scholarly journals Unexpected formation of polymeric silver(I) complexes of azine-type ligand via self-assembly of Ag-salts with isatin oxamohydrazide

2018 ◽  
Vol 5 (7) ◽  
pp. 180434 ◽  
Author(s):  
Saied M. Soliman ◽  
Jörg H. Albering ◽  
Assem Barakat
Keyword(s):  
Coordination Polymer ◽  
Self Assembly ◽  
Density Functional ◽  
Free Ligand ◽  
Alcoholic Solution ◽  
Unexpected Formation ◽  
Testing Metal ◽  
Complex Preparation ◽  
Complex Forms ◽  
Hydrolysis Of

Isatin oxamohydrazide ( L ) reacted with the aqueous solution of silver nitrate at room temperature afforded the polymeric silver(I) nitrato complex, [Ag 2 L′(NO 3 ) 2 ] n , (1) of the azine ligand ( L′ ). Similarly, the reaction of L with silver(I) perchlorate gave the [Ag 2 L′ 2 (ClO 4 ) 2 ] n , (2) coordination polymer. Careful inspection of the crystals from the nitrato complex preparation showed the presence of another crystalline product which is found to be [Ag(Isatin-3-hydrazone)NO 3 ], (3) suggesting that the reaction between silver(I) nitrate and L proceeds first by the hydrolysis of L to the isatin hydrazone which attacks another molecule of L to afford L′ . Testing metal salts such as Ni 2+ , Co 2+ , Mn 2+ , Cu 2+ and Cd 2+ did not undergo any reaction with L either under the same reaction conditions or with heating under reflux up to 24 h. Treatment of the warm alcoholic solution of L with few drops of 1 : 1 (v/v) hydrochloric acid gave the free ligand ( L′ ) in good yield. The [Ag 2 L′(NO 3 ) 2 ] n complex forms a two-dimensional infinite coordination polymer, while the [Ag 2 L′ 2 (ClO 4 ) 2 ] n forms one-dimensional infinite chains with an alternating silver-azine backbone. Quantitative analysis of the intermolecular interactions in their crystals is made using Hirshfeld surface analysis. Density functional theory studies were performed to investigate the coordination bonding in the studied complexes.

scholarly journals Molecular and Supramolecular Structures of Cd(II) Complexes with Hydralazine-Based Ligands; A New Example for Cyclization of Hydrazonophthalazine to Triazolophthalazine

Crystals ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 823
Author(s):  
Saied M. Soliman ◽  
Raghdaa A. Massoud ◽  
Hessa H. Al-Rasheed ◽  
Ayman El-Faham
Keyword(s):  
Coordination Polymer ◽  
Self Assembly ◽  
Chloride Ions ◽  
Supramolecular Structures ◽  
Trinuclear Complex ◽  
Monodentate Ligand ◽  
Topology Analysis ◽  
1D Coordination Polymer ◽  
Bidentate Chelate ◽  
Hydrolysis Of

Molecular and supramolecular structures of two polymeric and one trinuclear Cd(II) complex with hydralazine-type ligands were presented. Self-assembly of E-1-(2-(thiophen-2-ylmethylene)hydrazinyl)phthalazine (HL) and CdCl2 gave the 1D coordination polymer [Cd(H2L)Cl3]n*H2O, 1, in which the Cd(II) ion is hexa-coordinated with one cationic monodentate ligand (H2L+) and five chloride ions, two of them acting as connectors between Cd(II) centers, leading to the formation of a 1D coordination polymer along the a-direction. Using DFT calculations, the cationic ligand (H2L+) could be described as a protonated HL with an extra proton at the hydrazone moiety. Repeating the same reaction by heating under reflux conditions in the presence of 1 mL saturated aqueous KSCN solution, the ligand HL underwent cyclization to the corresponding [1,2,4]triazolo[3,4-a]phthalazine-3(2H)-thione (TPT) followed by the formation of [Cd(TPT)(SCN)2]n*H2O, 2, a 1D coordination polymer. In this complex, the Cd(II) is coordinated with one NS-donor TPT bidentate chelate and two bridged μ(1,3)-thiocyanate ions connecting the Cd(II) centers forming the 1D polymer array along the b-direction. Heating E-2-(1-(2-(phthalazin-1-yl)hydrazono)ethyl)phenol HLOH with CdCl2 under reflux condition gave the trinuclear complex [Cd3(Hydralazine)2(H2O)2Cl6], 3, indicating the hydrolysis of the hydrazonophthalazine ligand HLOH during the course of the reaction. Due to symmetry considerations, there are only two different Cd(II) centers having CdN2Cl3O and CdN2Cl4 coordination environments. Hirshfeld topology analysis was used to analyze the solid-state supramolecular structure of the studied complexes.

