scholarly journals Synthesis and Study in Solution of a New Dansyl-Modified Azacryptand

2016 ◽  
Vol 2016 ◽  
pp. 1-10 ◽  
Author(s):  
Greta Bergamaschi ◽  
Ana Miljkovic ◽  
Stefania Marcheggiani ◽  
Antonio Poggi

We report the synthesis of a new asymmetric azacryptand (L1), characterized by three p-xylyl spacers, one of which carries a dansyl side arm. The fluorescent sensor has been studied by potentiometric, UV-Vis, and emission studies in MeOH : water 3 : 2 mixture (0.07 M NaNO3), determining, in particular, the protonation constants of the free ligand and metal ion complexation equilibria. Interestingly, the obtained results revealed that the new receptor is fluorescent at neutral pH with a typical emission band of the dansyl group. Metal addition induced a partial quenching of the dansyl emission band; this behavior is more pronounced with Cu(II) that reduces the receptor’s emission by 60%. With all the studied cations, quenching follows the formation of a dimetallic complex. Similar studies on the model compound L2 confirmed that fluorescence quenching is mainly driven by a static mechanism, attributable to the formation of the inclusion dicopper complex [L1Cu2]4+. In order to test the stability of copper complexes under physiological conditions, spectrofluorimetric titrations with Cu(II) were performed in water buffered at pH = 8 (HEPES 0.07 M) and the values of binding constants, K11 and K12, were determined.

2007 ◽  
Vol 2007 ◽  
pp. 1-7 ◽  
Author(s):  
Sulekh Chandra ◽  
Smriti Raizada ◽  
Monika Tyagi ◽  
Archana Gautam

A series of metal complexes of Cu(II) and Ni(II) having the general composition[M(L)X2]with benzil bis(thiosemicarbazone) has been prepared and characterized by element chemical analysis, molar conductance, magnetic susceptibility measurements, and spectral (electronic, IR, EPR, mass) studies. The IR spectral data suggest the involvement of sulphur and azomethane nitrogen in coordination to the central metal ion. On the basis of spectral studies, an octahedral geometry has been assigned for Ni(II) complexes but a tetragonal geometry for Cu(II) complexes. The free ligand and its metal complexes have been tested in vitro against a number of microorganisms in order to assess their antimicrobial properties.


1985 ◽  
Vol 50 (2) ◽  
pp. 445-453 ◽  
Author(s):  
Jana Podlahová ◽  
Josef Šilha ◽  
Jaroslav Podlaha

Ethylenediphosphinetetraacetic acid is bonded to metal ions in aqueous solutions in four ways, depending on the type of metal ion: 1) through an ionic bond of the carboxylic groups to form weak complexes with a metal:ligand ratio of 1 : 1 (Ca(II), Mn(II), Zn(II), Pb(II), La(III)); 2) through type 1) bond with contributions from weak interaction with the phosphorus (Cd(II)); 3) through coordination of the ligand as a monodentate P-donor with the free carboxyl groups with formation of 2 : 1 and 1 : 1 complexes (Cu(I), Ag(I)); 4) through formation of square planar or, for Hg(II), tetrahedral complexes with a ratio of 1 : 2 with the ligand as a bidentate PP-donor with the free carboxyl groups (Fe(II), Co(II), Ni(II), Pd(II), Pt(II)). On acidification of the complex solution, the first two protons are bonded to the carboxyl groups. The behaviour during further protonation depends on the type of complex: in complexes of types 1) and 2) phosphorus is protonated and the complex dissociates; in complexes of types 3) and 4) the free carboxyl groups are protonated and the phosphorus-metal bond remains intact. The results are based on correlation of the stability constants, UV-visible, infrared, 1H and 31P NMR spectra and magnetic susceptibilities of the complexes in aqueous solution.


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 ◽  
...  

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.


2019 ◽  
Vol 32 (1) ◽  
pp. 209-214
Author(s):  
Deepak Kumar ◽  
Arun Kumar Singh ◽  
Ajay Kumar ◽  
Dayanand Prasad ◽  
Vijay Kumar ◽  
...  

