Diethylenetriamine Derivatives Research Articles

Synthesis and Evaluation of the Antimicrobial Activity of Cationic Amphiphiles Based on Bivalent Diethylenetriamine Derivatives

Synthesis and Evaluation of the Antimicrobial Activity of Cationic Amphiphiles Based on Bivalent Diethylenetriamine Derivatives

Exploring the synthesis and characterization of fac-Re(CO)3L complexes using diethylenetriamine derivative functionalized at the central nitrogen

The aim of this research is to develop new rhenium complexes with favorable bio-distribution properties which can be used as radiometal complexes or for conjugation with biomolecules for the development of targeted radiolabelled biopharmaceuticals. Two metals of interest utilized in radiopharmaceuticals are technetium and rhenium, both of which share similar chemical and structural properties. The coordination chemistry of these metals is highly dependent upon ligands that are structurally and chemically robust among other factors. The synthesis of new symmetrical tridentate ligands and ligand conjugation methods will expand the likelihood of developing suitable fac-[Re(CO)3L]n compounds with promising biomedical properties and were consequently the subject of this investigation. In order to accomplish this, the design, synthesis, characterization and X-ray structure of new water-soluble rhenium complexes for assessing metal binding to biomolecules were investigated. Three diethylenetriamine (dien) derivatives, 2-(bis(2-aminoethyl)amino)-N-(2-oxo-4-(trifluoromethyl)-2H-chromen-7-yl)acetamide (atfcdien, 3), 2-(bis(2-aminoethyl)amino)-N-(3,5-bis(trifluoromethyl)benzyl)acetamide (tfmedien, 6), and N-benzyl-2-(bis(2-aminomethyl)amino)acetamide (badien, 9) and their rhenium complexes were synthesized. 1H NMR spectroscopy, mass spectrometry and X-ray crystallography techniques were employed to characterize the ligands and their rhenium complexes [Re(CO)3atfcdien]Br (10), [Re(CO)3tfmedien]Br (11) and [Re(CO)3badien]Br (12). 1H NMR studies were conducted to examine chelated Re complexes revealed a consistent downfield shift of the CH signal of the dien moiety for all three new ligands.

Synthesis and Catalytic Application of Two Mononuclear Complexes Bearing Diethylenetriamine Derivative Ligand.

Two mononuclear zero-dimensional Ni(II) and Zn(II) complexes bearing diethylenetriamine derivative ligand, namely [NiL(CH3COO)2(H2O)] (1) and [ZnL(CH3COO)2] (2) [L = N, N’-bis(2-hydroxybenzyl)diethylenetriamine], were synthesized under reflux conditions. The molecular composition and structure of the complexes were identified by IR, PXRD, elemental analyses, and single crystal X-ray diffraction. Complex 1 belongs to a monoclinic crystal system with the P21/n space group, and Complex 2 belongs to a monoclinic crystal system with the C2/c space group. The Henry reaction of nitromethane with aromatic aldehydes was explored with Complexes 1 and 2 as the catalyst. Results from the catalytic reaction revealed that the complexes displayed excellent catalytic activities under the optimized conditions and that the substrate scope of aromatic aldehydes could be extended to a certain extent. In addition, the possible catalytic mechanism of the Henry reaction was also deduced.

A facile synthesis of bis-(pththalimidoethyl)-amine functionalized graphene oxide and its dual performance as a supercapacitor electrode and fluorescence sensor

In the work, we report a facile synthesis of Bis-(pththalimidoethyl)-amine functionalized graphene oxide (GO-bis(PIEA)) using a masked diethylenetriamine derivative as an intercalating agent on the surface of GO for the supercapacitor applications. The prepared material was fully characterized by XRD, XPS, Raman and microscopic techniques and its fluorescence behaviour due to the presence of phthalimide conjugate was also studied. The GO-bis(PIEA) material shows the sheets like nanostructure with d-spacing of 1.1 nm (2θ = 8.7 deg.) between the sheets due to the covalent intercalation and thereby exhibits better specific capacitance of 287 F g−1 at a specific current density of 1 A g−1 in 6 M KOH. A very low capacitance degradation of 5.5% was noted up to 1000 cycles. The GO-bis(PIEA) material was also working well as a selective fluorescent chemosensor for Ni2+ ion in aqueous solution at neutral pH and proves no cross-reaction with any of the potential interfering metal ions. The dual enhancement of dissimilar properties such as capacitance and fluorescence emphasized the continued significance of covalent functionalization towards tuning the properties of graphene-based materials.

