[AnI3(THF)4] (An = Np, Pu) Preparation Bypassing An0 Metal Precursors: Access to Np3+/Pu3+ Nonaqueous and Organometallic Complexes

Author(s):  
Conrad A. P. Goodwin ◽  
Michael T. Janicke ◽  
Brian L. Scott ◽  
Andrew J. Gaunt
2015 ◽  
Vol 74 (5) ◽  
pp. 431-443 ◽  
Author(s):  
A.V. Momotenko ◽  
N. P. Klochko ◽  
V.M. Lyubov ◽  
V. R. Kopach ◽  
G.S. Khrypunov

2018 ◽  
Author(s):  
Dominic Bara ◽  
Claire Wilson ◽  
Max Mörtel ◽  
Marat M. Khusniyarov ◽  
ben slater ◽  
...  

Phase control in the self-assembly of metal-organic frameworks (MOFs) – materials wherein organic ligands connect metal ions or clusters into network solids with potential porosity – is often a case of trial and error. Judicious control over a number of synthetic variables is required to select for the desired topology and control features such as interpenetration and defectivity, which have significant impact on physical properties and application. Herein, we present a comprehensive investigation of self-assembly in the Fe-biphenyl-4,4'-dicarboxylate system, demonstrating that coordination modulation, the addition of competing ligands into solvothermal syntheses, can reliably tune between the kinetic product, non-interpenetrated MIL-88D(Fe), and the thermodynamic product, two-fold interpenetrated MIL-126(Fe). DFT simulations reveal that correlated disorder of the terminal anions on the metal clusters in the interpentrated phase results in H-bonding between adjacent nets and is the thermodynamic driving force for its formation. Coordination modulation slows self-assembly and therefore selects the thermodynamic product MIL-126(Fe), while offering fine control over defectivity, inducing mesoporosity, but electron microscopy shows the MIL-88D(Fe) phase persists in many samples despite not being evident in diffraction experiments, suggesting its presence accounts for the lower than predicted surface areas reported for samples to date. Interpenetration control is also demonstrated by utilizing the 2,2'-bipyridine-5,5'-dicarboxylate linker; DFT simulations show that it is energetically prohibitive for it to adopt the twisted conformation required to form the interpenetrated phase, and are confirmed by experimental data, although multiple alternative phases are identified due to additional coordination of the Fe cations to the N-donors of the ligand. Finally, we introduce oxidation modulation – the concept of using metal precursors in a different oxidation state to that found in the final MOF – as a further protocol to kinetically control self-assembly. Combining coordination and oxidation modulation allows the synthesis of pristine MIL-126(Fe) with BET surface areas close to the predicted maximum capacity for the first time, suggesting that combining the two may be a powerful methodology for the controlled self-assembly of high-valent MOFs.<br><br>


2020 ◽  
Vol 24 (21) ◽  
pp. 2508-2523
Author(s):  
Johana Gómez ◽  
Diego Sierra ◽  
Constanza Cárdenas ◽  
Fanny Guzmán

One area of organometallic chemistry that has attracted great interest in recent years is the syntheses, characterization and study of organometallic complexes conjugated to biomolecules with different steric and electronic properties as potential therapeutic agents against cancer and malaria, as antibiotics and as radiopharmaceuticals. This minireview focuses on the unique structural diversity that has recently been discovered in α- amino acids and the reactions of metallocene complexes with peptides having different chemical behavior and potential medical applications. Replacing α-amino acids with metallocene fragments is an effective way of selectively influencing the physicochemical, structural, electrochemical and biological properties of the peptides. Consequently, research in the field of bioorganometallic chemistry offers the opportunity to develop bioactive metal compounds as an innovative and promising approach in the search for pharmacological control of different diseases.