2,4,5-Trimethoxybenzaldehyde was condensed with S-benzyldithiocarbazate to give Schiff base 2,4,5-trimethoxy benzaldehyde-S-benzyldithiocarbazone (BBTC), which was used for complexation with Mn(II), Fe(II) and Co(II) metal ions. The complexes were formulated as M(BBTC)2X2 where X is Cl−, NO3− and CH3COO−. The FTIR spectra of the metal complexes in comparison to that of free ligand suggested the coordination through azomethine nitrogen and thion sulphur forming six membered chelating with metal ion. The magnetic susceptibility and electronic spectral bands revealed octahedral symmetry (Oh) around Mn(II) but tetragonally distorted octahedral symmetry (D4h) of Fe(II) and Co(II) complexes. The positive value of Dt for Fe(II) (68.42-135.2 cm-1) and Co(II) (263-280 cm-1) clearly indicated elongation along z-axis in these complexes which was also supported by the less value of Dq(z) than Dq(xy) for the metal complexes. The ligand as well as its metal complexes have been found active against the bacteria Escherichia coli and Staphylococcus aureus, and antibacterial activity of the free ligand has been observed to have enhanced in metal complexes.


2007 ◽  
Vol 3 (1) ◽  
pp. 133-142 ◽  
Author(s):  
Ishaq Abdullah Zaafarany

Abstract          The kinetics of sol-gel transformation between A13+, La 3+ and Th4+ metal ion electrolytes and sodium alginate sol have been studied complexometrically at various  temperatures. In the presence of a large excess of sodium alginate sol concentration over that of metal ion electrolyte, the pseudo first–order plots of exchange showed sigmoidal curves with two distinct stages. The initial part was relatively fast and curved significantly at early times, followed by a slow decrease in the rates of exchange over longer time periods. The rate constants of gelation showed second-order overall kinetics which was first order in the concentration of both reactants. The thermodynamic parameters have been evaluated and tentative gelation mechanisms consistent with the kinetic results of gelation are suggested. The stability of these ionotropic metal-alginate complexes has been discussed in terms of the coordination geometry and strength of chelated bonds.


2010 ◽  
Vol 29 (2) ◽  
pp. 215 ◽  
Author(s):  
Tatjana Anđelković ◽  
Ružica Nikolić ◽  
Aleksandar Bojić ◽  
Darko Anđelković ◽  
Goran Nikolić

The binding of Cd(II) to soil humic acid (HA) at pH 6.5 and in 0.1 mol/L KNO3 ionic medium, was studied by potentiometric titration with a cadmium ion selective electrode. The influence of carboxyl groups in cation-humic interactions was investigated by selective blocking of humic acid carboxyl groups with thionyl chloride and methanol. Infrared spectroscopic analysis confirmed that esterification took place. Differences between underivatized and derivatized HA complexation properties are ascribed to carboxyl groups. The Scatchard plots and incremental formation constants were used to obtain values for Cd-binding constants, for both HAs. The derivatization decreased the number of HA complexing sites by approximately 60 %, which correlates with acid-base properties of both HAs, studied by barium hydroxide and calcium acetate exchange methods. The stability constants for binding at the strongest sites (logKINT) was larger for underivatized HA (5.40) than for derivatized HA (4.92), indicating greater stability in the case when carboxyl groups are involved in complexation reaction.


2010 ◽  
Vol 4 (2) ◽  
pp. 37-45
Author(s):  
Matheel D. Al-Sabti ◽  
Ahmed A. H. Al-Amiery ◽  
Thorria R. Marzoog ◽  
Yasmien K. Al-Majedy

This study involves the chemical synthesis of the novel ligand 5-(2-diphenylphosphino) phenyl-1,2-dihydro-1,2,4-triazole-3-thione (DPDTT) by the reaction of 2-diphenylphosphino benzoic acid with absolute ethanol that yield ethyl 2-diphenylphosphino benzoate and by cyclization of this compound with thiosemicarbazide, DPDTT will be produced. The chelating complexes of this ligand with Cr(III), Co(II), Ni(II), Cu(II) and Cd(II) were also prepared and studied. The new complexes were characterized by FT-IR, UV/visible spectra, and room temperature magnetic susceptibility. The stability for the prepared complexes was also measured using the density function theory and it was found that the cadmium complex is the most stable and the chromium complex is the least stable. Free ligand and its metal complexes have been tested in vitro against a number of microorganisms, like gram positive bacteria Staphylococcus aureus and gram negative bacteria E. coli, Proteus vulgaris, Pseudomonas and Klebsiella in order to assess their antimicrobial properties. All complexes showed considerable activity against all the studied bacteria.


