Ethylenediamine Molecules Research Articles

Insights into the flotation performance of ethylenediamine surface modified hemimorphite: Experimental and DFT study

Upon utilizing micro-flotation, contact angle, AFM, ToF-SIMS, XPS, ICP-OES, and DFT calculations, the influence of ethylenediamine (EDA) on the flotation mechanism of hemimorphite was investigated. The addition of EDA to the flotation system led to a 25.15 % increase in flotation recovery efficiency. Contact angle and AFM analysis indicated that EDA enhanced both the hydrophobicity and surface roughness of hemimorphite. Subsequently, ToF-SIMS deep profiling analysis indicated that EDA modification facilitated the incorporation of sulfur ions into the internal structure of hemimorphite, forming a uniform zinc sulfide film. Furthermore, XPS and ICP-OES analysis demonstrates an increase in sulfides on the surface of the hemimorphite after EDA modification. Additionally, the results of DFT calculations showed that the adsorption energy of an EDA molecule on the hemimorphite (1 1 0) surface was −956.492 kJ/mol.

1H, 13C, 15N NMR, and DFT Studies on Complex Formation of Zinc(II) Ion with Ethylenediamine in Ionic Liquid [C2mIm][TFSA

In bis(trifluoromethylsulfonyl)amide (TFSA-)-based ionic liquid (IL), 1-ethyl-3-methylimidazolium TFSA- ([C2mIm][TFSA]), the complex formation equilibria of zinc(II) ion (Zn2+) with ethylenediamine (EN) have been investigated. An EN molecule may coordinate with Zn2+ as a bidentate ligand. First, the formation of Zn2+-EN complexes in [C2mIm][TFSA] was confirmed from the difference of 1H and 13C NMR chemical shift values of EN molecules between [C2mIm][TFSA]-EN binary solvents and the 0.1 mol dm-3 Zn(TFSA)2/[C2mIm][TFSA]-EN solutions as a function of EN mole fraction xEN. Second, the stability constants of Zn2+-EN complexes formed in the IL were determined from the concentration ratio [EN]/[Zn2+] dependence of 15N NMR chemical shift values of the TFSA- N atom in the Zn2+/IL-EN solutions. In the IL, mono-, bis-, and tris-EN complexes are successively formed by 1:1 replacement of TFSA- anions coordinated with Zn2+ by EN molecules with increasing EN content. Third, 1H and 13C NMR measurements with the help of density functional theory (DFT) calculations were made on [C2mIm][TFSA]-EN binary solvents as a function of xEN to clarify key interactions to the mechanism of the complex formation. Fourth, the stability constants of Zn2+-EN complexes in the IL were compared with those in aqueous solutions. It was suggested that the hydrogen bonding of the EN molecule with the imidazolium ring H atoms and the TFSA- O atoms reduces the stability of the mono-EN complex in the IL. In contrast, the intracomplex hydrogen bonds between EN and TFSA- in the first coordination shell contribute to the higher stability of the bis-EN complex in the IL than that in aqueous solutions. The difference in the stability constants between the tris-EN complexes and hexaacetonitrile complexes, where acetonitrile (AN) molecules act as monodentate ligands, was interpreted in terms of the higher electron donicity of EN. Finally, to verify the present evaluation, the experimental 13C NMR chemical shift values of EN molecules in the solutions were compared with the theoretical values calculated by DFT using the stability constants determined.

