-07 DOI: 10.3390/inorganics11090364
M. Alvarez, M. E. García, Daniel García-Vivó, Miguel A. Ruiz, Patricia Vega
Heterometallic phosphinidene complexes are appealing species for the construction of novel organophosphorus ligands thanks to the high reactivity expected from the combination of M-P multiple bonding and the intrinsically different electronic and coordination preferences of the distinct metals. In a preliminary study, we found that the heterobimetallic complex [MoReCp(μ-PMes*)(CO)6] (Mes* = 2,4,6-C6H2tBu3) reacted with CN(p-C6H4OMe) via [2+1]-cycloaddition to form a novel azaphosphallene complex. We have now examined in detail the reactions of the above complex and those of its MoMn analogue with different isocyanides, which turned out to be strongly dependent on experimental conditions and on the size of the substituent at the isocyanide. All the products formed follow from one or several of the following reaction pathways: (i) CO substitution by CNR; (ii) addition of CNR at the group 7 metal centre; and (iii) [2+1] cycloaddition of isocyanide at a Mo=P bond to form azaphosphallene groups, with the former process being dominant in reactions at room temperature and for the Mn system. In contrast, low-temperature reactions of the Re system favoured the addition processes, with the [2+1] cycloaddition at Mo=P bonds only taking place at substrates without metal-metal bonds and when the size of the CNR group does not cause unbearable steric clashes when placed in between the Cp and Mes* groups.
杂金属膦配合物是构建新型有机磷配体的有吸引力的物种,这是因为M-P多键组合所期望的高反应性以及不同金属本质上不同的电子和配位偏好。在初步研究中,我们发现杂双金属配合物[MoReCp(μ-PMes*)(CO)6] (Mes* = 2,4,6- c6h2tbu3)与CN(p-C6H4OMe)通过[2+1]-环加成反应生成新的氮磷配合物。我们现在已经详细研究了上述配合物及其MoMn类似物与不同异氰酸酯的反应,结果表明,这些反应强烈地依赖于实验条件和异氰酸酯上取代基的大小。所有生成的产物都遵循以下一种或几种反应途径:(i) CNR取代CO;(ii)在第7类金属中心加设“北车轨道”;(3)异氰化物在Mo=P键处进行[2+1]环加成,形成氮杂烯基团,在室温和Mn体系中,前者占主导地位。相比之下,Re体系的低温反应有利于加成过程,在Mo=P键处的[2+1]环加成只发生在没有金属-金属键的底物上,并且当CNR基团的大小在Cp和Mes*基团之间时不会引起难以忍受的位阻冲突。
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引用次数: 0
Luminescent Cadmium(II)-Based 12-MC-4 Metallacrown Complex with 2-Methylmercaptobenzohydroxamic Acid Ligand 发光镉(II)基12-MC-4金属丙烯与2-甲基巯基苯甲酰胺酸配体的配合物
IF 2.9 4区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2023-09-05 DOI: 10.3390/inorganics11090362
S. Sundaresan, C. Gamer, Mortiz J. Förster, Luca M. Carrella, E. Rentschler
We reported herein the synthesis, structure determination and emission properties of a cubic molecular Cd(II) coordination cluster whose faces are composed of 12-MC-4 metallacrown units built up from Cd2+ and 2-methylmercaptobenzohydroxamic acid (LmmbHA), resulting in [CdII14(LmmbHA)12(µ6−O)(DMF)10](ClO4)2·3H2O. The polynuclear complex obtained was characterised by single crystal X-ray diffraction at 193 K. The bulk sample was also analysed by elemental analysis. UV-Vis and emission spectra of the complex were measured in chloroform, as well as the emission spectra of the ligand for comparison. The results of the emission studies revealed that both the ligand and the complex are weakly emissive.
本文报道了一种立方分子Cd(II)配位簇的合成、结构测定和发射性能,其表面由Cd2+和2-甲基巯基苯甲酰胺酸(LmmbHA)形成的12-MC-4金属大分子单元组成,得到[CdII14(Lmmb HA)12(µ6−O)(DMF)10](ClO4)2ß3H2O。通过193K下的单晶X射线衍射对所获得的多核配合物进行了表征。还通过元素分析对大块样品进行了分析。测定了配合物在氯仿中的紫外-可见光谱和发射光谱,并与配体的发射光谱进行了比较。发射研究的结果表明,配体和配合物都是弱发射的。
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引用次数: 0
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Inorganics
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