The Analyst ◽  
2010 ◽  
Vol 135 (1) ◽  
pp. 140-148 ◽  
Author(s):  
Wei Zhang ◽  
Jian-Feng Chen ◽  
Liu-Yin Fan ◽  
Cheng-Xi Cao ◽  
Ji-Cun Ren ◽  
...  

1999 ◽  
Vol 6 (6) ◽  
pp. 321-328 ◽  
Author(s):  
Bin Song ◽  
Jing Zhao ◽  
Fridrich Gregáň ◽  
Nadja Prónayová ◽  
S. Ali A. Sajadi ◽  
...  

The stability constants of the 1:1 complexes formed between methylphosphonylphosphate (MePP3-), CH3P(O)2--O-PO32- , and Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+,​ or Cd2+ (M2+) were determined by potentiometric pH titration in aqueous solution (25 C° ; l = 0.1 M, NaNO3 ). Monoprotonated M(H;MePP) complexes play only a minor role. Based on previously established correlations for M2+ -diphosphate monoester complex-stabilities and diphosphate monoester β-group. basicities, it is shown that the M(Mepp)- complexes for Mg2+ and the ions of the second half of the 3d series, including Zn2+ and Cd2+, are on average by about 0.15 log unit more stable than is expected based on the basicity of the terminal phosphate group in MePP3-. In contrast, Ba(Mepp)- and Sr(Mepp)- are slightly less stable, whereas the stability for Ca(Mepp)- is as expected, based on the mentioned correlation. The indicated increased stabilities are explained by an increased basicity of the phosphonyl group compared to that of a phosphoryl one. For the complexes of the alkaline earth ions, especially for Ba2+, it is suggested that outersphere complexation occurs to some extent. However, overall the M(Mepp)- complexes behave rather as expected for a diphosphate monoester ligand.


1995 ◽  
Vol 308 (1) ◽  
pp. 237-241 ◽  
Author(s):  
R Ramkumar ◽  
A Surolia ◽  
S K Podder

The thermodynamics of the binding of derivatives of galactose and lactose to a 14 kDa beta-galactoside-binding lectin (L-14) from sheep spleen has been studied in 10 nM phosphate/150 mM NaCl/10 mM beta-mercaptoethanol buffer, pH 7.4, and in the temperature range 285-300 K using titration calorimetry. The single-site binding constants of various sugars for the lectin were in the following order: N-acetyl-lactosamine thiodigalactoside > 4-methylumbelliferyl lactoside > lactose > 4-methylumbelliferyl alpha-D-galactoside > methyl-alpha-galactose > methyl-beta-galactose. Reactions were essentially enthalpically driven with the binding enthalpies ranging from -53.8 kJ/mol for thiodigalactoside at 301 K to -2.2 kJ/mol for galactose at 300 K, indicating that hydrogen-bonding and van der Waals interactions provide the major stabilization for these reactions. However, the binding of 4-methylumbelliferyl-alpha-D-galactose displays relatively favourable entropic contributions, indicating the existence of a non-polar site adjacent to the galactose-binding subsite. From the increments in the enthalpies for the binding of lactose, N-acetyl-lactosamine and thiodigalactoside relative to methyl-beta-galactose, the contribution of glucose binding in the subsite adjacent to that for galactose shows that glucose makes a major contribution to the stability of L-14 disaccharide complexes. Observation of enthalpy-entropy compensation for the recognition of saccharides such as lactose by L-14 and the absence of it for monosaccharides such as galactose, together with the lack of appreciable changes in the heat capacity (delta Cp), indicate that reorganization of water plays an important role in these reactions.


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