Excess properties and intermolecular interactions of 2-methoxyethanol + ethylenediamine binary system: Density, viscosity, spectral analyses, computational chemistry, and CO2 absorption property

To examine the fundamental physicochemical properties as well as intermolecular interactions for the 2-methoxyethanol (EGME) (1) + ethylenediamine (EDA) (2) binary system, this work systemically measured the density (ρ) and viscosity (η) values of the binary system with various mole ratios at P = 100.5 kPa and T = (298.15–318.15) K with the growth gap of 5 K. The as-measured values of the pure substances were compared with literature data. Multiple semi-empirical formulas were used to fit ρ and η values, and the absolute average deviations (AAD%) were calculated. After that, the excess molar volume (VmE), partial molar volume (V¯), apparent molar volume (Vφ), viscosity deviation (Δη), excess activation of Gibbs free energy (ΔG∗E), and several thermodynamic properties of the binary system were systemically analyzed. According to analysis results, it has been proven that the interaction exists between EGME and EDA molecules. And then, excess properties were fitted to the Redlich-Kister equation using multi-parametric nonlinear regression analyses, and standard deviations (σ) were calculated. In addition, based on various characterization methods including Raman, ultraviolet (UV), and nuclear magnetic resonance hydrogen (1H NMR) spectral analyses and density functional theory (DFT) calculation results, it is demonstrated that there is intermolecular hydrogen bonds in EGME (1) + EDA (2) binary system as the form of –OH⋯NH2–, which was consistent with the existence forms of intermolecular hydrogen bonds in different alcohol-amine systems from references. Finally, CO2 absorption capacity by pure EDA, pure EGME, and the EGME (1) + EDA (2) binary system were severally determined.

Ethylenediamine control of the solid-state supramolecular chemistry of zinc phthalocyanine

The two axially ligated H-shaped and T-shaped zinc phthalocyanine derivatives, ZnPc(EDA)ZnPc and ZnPc(EDA), were obtained directly by thermal reaction of ZnPc in ethylenediamine (EDA) solution. Both complexes, ZnPc(EDA)ZnPc and ZnPc(EDA), co-crystallize with the EDA and water molecules yielding good-quality single crystals [ZnPc(EDA)ZnPc][ZnPc(EDA)]2∙2EDA·6H2O − 1. The interaction of Zn center of ZnPc with the axial substituent containing lone electron pair on NH2 groups with zinc phthalocyanine in both zinc phthalocyanine derivatives, ZnPc(EDA)ZnPc and ZnPc(EDA), leads to a deviation of Zn from the centre of cavity by 0.442(3) and 0.514(3) Å in the T- and H-shaped molecules as well as causes, as expected, the deformation of the planar molecule ZnPc into a saucer-shape conformation. Thus, in both types of molecules the central Zn atom of ZnPc complexes with EDA molecule exhibits 4 + 1 coordination formed by the four isoindole nitrogen atoms of the Pc macrocycle at the equatorial position and the nitrogen atom of the amino group of the EDA molecule at the axial position. Supramolecular arrangement of the T-shaped and H-shaped ZnPc-derivatives in crystal is characterized by a reduction of π···π interactions and an improvement in inter-system crossing in relation to parent ZnPc, and is controlled by the NH∙∙∙O, NH∙∙∙N and OH∙∙∙O hydrogen bonds formed between the T- and H-shaped molecules and lattice EDA and water molecules, which results in increase its solubility and improved photophysical and photochemical properties. The aggregation behaviour of T- and H-shaped ZnPc derivatives building crystals 1 in solutions was investigated by UV–Vis spectroscopy. In order to support and verify the experimental results, the DFT and time-dependent (TD) DFT calculations were performed.

Twisting two-dimensional iron sulfide layers into coincident site superlattices via intercalation chemistry.

Layered van der Waals (vdW) materials are susceptible not only to various stacking polymorphs through translations but also twisted structures due to rotations between layers. Here, we study the influence of such layer-to-layer twisting through the intercalation of ethylenediamine (EDA) molecules into tetragonal iron sulfide (Mackinawite FeS). Selected area electron diffraction patterns of intercalated FeS display reflections corresponding to multiple square lattices with a fixed angle between them, contrary to a single square lattice seen in the unintercalated phase. The observed twist angles of 49.13° and 22.98° result from a superstructure formation well described by the coincident site lattice (CSL) theory. According to the CSL theory, these measured twist angles lead to the formation of larger coincident site supercells. We build these CSL models for FeS using crystallographic group-subgroup transformations and find simulated electron diffraction patterns from the model to agree with the experimentally measured data.