Biosorption of Acid Dyes Using Modified Chitosan: Effect of Dye Structure, Hydrogen Bonding and PH

This work investigated sorption properties of diethylenetriamine derivative of chitosan (CTSN) for removal of acid dyes (Acid Green 25 (AG25), Acid Red 18 (AR18) and Acid Orange 10 (AO10)) from aqueous solutions. Sorption kinetics was firstly evaluated. It was found that pseudo-second-order model fits well with these dyes adsorbed on CTSN. Compared with normal chitosan, CTSN has higher capacity for AR18 and AO10, but a lower value for AG25. Mechanisms and interactions of dyes with CTSN were also discussed by study the effect of pH, influence of hydrogen-bonding and comparing the sorption capacities.

Methoxyquinoline-diethylenetriamine conjugate as a fluorescent zinc sensor

A 6-methoxyquinoline conjugated diethylenetriamine derivative, N,N''-bis(6-methoxy-2-quinolylmethyl)diethylenetriamine (6-MeOBQDIEN) has been synthesized and its fluorescent response toward zinc ion was investigated. In the presence of zinc ion, 6-MeOBQDIEN exhibits fluorescence (λ(ex) = 329 nm, λ(em) = 418 nm, φ = 0.039). The fluorescent intensity of the zinc complex of the compound is two times higher than the parent BQDIEN (φ = 0.021) under the same conditions. The crystal structure of 6-MeOBQDIEN-Zn complex shows that all five nitrogen atoms participate to the metal coordination in a distorted square-pyramidal geometry (τ = 0.145) with the aliphatic nitrogen in an apical position. Fluorescent microscopic analysis using 6-MeOBQDIEN reveals the zinc ion concentration change in living cells.

Extraction of rhodium(III) by a bisacylated diethylenetriamine derivative from hydrochloric acid solutions

The extraction of rhodium(III) with a bisacylated diethylenetriamine derivative from hydrochloric acid solutions was studied. Optimum conditions for rhodium(III) extraction were determined. It was found that, at a contact time to 10 min, the extraction occurred by an ion-association mechanism. At a contact time longer than 10 min, rhodium(III) was extracted by a mixed mechanism with the insertion of an extractant molecule into the inner coordination sphere of the rhodium(III) ion. The composition of the extracted compound was determined using electronic, 1H and 13C NMR, and IR spectroscopy and elemental analysis, and the structure of this compound was proposed.

Exploring water-soluble Pt(II) complexes of diethylenetriamine derivatives functionalized at the central nitrogen. Synthesis, characterization, and reaction with 5′-GMP

Abstract The aims of our program are to develop coordination complexes that can be used as selective probes, fluorescent agents and inorganic medicinal agents. In order to accomplish this, the design, synthesis, characterization and X-ray structure of new water-soluble monofunctional Pt(II) complexes with useful spectroscopic properties for assessing metal binding to biomolecules were investigated. Two diethylenetriamine (dien) derivatives, 2-(bis(2-aminoethyl)amino)acetic acid (acdien) and N′-[7-(acetamido)-4-(trifluoromethyl)coumarin]diethylenetriamine (atfcdien), were used. The latter was designed to allow the fluorophore group, 7-amino-4-(trifluoromethyl)coumarin (atfc), to be attached to metal centers through the dien moiety. 1H NMR spectroscopy and X-ray crystallography were employed to characterize the [Pt(atfcdien)Br][Pt(Me2SO)Br3] (8a) and [Pt(acdien)Br]Br (9a) complexes. 1H NMR and fluorescence spectroscopic methods were used to characterize the [Pt(atfcdien)Br]Br (8b) and [Pt(acdien)Br]Br (9a) complexes. 1H NMR studies of the monofunctional [Pt(acdien)Br]Br (9a) complex conducted to examine its interaction with guanosine 5′-monophosphate (5′-GMP) in D2O solutions revealed one downfield-shifted H8 and one downfield-shifted H1′ signal, consistent with 5′-GMP binding via N7 and fast rotation about the Pt–N7 bond.