Theoretical Study of the Process of Passage of Glycoside Amides through the Cell Membrane of Cancer Cell

2020 ◽  
Vol 20 ◽  
Author(s):  
Vasil Tsanov ◽  
Hristo Tsanov
Keyword(s):  
Cell Membrane ◽  
Cancer Cells ◽  
Cancer Cell ◽  
Quantum Chemical ◽  
Density Functional ◽  
Enzyme Regulation ◽  
Amide Derivatives ◽  
Pass Through ◽  
Hydrolysis Of ◽  
Derivatives Of

Background:: This article concentrates on the processes occurring in the medium around the cancer cell and the transfer of glycoside amides through their cell membrane. They are obtained by modification of natural glycoside-nitriles (cyano-glycosides). Hydrolysis of starting materials in the blood medium and associated volume around physiologically active healthy and cancer cells, based on quantum-chemical semi-empirical methods, is considered. Objective:: Based on the fact that the cancer cell feeds primarily on carbohydrates, it is likely that organisms have adapted to take food containing nitrile glycosides and / or modified forms to counteract "external" bioactive activity. Cancers, for their part, have evolved to create conditions around their cells that eliminate their active apoptotic forms. This is far more appropriate for them than changing their entire enzyme regulation to counteract it. In this way, it protects itself and the gene sets and develops according to its instructions. Methods:: Derived pedestal that closely defines the processes of hydrolysis in the blood, the transfer of a specific molecular hydrolytic form to the cancer cell membrane and with the help of time-dependent density-functional quantum- chemical methods, its passage and the processes of re-hydrolysis within the cell itself, to forms causing chemical apoptosis of the cell - independent of its non-genetic set, which seeks to counteract the process. Results:: Used in oncology it could turn a cancer from a lethal to a chronic disease (such as diabetes). The causative agent and conditions for the development of the disease are not eliminated, but the amount of cancer cells could be kept low for a long time (even a lifetime). Conclusion:: The amide derivatives of nitrile glycosides exhibit anti-cancer activity, the cancer cell probably seeks to displace hydrolysis of these derivatives in a direction that would not pass through its cell membrane and the amide- carboxyl derivatives of nitrile glycosides could deliver extremely toxic compounds within the cancer cell itself and thus block and / or permanently damage its normal physiology.

DFT study on the hydrolysis of metsulfuron-methyl: A sulfonylurea herbicide

2018 ◽  
Vol 17 (08) ◽  
pp. 1850050 ◽  
Author(s):  
Qiuhan Luo ◽  
Gang Li ◽  
Junping Xiao ◽  
Chunhui Yin ◽  
Yahui He ◽  
...  
Keyword(s):  
Free Energy ◽  
Water Molecule ◽  
Carbonyl Group ◽  
Energy Barrier ◽  
Density Functional ◽  
Free Energy Barrier ◽  
Functional Theory ◽  
Metsulfuron Methyl ◽  
Catalytic Role ◽  
Hydrolysis Of