Crystal Field Splitting Energy (Δo) and Racah Parameters (B) of Some Metal-Saccharine and Metal-Saccharine-Ethylenediamine Complexes

[M(sac)2(H2O)4].2H2O [sac = saccharinato anion, M = Fe(II), Co(II), Ni(II), and Cu(II)], and [M(sac)2(en)2].2H2O [sac = saccharinato anion, en = ethylenediamine, M = Fe(II), Co(II), Ni(II) and Cu(II)] were prepared in an aqueous medium. The compounds are crystalline of different colors and are ambiently stable. By examining their physico-chemical properties and relevant literature, the metal(II) ions in both [M(sac)2(H2O)4].2H2O and [M(sac)2(en)2].2H2O complexes are octahedrally coordinated. In the former by four neutral H2O molecules and two monoanionic sac ligands while in later, the octahedral sites fulfilled by two neutral bidentate ethylenediamine molecules and two monoanionic sac ligands. Splitting of the crystal field (Δo) and Racah parameter (B) of two sets of complexes [M(sac)2(H2O)4].2H2O and [M(sac)2(en)2].2H2O are estimated from their electronic spectra using Tanabe-Sugano diagram of Co(II) and Ni(II) complexes while Δo values of Fe(II) and Cu(II) derivatives are calculated directly from their absorption maxima. Our experimental results show that for the studied ligands and the divalent transition metal ions, the Δo values vary according to the following order: Cu(II) > Fe(II) > Co(II) > Ni(II). Dhaka Univ. J. Sci. 71(1): 6-12, 2023 (Jan)

Dynamical properties of the magnesium borohydride – ethylenediamine compound Mg(en)1.2(BH4)2: A nuclear magnetic resonance study

The magnesium borohydride – ethylenediamine (en) compound Mg(en)1.2(BH4)2 exhibits high Mg-ion conductivity above room temperature. To study the dynamical properties of this compound and its partially deuterium-substituted counterpart, we have measured the 1H, 2D, and 11B nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates over a wide temperature range (6–324 K). Our measurements have revealed a coexistence of four types of BH4 reorientational jump processes with different activation energies. For the fastest of these processes characterized by the activation energy of 47(3) meV, the unusually high reorientational mobility is retained down to low temperatures, so that the corresponding H jump rate is of the order of 108 s−1 near 70 K. The presence of fast reorientational motion of [BH4]− anions in Mg(en)1.2(BH4)2 supports the idea that anion reorientations may facilitate the cation diffusion. In the studied temperature range, we have not found any distinct signs of localized motion of the ethylenediamine molecules or their fragments at the NMR frequency scale.

CO2 Methanation: Solvent-Free Synthesis of Nickel-Containing Catalysts from Complexes with Ethylenediamine.

CO2 methanation was studied in the presence of nickel catalysts obtained by the solid-state combustion method. Complexes with a varying number of ethylenediamine molecules in the coordination sphere of nickel were chosen as the precursors of the active component of the catalysts. Their synthesis was carried out without the use of solvents, which made it possible to avoid the stages of their separation from the solution and the utilization of waste liquids. The composition and structure of the synthesized complexes were confirmed by elemental analysis, IR spectroscopy, powder XRD and XPS methods. It was determined that their thermal decomposition in the combustion wave proceeds in multiple stages with the formation of NiO and Ni(OH)2, which are reduced to Ni0. Higher ethylenediamine content in the complex leads to a higher content of metal in the solid products of combustion. However, different ratios of oxidized and reduced forms of nickel do not affect the initial activation temperature of nickel catalysts in the presence of CO2. It was noted that, after activation, the sample obtained from [Ni(C2H8N2)2](NO3)2 exhibited the highest activity in CO2 methanation. Thus, this complex is a promising precursor for CO2 methanation catalysts, and its synthesis requires only a small amount of ethylenediamine.