Synthesis of mono- and bibrachial naphthalene-based macrocycles with pyrene or ferrocene units for anion detection

Three bibrachial cyclobisintercaland-type macrocycles with a 2,6-naphthylene scaffold and pyrene, ferrocene, or primary amino groups in side chains were synthesized by a [2+2]-cyclocondensation of functionalized diethylenetriamine derivatives with naphthalene-2,6-dialdehyde, whereas their monobrachial counterparts were prepared by a [1+1]-cyclocondensation of polyamines with a corresponding dialdehyde building block. The pyrene-functionalized macrocycles are able to bind orthophthalate and terephthalate anions in aqueous medium, as monitored by the changes in their fluorescence (excimer or monomer) properties.

Molecular Design of Tetraazamacrocyclic Derivatives Bearing a Spirobenzopyran and Three Carboxymethyl Moieties and Their Metal-Ion Complexing Behavior

Tetraazacyclododecane and tetraazacyclotetradecane derivatives bearing a spirobenzopyran and three carboxymethyl moieties, 1 and 2, and a diethylenetriamine derivative bearing a spirobenzopyran and four carboxymethyl moieties 3 were synthesized. The isomerization behaviors based on the spirobenzopyran moiety of these ligands were studied by UV-visible spectrophotometry in aqueous solutions containing various metal ions at neutral pH. These ligands formed stable 1:1 complexes with lanthanide ions, while the spirobenzopyran moiety was isomerized to its corresponding merocyanine form even under dark conditions. In aqueous solutions containing a lanthanide ion, the absorption spectra of 1 or 2 showed remarkable blue shifts, while absorbances at the maximum absorption wavelengths in the visible region were enhanced; such changes are attributable to the isomerization to the merocyanine form of the spirobenzopyran moiety. These results suggest that the phenolate anion of the merocyanine moiety interacts very strongly with a lanthanide ion bound by the complexing moiety because of the high charge density of lanthanide ions. In contrast, the absorbance of merocyanine form was decreased by the complexation of the macrocyclic ligand with transition metal ions, such as Cu2+ and Zn2+. This result indicates that macrocyclic ligands, 1 and 2, formed complexes with transition metal ions only by the aminocarboxylate moieties, and the phenolate ion of merocyanine moiety was not able to participate in the complexation. This conclusion was also demonstrated by density functional theory calculations.

Catalysis of Aryl Ester Hydrolysis in the Presence of Metallomicelles Containing a Copper(II) Diethylenetriamine Derivative

The novel metallosurfactant Cu(II)-1-tetradecyldiethylenetriamine (Cu(II)TDET) was prepared, and the hydrolyses of 2-acetoxy-5-nitrobenzoic acid (1), 4-acetoxy-3-nitrobenzoic acid (2), 4-nitrophenyl acetate (3), and 2-nitrophenyl acetate (4) in the presence of micellar Cu(II)TDET were examined. The rate of ester hydrolysis for the series followed the order 1 approximately 2>3>4. The larger observed rate (kpsi) for 1 and 2 was attributed to (i) electrostatic interaction between the carboxylate anion and the cationic metallomicelle surface and (ii) the formation of a ternary complex metal:surfactant ligand:substrate (MLnS). The position of the carboxylate anion in the substrate did not significantly affect catalysis. Similar rates were observed when the carboxylate anion was ortho to the acyl ester 1 or para to the reaction center 2. The absence of a significant difference may be associated with the ternary complex coordination geometry, which unfavorably aligned the ligated substrate and the metal-bound hydroxyl. Mixed micellar solutions containing Cu(II)TDET and MTAB or Triton X-100 were examined. Added cosurfactants have a pronounced effect on the catalytic activity of Cu(II)TDET. At a low concentration of Cu(II)TDET the addition of MTAB or Triton X-100 increased the pseudo-first-order rate constant (kpsi) for the hydrolysis of 1 and 3 relative to the rate in pure Cu(II)TDET. The addition of a cosurfactant increased the total micellar volume (VM), promoting substrate incorporation within the pseudophase. At higher metallosurfactant concentration, the rate enhancement was smaller due to the dilution of the substrate within the co-micellar pseudophase.