Sulfonylureas are an important group of herbicides widely used for a range of weeds and grasses control particularly in cereals. However, some of them tend to persist for years in environments. Hydrolysis is the primary pathway for their degradation. To understand the hydrolysis behavior of sulfonylurea herbicides, the hydrolysis mechanism of metsulfuron-methyl, a typical sulfonylurea, was investigated using density functional theory (DFT) at the B3LYP/6-31[Formula: see text]G(d,p) level. The hydrolysis of metsulfuron-methyl resembles nucleophilic substitution by a water molecule attacking the carbonyl group from aryl side (pathway a) or from heterocycle side (pathway b). In the direct hydrolysis, the carbonyl group is directly attacked by one water molecule to form benzene sulfonamide or heterocyclic amine; the free energy barrier is about 52–58[Formula: see text]kcal[Formula: see text]mol[Formula: see text]. In the autocatalytic hydrolysis, with the second water molecule acting as a catalyst, the free energy barrier, which is about 43–45[Formula: see text]kcal[Formula: see text]mol[Formula: see text], is remarkably reduced by about 11[Formula: see text]kcal[Formula: see text]mol[Formula: see text]. It is obvious that water molecules play a significant catalytic role during the hydrolysis of sulfonylureas.

scholarly journals Solid-Phase “Self-Hydrolysis” of [Zn(NH3)4MoO4@2H2O] Involving Enclathrated Water—An Easy Route to a Layered Basic Ammonium Zinc Molybdate Coordination Polymer

Molecules ◽  
2021 ◽  
Vol 26 (13) ◽  
pp. 4022
Author(s):  
Kende Attila Béres ◽  
István E. Sajó ◽  
György Lendvay ◽  
László Trif ◽  
Vladimir M. Petruševski ◽  
...  
Keyword(s):  
Coordination Polymer ◽  
Solid Phase ◽  
Water Molecules ◽  
Temperature Dependent ◽  
Dynamic Interactions ◽  
Ammonia Release ◽  
Successive Substitution ◽  
Red Dye ◽  
Hydrolysis Of ◽  
Zinc Molybdate

An aerial humidity-induced solid-phase hydrolytic transformation of the [Zn(NH3)4]MoO4@2H2O (compound 1@2H2O) with the formation of [(NH4)xH(1−x)Zn(OH)(MoO4)]n (x = 0.92–0.94) coordination polymer (formally NH4Zn(OH)MoO4, compound 2) is described. Based on the isostructural relationship, the powder XRD indicates that the crystal lattice of compound 1@2H2O contains a hydrogen-bonded network of tetraamminezinc (2+) and molybdate (2−) ions, and there are cavities (O4N4(μ-H12) cube) occupied by the two water molecules, which stabilize the crystal structure. Several observations indicate that the water molecules have no fixed positions in the lattice voids; instead, the cavity provides a neighborhood similar to those in clathrates. The @ symbol in the notation is intended to emphasize that the H2O in this compound is enclathrated rather than being water of crystallization. Yet, signs of temperature-dependent dynamic interactions with the wall of the cages can be detected, and 1@2H2O easily releases its water content even on standing and yields compound 2. Surprisingly, hydrolysis products of 1 were observed even in the absence of aerial humidity, which suggests a unique solid-phase quasi-intramolecular hydrolysis. A mechanism involving successive substitution of the ammonia ligands by water molecules and ammonia release is proposed. An ESR study of the Cu-doped compound 2 (2#dotCu) showed that this complex consists of two different Cu2+(Zn2+) environments in the polymeric structure. Thermal decomposition of compounds 1 and 2 results in ZnMoO4 with similar specific surface area and morphology. The ZnMoO4 samples prepared from compounds 1 and 2 and compound 2 in itself are active photocatalysts in the degradation of Congo Red dye. IR, Raman, and UV studies on compounds 1@2H2O and 2 are discussed in detail.