Ethylenediamine-oxidized sodium alginate hydrogel cross-linked graphene oxide nanofiltration membrane with self-healing property for efficient dye separation

The filtration membrane formed by stacking graphene oxide (GO) nanosheets with two-dimensional layered structure and single-atom thickness has great application prospects for the purification of dye wastewater. In this study, GO was first grafted with ethylenediamine (EDA) to obtain EGO nanosheets, and then oxidized sodium alginate (OSA) was introduced. The aldehyde groups on the OSA molecular chain reacted with the active amino groups to form a hydrogel network structure between adjacent GO layers through Schiff base reaction. Afterwards, a hydrogel-supported layered modified GO nanofiltration membrane was obtained by vacuum-assisted filtration. By changing the addition amount of OSA molecules, the EGO-OSA3 composite membrane with the best performance was selected, which not only had a water flux 9.17 times that of the original GO membrane, but also did not sacrifice the separation performance of dyes. After mechanical damage, by adding a very small amount of OSA, the composite membrane could self-heal by the synergistic effect of dynamic Schiff base and hydrogen bonding interactions between OSA chains and EDA molecules. In addition, due to the stability of the membrane structure brought about by chemical cross-linking, the composite membrane still maintained excellent water purification performance after 100 h of operation.

Исследование оптических свойств аминированных углеродных точек на основе лимонной кислоты и этилендиамина

The most important parameter determining the efficiency of carbon dots as light absorbers in photocatalytic systems is the strength of their binding to the catalyst. It is rather difficult to estimate the contribution of this parameter of carbon dots to the overall efficiency of the photocatalytic system, since the post-synthetic modification of the surface of carbon dots is accompanied by a significant change in their optical and structural properties. In this work, we performed post-synthetic modification of the surface of carbon dots based on citric acid by amination with ethylenediamine molecules by activating the carboxyl groups of carbon dots with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide molecules. The use of this amination approach made it possible to change the charge of carbon dots without changing their main optical and structural properties, which can be further used to assess the contribution of the strength of their binding with Dubois-type molecular catalysts to the overall efficiency of the photocatalytic system.

The Use of Hybrid Genetic Algorithm in the Kinetic Analysis of Thermal Decomposition of [Ni(C2H8N2)3](ClO4)2 with Overlapping Stages.

This work describes the mathematical modeling of the thermal decomposition of the complex compound [Ni(En)3](ClO4)2 (En = C2H8N2 = ethylenediamine) in an inert atmosphere under non-isothermal conditions. This process is characterized by several simultaneous and intense stages: elimination of ethylenediamine from the nickel coordination sphere, decomposition of perchlorate anions, and explosive-like oxidation of free or bound ethylenediamine. These stages overlap and merge into a one step on the differential thermogravimetric curve. Typically, this curve is modeled as a one-stage process during kinetic analysis. In this paper, for the first time, the data from the dynamic mass-spectral thermal analysis and thermogravimetric analysis were modeled using the hybrid genetic algorithm, and the results were compared. A two-stage scheme of [Ni(En)3](ClO4)2 thermolysis was proposed and the kinetic parameters for each stage were obtained. It was shown that the decomposition of [Ni(En)3](ClO4)2 begins with the elimination of one molecule of ethylenediamine (stage A), then the perchlorate anions quickly decompose with the evolution of oxygen (stage B). We believe that the resulting ClO4-x- (x = 1-3), as stronger oxidizing agents, instantly start an explosive-like exothermic process of ethylenediamine oxidation (stage B).

Synthesis and Crystal Structure of two Copper (II) Carboxylate Complexes with Ethelyenediamine

A new crystal of, [Cu (OH2)2 (en)2] 4-oxidobenzoate and [Cu(OH2)2 (en)2] (3,5-dinitrobenzoate)2 Where (en = ethylenediamine) have- been synthesize, and the resulting complexes has been analyzed on the base of CHN analyses, IR spectral, Electronic spectra, single- crystal X-ray- diffraction method and magnetic susceptibility. In both complexes cations have a distorted octahedral CuN4O2 around copper (II), surrounded by two molecules of ethylenediamine and two water molecules. The cations [Cu (en) 2(OH2)2]2+ of both complexes are associated to carboxylate anions by hydrogen bonding in addition to electrostatic forces.