Author(s):  
Thoria Diab ◽  
Tarek M. Mohamed ◽  
Alaa Hamed ◽  
Mohamed Gaber

Background: Chemotherapy is currently the most utilized treatment for cancer. Therapeutic potential of metal complexes in cancer therapy has attracted a lot of interest. The mechanisms of action of most organometallic complexes are poorly understood. Objective: This study was designed to explore the mechanisms governing the anti-proliferative effect of the free ligand N1,N6‐bis((2‐hydroxynaphthalin‐1‐yl)methinyl)) adipohydrazone (H2L) and its complexes of Mn(II), Co(II), Ni(II) and Cu(II). Methods: Cells were exposed to H2L or its metal complexes where cell viability determined by MTT assay. Cell cycle was analysed by flow cytometry. In addition, qRT-PCR was used to monitor the expression of Bax and Bcl-2. Moreover, molecular docking was carried out to find the potentiality of Cu(II) complex as an inhibitor of Adenosine Deaminase (ADA). ADA, Superoxide Dismutase (SOD) and reduced Glutathione (GSH) levels were measured in the most affected cancer cell line. Results: The obtained results demonstrated that H2L and its Cu(II) complex exhibited a strong cytotoxic activity compared to other complexes against HepG2 cells (IC50 = 4.14±0.036μM/ml and 3.2±0.02μM/ml), respectively. Both H2L and its Cu(II) complex induced G2/M phase cell cycle arrest in HepG2 cells. Additionally, they induced apoptosis in HepG2 cells via upregulation of Bax and downregulation of Bcl-2. Interestingly, the activity of ADA was decreased by 2.8 fold in HepG2 cells treated with Cu(II) complex compared to untreated cells. An increase of SOD activity and GSH level in HepG2 cells compared to control was observed. Conclusion: The results concluded that Cu(II) complex of H2L induced apoptosis in HepG2 cells. Further studies are needed to confirm its anti-cancer effect in vivo.


ChemInform ◽  
2004 ◽  
Vol 35 (15) ◽  
Author(s):  
E.-I. Negishi ◽  
T. Takahashi

2021 ◽  
Vol 11 (2) ◽  
Author(s):  
E. Y. Shaba ◽  
J. O. Jacob ◽  
J. O. Tijani ◽  
M. A. T. Suleiman

AbstractIn this era, nanotechnology is gaining enormous popularity due to its ability to reduce metals, metalloids and metal oxides into their nanosize, which essentially alter their physical, chemical, and optical properties. Zinc oxide nanoparticle is one of the most important semiconductor metal oxides with diverse applications in the field of material science. However, several factors, such as pH of the reaction mixture, calcination temperature, reaction time, stirring speed, nature of capping agents, and concentration of metal precursors, greatly affect the properties of the zinc oxide nanoparticles and their applications. This review focuses on the influence of the synthesis parameters on the morphology, mineralogical phase, textural properties, microstructures, and size of the zinc oxide nanoparticles. In addition, the review also examined the application of zinc oxides as nanoadsorbent for the removal of heavy metals from wastewater.


Author(s):  
Rehab I. Yousef ◽  
Naglaa F.H. Mahmoud ◽  
Fouad I. El-Hosiny ◽  
Fritz E. Kühn ◽  
Ghada Bassioni

2020 ◽  
Vol 40 (3) ◽  
pp. 107-151
Author(s):  
Hira Anwar ◽  
Rosenani A. Haque ◽  
Rahman Shah Zaib Saleem ◽  
Muhammad Adnan Iqbal

AbstractThe indium complexes are being used in many applications like catalysis, optoelectronics, sensors, solar cells, biochemistry, medicine, infrared (IR) mirrors and thin-film transistors (TFTs). In organometallic complexes of indium, it forms different types of complexes with single, double, triple and tetra linkages by coordinating with numerous elements like C, N, O and S and also with some other elements like Se and Ru. So, the present study comprises all the possible ways to synthesize the indium complexes by reacting with different organic ligands; most of them are N-heterocyclic carbenes, amines, amides and phenols. The commonly used solvents for these syntheses are tetrahydrofuran, dichloromethane, toluene, benzene, dimethyl sulfoxide (DMSO) and water. According to the nature of the ligands, indium complexes were reported at different temperatures and stirring time. Because of their unique characteristics, the organometallic chemistry of group 13 metal indium complexes remains a subject of continuing interest in synthetic chemistry as well as material science.


Molecules ◽  
2020 ◽  
Vol 25 (3) ◽  
pp. 593
Author(s):  
Juan Miranda-Pizarro ◽  
Macarena G. Alférez ◽  
M. Dolores Fernández-Martínez ◽  
Eleuterio Álvarez ◽  
Celia Maya ◽  
...  

A straightforward method for the preparation of trisphosphinite ligands in one step, using only commercially available reagents (1,1,1-tris(4-hydroxyphenyl)ethane and chlorophosphines) is described. We have made use of this approach to prepare a small family of four trisphosphinite ligands of formula [CH3C{(C6H4OR2)3], where R stands for Ph (1a), Xyl (1b, Xyl = 2,6-Me2-C6H3), iPr (1c), and Cy (1d). These polyfunctional phosphinites allowed us to investigate their coordination chemistry towards a range of late transition metal precursors. As such, we report here the isolation and full characterization of a number of Au(I), Ag(I), Cu(I), Ir(III), Rh(III) and Ru(II) homotrimetallic complexes, including the structural characterization by X-ray diffraction studies of six of these compounds. We have observed that the flexibility of these trisphosphinites enables a variety of conformations for the different trimetallic species.


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