A multi-responsive organogel and colloid based on the self-assembly of a Ag(i)-azopyridine coordination polymer

Soft Matter ◽  
2021 ◽  
Vol 17 (13) ◽  
pp. 3654-3663
Author(s):  
Botian Li ◽  
Da Xiao ◽  
Xiaodong Gai ◽  
Bo Yan ◽  
Haimu Ye ◽  
...  
Keyword(s):  
Coordination Polymer ◽  
Self Assembly ◽  
The Self

A multi-responsive self-healable organogel and colloid were fabricated by the assembly of a coordination polymer derived from Ag(i) and azopyridine ligands.

scholarly journals Photoluminescent Coordination Polymers Based on Group 12 Metals and 1H-Indazole-6-Carboxylic Acid

Inorganics ◽  
2021 ◽  
Vol 9 (3) ◽  
pp. 20
Author(s):  
Antonio A. García-Valdivia ◽  
Estitxu Echenique-Errandonea ◽  
Gloria B. Ramírez-Rodríguez ◽  
José M. Delgado-López ◽  
Belén Fernández ◽  
...  
Keyword(s):  
Carboxylic Acid ◽  
Coordination Polymers ◽  
Density Functional ◽  
Free Ligand ◽  
Emission Spectra ◽  
Point Of View ◽  
Theoretical Point ◽  
Fourier Transformed Infrared Spectroscopy ◽  
3D Network ◽  
The Stability

Two new coordination polymers (CPs) based on Zn(II) and Cd(II) and 1H-indazole-6-carboxylic acid (H2L) of general formulae [Zn(L)(H2O)]n (1) and [Cd2(HL)4]n (2) have been synthesized and fully characterized by elemental analyses, Fourier transformed infrared spectroscopy and single crystal X-ray diffraction. The results indicate that compound 1 possesses double chains in its structure whereas 2 exhibits a 3D network. The intermolecular interactions, including hydrogen bonds, C–H···π and π···π stacking interactions, stabilize both crystal structures. Photoluminescence (PL) properties have shown that compounds 1 and 2 present similar emission spectra compared to the free-ligand. The emission spectra are also studied from the theoretical point of view by means of time-dependent density-functional theory (TD-DFT) calculations to confirm that ligand-centred π-π* electronic transitions govern emission of compound 1 and 2. Finally, the PL properties are also studied in aqueous solution to explore the stability and emission capacity of the compounds.

Anion-Directed Self-Assembly of Coordination Polymer into Tunable Secondary Structure

2004 ◽  
Vol 126 (22) ◽  
pp. 7009-7014 ◽  
Author(s):  
Ho-Joong Kim ◽  
Wang-Cheol Zin ◽  
Myongsoo Lee
Keyword(s):  
Secondary Structure ◽  
Coordination Polymer ◽  
Self Assembly

scholarly journals Self-assembly of N-heterocyclic carbenes on Au(111)

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Alex Inayeh ◽  
Ryan R. K. Groome ◽  
Ishwar Singh ◽  
Alex J. Veinot ◽  
Felipe Crasto de Lima ◽  
...  
Keyword(s):  
Self Assembly ◽  
Density Functional ◽  
Surface Coverage ◽  
High Mobility ◽  
Heterocyclic Carbenes ◽  
Scanning Tunneling ◽  
Tunneling Microscopy ◽  
Surface Geometry ◽  
Functional Theory ◽  
Interesting Alternative

AbstractAlthough the self-assembly of organic ligands on gold has been dominated by sulfur-based ligands for decades, a new ligand class, N-heterocyclic carbenes (NHCs), has appeared as an interesting alternative. However, fundamental questions surrounding self-assembly of this new ligand remain unanswered. Herein, we describe the effect of NHC structure, surface coverage, and substrate temperature on mobility, thermal stability, NHC surface geometry, and self-assembly. Analysis of NHC adsorption and self-assembly by scanning tunneling microscopy and density functional theory have revealed the importance of NHC-surface interactions and attractive NHC-NHC interactions on NHC monolayer structures. A remarkable way these interactions manifest is the need for a threshold NHC surface coverage to produce upright, adatom-mediated adsorption motifs with low surface diffusion. NHC wingtip structure is also critical, with primary substituents leading to the formation of flat-lying NHC2Au complexes, which have high mobility when isolated, but self-assemble into stable ordered lattices at higher surface concentrations. These and other studies of NHC surface chemistry will be crucial for the success of these next-generation monolayers.

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