Cooperative Intrinsic Basicity and Hydrogen Bonding Render SmI2 More Azaphilic than Oxophilic.

It has been recently shown that SmI2 is more azaphilic than oxophilic. Density functional theory calculations reveal that coordination of 1-3 molecules of ethylenediamine is more exothermic by up to 10 kcal/mol than coordination of the corresponding number of ethylene glycol molecules. Taking into account also hydrogen bonds between ligands and tetrahydrofuran doubles this preference. The intrinsic affinity parallels the order of basicity. The cooperativity with the hydrogen bonding makes SmI2 more azaphilic than oxophilic.

Tetrahydrated bis(monoaqua-bis(ethylenediamine)copper(II))-diaqua-bis(ethylenediamine)copper(II) dicitrate: Preparation, crystal structure, Raman and FTIR spectra and paramagnetic behavior

The crystals of the first copper(II) ethylenediamine complex containing citrate anion have been prepared and characterized. Despite the archetypical character of the copper(II) ethylenediamine complexes, some structural peculiarities were found to be interesting since they are quite rare even among the mentioned type of the complex compounds i.e. a presence of both mono and diaqua-bis(ethylenediamine)copper(II) cations together in the same crystal structure, intramolecular hydrogen bonding of the citric anion, cis,trans-configuration of the citric anion and the disordered C-C bond of the ethylenediamine molecule in the monoaqua-bis(ethylenediamine)copper(II) cation, which in fact is a co-existence of two energetically close δδ and δλ conformers. The Raman as well as FTIR spectra were recorded and discussed. Finally, the magnetic measurements have shown paramagnetic behavior of the prepared complex in a wide range of temperatures.

Fascinating 3D energetic [Ag2(N5)2(EDA)]n: filling the ethylenediamine molecules into a [Ag(N5)]nframework

The ethylenediamine (EDA) molecules are “filled” into [Ag(N5)]nto synthesize an interesting 3D motif, [Ag2(N5)2(EDA)]n. Moreover, the fantastic architectures and properties of the three 3D Ag–N5frameworks are compared.

Functionalization of Mono- and Bimetallic MIL-100(Al,Fe) MOFs by Ethylenediamine: Postfunctionalization, Brønsted Acido-Basicity, and Unusual CO2 Sorption Behavior.

The metal sites of MIL-100(Fe), MIL-100(Fe,Al), and MIL-100(Al) metal-organic frameworks (MOFs) were decorated with ethylenediamine (EN). Interestingly, the Al-containing MOFs presented hierarchized porosity, and their structural integrity was maintained upon functionalization. Solution and solid-state NMR confirmed the grafting efficiency in the case of MIL-100(Al) and the presence of a free amine group. It was shown that MIL-100(Al) can be functionalized by only one EN molecule in each trimeric Al3O cluster unit, whereas the other two aluminum sites are occupied by a hydroxyl and a water molecule. The -NH2 sites of the grafted ethylenediamine can be used for further postfunctionalization through amine chemistry and are responsible for the basicity of the functionalized material as well as increased affinity for CO2. Furthermore, the presence of coordinated water molecules on the Al-MOF is responsible for simultaneous Brønsted acidity. Finally, the Al-containing MOFs show an unusual carbon dioxide sorption mechanism at high pressures that distinguishes those materials from their iron and chromium counterparts and is suspected to be due to the presence of polarized Al-OH bonds.