Synthesis of tridentate amine Pt(II) complexes and study of their reactions with purine and pyrimidine bases

Complexes of the type [Pt(L)X] where L is a tridentate N ligand and X = Cl or I, were synthesized and characterized. Three of the ligands are N-derivatives of diethylenetriamine, (2-aminoethyl)(N-dimethyl-2-aminoethyl)amine, (2-aminoethyl)(N-diethyl-2-aminoethyl)amine, and (2-aminoethyl)(N-methyl-2-aminoethyl)N-methylamine. The other two ligands are di(3-amino-propyl)amine and (2-aminoethyl)(3-aminopropyl)amine. A new method for the synthesis of the chloro complexes from the direct reaction of the amine with K2[PtCl4] was developed. The reactions of these five compounds with several purine and pyrimidine bases were studied by NMR techniques. The Pt(II) complexes containing two five-membered chelates were shown to be more reactive than the one containing two six-membered rings, while the complex containing one five- and one six-membered chelates showed intermediate reactivity. For the diethylenetriamine derivatives, the complexes containing ligands with two alkyl groups on the same terminal N atom were more reactive than the one containing one methyl group on a terminal N atom and one methyl group on a non-terminal N atom.

New synthetic, selective, high-affinity ligands for effective trivalent metal ion binding and transport

A series of new ligands containing 3-hydroxy-2-pyridylmethyl donor groups has been synthesized which form complexes of iron(III) having thermodynamic stabilities comparable to and greater than those of natural catecholtype siderophores. When this functional group is substituted on the triazacyclononane framework the resulting hexadentate ligand has an affinity for iron(III) which exceeds that of the natural siderophore, enterobactin, at physiological pH. Ethylenediamine and diethylenetriamine derivatives containing hydroxypyridyl and acetate donors also show high affinity for Fe(III) and other trivalent metal ions. The stabilities of the iron(III) chelates of the new ligands, particularly the triazacyclononane derivatives, are compared with those of other highly effective iron chelators published in the literature, such as the trishydroxamates and triscatecholate ligands.

Catalytic Epoxidation of Olefins with t-Butyl Hydroperoxide in the Presence of Polymer-supported Vanadium(V) and Molybdenum(VI) Complexes

Abstract Oxovanadium(V) and oxomolybdenum(VI) ions have been incorporated into cross-linked polystyrene resins functionalized with iminodiacetic acid or diethylenetriamine derivatives. The polymer complexes have been used as catalysts in the epoxidation of olefins with t-butyl hydroperoxide. Vanadium(V) complexes promote epoxidation of allylic alcohols in a highly regioselective manner, e.g., 2,3-epoxide has been preferentially obtained in 98% selectivity from (E)-geraniol at 80 °C. The catalytic activity of the vanadium(V) complexes is generally higher than that of the molybdenum(VI) complexes in the epoxidation of allylic alcohols whereas an opposed trend holds for the epoxidation of cyclohexene. Life time of catalysts have been examined by repeated use of the complexes in the epoxidation of (E)-geraniol at 80 °C in benzene. Approximately 15–25% of vanadium has been leaked out of the polymer beads on five time recycles leading to the decrease in the yield of 2,3-epoxide from initial value of 98% to 95–93%. Neither appreciable loss of metal nor reduction of catalytic activity has been observed in the molybdenum complex systems over five runs.

Preparation and complexation properties of polystyrene resins containing diethylenetriamine derivatives

Styrene-divinylbenzene copolymer resins containing a series of diethylenetriamine derivatives have been prepared and characterized. The multidentate ligands are covalently bound to the polymer matrix without causing inter- and intrastrand bridging structures. The properties of the present chelating resins have been examined with respect to the uptake of transition metal ions.