Extended ensemble molecular dynamics study of cellulose I–ethylenediamine complex crystal models: atomistic picture of desorption behaviors of ethylenediamine

Cellulose I crystals swell on exposure to ethylenediamine (EDA) molecules to form a cellulose I–EDA complex, and successive extraction of EDA molecules converts the complex crystalline phase to either original cellulose I or cellulose IIII, depending on the treatment procedure. The present study reports the extended ensemble molecular dynamics (MD) simulation of the cellulose I–EDA complex models. An accelerated MD simulation allows most of the EDA molecules to desorb from the crystal model through a hydrophilic channel between the piles of cellulose chains, one at a time. Migration of a single EDA molecule along the channel is simulated by the adopted steered MD method combined with the umbrella sampling method to evaluate the potential of mean force (PMF) or free energy change on its movement. The PMF continues to increase during the migration of an EDA molecule to give a final PMF value of more than 30 kcal/mol. The PMF profiles are largely lowered by the removal of EDA molecules in the neighboring channels and by the widening of the channel. The former suggests that the EDA desorption cooperates with that in the neighboring channels, and, in the latter case, an EDA migration is efficiently promoted by solvation with water molecules in the expanded channel. We conclude that the atomistic picture of the EDA desorption behaviors observed in the crystal models is applicable to the real crystalline phase. Graphic abstract

On the Nature of Crystals Precipitating from Aqueous Silver Ethylenediamine Oxalate Complex Solutions

AbstractAqueous silver ethylene diamine oxalate complex solution is a critical precursor in the production of supported silver catalysts. Crystals precipitating from such complex solutions are characterized by single‐crystal structure analysis as [Ag(μ‐en)]2(C2O4)×2H2O. Silver atoms are bridged by ethylenediamine molecules in a molar ratio of 1 : 1 forming slightly distorted one‐dimensional polymeric Ag(μ‐en)‐chains along the c axis. Oxygen atoms of oxalate groups show no direct coordination to silver atoms. Oxygen atoms of lattice water molecules show a weak lateral coordination to silver atoms within slightly bent N−Ag−N fragments.

Bioactive and biopassive treatment of poly(ethylene terephthalate) multifilament textile yarns to improve/prevent fibroblast viability.

To modulate the physicochemical features of poly(ethylene terephthalate) (PET) multifilaments surface composing a complex textile structure (core and shell system), intended to improve upon current implants for high extension injuries of the Achilles tendon or even for its total replacement, two surface treatments with different purposes (bioactive and biopassive) were studied. The first treatment is based on amino groups grafting using ethylenediamine molecules to be applied in the structure core to improve cell adhesion and proliferation. The other treatment relates to a polytetrafluoroethylene (PTFE) coating to be applied in the structure shell to decrease its coefficient of friction and avoid adhesions. Both treatments were optimized to reach their purposed goals without harming the tensile properties of PET yarns, which were evaluated by static tensile tests. The resazurin assay and scanning electron microscopy analysis showed that the purposed goals related to fibroblast adhesion were achieved for both treatments and in the case of PTFE coating, the abrasion resistance was also improved according to the yarn-on-yarn abrasion tests.

Non-innocent Intercalation of Diamines into Tetragonal FeS Superconductor

We report two solvothermal pathways toward intercalated iron sulfide, [Fe8S10]Fe(en)3·en0.5 (en = ethylenediamine), featuring [Fe8S10]2– layers stacked by [Fe(en)3]2+ cations and free ethylenediamine molecules. [Fe8S10]Fe(en)3·en0.5 is synthesized in a simple single-step method from Fe and S in ethylenediamine with addition of NH4Cl mineralizer as well as from solvothermal treatment of mackinawite, tetragonal FeS. In situ synchrotron powder X-ray diffraction experiments reveal a clear transformation of tetragonal FeS into [Fe8S10]Fe(en)3·en0.5 upon reaction with ethylenediamine. In-house control synthetic experiments confirmed the chemical process, whereby ethylenediamine leaches iron solely from the tetragonal Fe–S layers to form [Fe(en)3]2+ complexes and thereby oxidize the intralayer iron to Fe2.25+. Our report emphasizes that, in layered iron chalcogenides, diamines can intercalate as charged coordination complexes in tandem with neutral diamine molecules.