Studies on Tl (I), Pb (II) and Bi (III) complexes

164

15. Neil, Burford; Journal of Inorganic Biochemistry, 99, 1992-1997

(2005)

2.1: Literature Survey

H. Ellison and A.E. Maetell1 determined the equilibrium measurements of the

interactions of the polyphosphate anion with Mg(ll), Ca(ll), Sr(ll), Ba(ll),

Mn(ll), Co(ll), Ni(ll), Cu(ll), Cd(ll) and Zn(ll) ions Potentiometrically and

data was interpreted in terms of equilibrium constants for the formation of a

chelate compound containing both a metal and a hydrogen ion together with

the normal chelating agent from which all dissociable hydrogen‟s are

displaced.

Joshi and Bhattacharya2 determined the formation constants of Cd(ll), Cu(ll),

Ni(ll), Zn(ll), Be(ll) and Ag(l) by using the Irving-Rossotti titration method.

They reported that above mentioned complexes are more stable than the

corresponding hydroxyacid complexes, indicating there by a general

preference of these metal ions for coordination with nitrogen in comparision

to oxygen.

Von Euler3, in addition to Potentiometric method also used the solubility

measurements to determine overall stability constants of complexes of Ag (l)

with ammonia and several amines. He also studied ammonia and pyridine

complexes of zinc, cadmium & nickel.

Albert4

determined the stability constant of the complexes of divalent metal

ions of Mg, Mn, Fe, Co, Ni, Cu and Zn with serine, -alanine, phenylalanine

and methionine, using Bjerrum‟s method. The following order of stability of

complex formation amongst the metal ions was found:

Mg(ll) Mn(ll) Fe(ll) Co(ll) Zn(ll) Ni(ll) Cu(ll).

Studies on Tl (I), Pb (II) and Bi (III) complexes

165

Ahmed et al.5-6

have conducted a detailed study of the amino acids complexes

of certain metals in their unusual oxidation states by using pH-metric and

Potentiometric methods. Stability constants were calculated by Bjerrum‟s

method. They found that there seems to be no definite relationship between

the nature of an amino acid and the stability constant of its resulting complex.

Barrio et al.7 determined the stability constants of Zn(ll) and Pb(ll) complexes

with several amino acids by Potentiometric method. This method gives not

only the apparent stability constants of ML type complex but also the acid

constants of MLHx type complex. A hanging drop Pb or Zn amalgam

electrode was used as the indicator electrode of pPb and pZn respectively.

Rey and Co-worker8 investigated the complexation equilibrium of L-Serine

and L-Leucine with Ca(ll), Mg(ll), Co(ll), Ni(ll), Cu(ll), Zn(ll), Cd(ll) and

Pb(ll) at 25oC, I=0.1M KNO3 in various ethanol-water media. The

equilibrium constants of the complexes formed were discussed in terms of the

acid-base characteristics of the amino acids and the properties of the cations

concered.

Ahmed Malik and Farooq9-13

have investigated systematically the chelating

behavior of a number of amino acids with various metal ions in unusual

oxidation states. The stability constants of the complexes were evaluated by

studying the formation curves obtained from pH-metric and Potentiometric

methods. No definite trend and correlation have been suggested as the

resulting complexes were not isolated and characterized.

Tombeax et al.14

carried out the Potentiometric study of Ag(l) complexes of

sulphur containing amino acids in aqueous phase by simultaneous pH and pM

measurements at 25oC and 0.5 M KNO3. Complexes, in the acid medium, are

formed only through the thioether group and the carboxylate group is not

involved. In alkaline medium, both the thioether and amino groups are bound

in the tetrahedral chelates.

Studies on Tl (I), Pb (II) and Bi (III) complexes

166

Perrin15

calculated the stability constants of divalent and trivalent-Iron

complexes with 20 amino acids by Potentiometric titration method. Molar

electrode potentials for Fe3+

/Fe2+

amino acids complexes show a linear

relationship with logarithm of dissociation constants of amino acids, as

computed from these result.

Clarke and Martell16

studied the Chelate systems resulting from the

interactions of Ca(ll), Mg(ll), Mn(ll), Co(ll), Ni(ll), Cu(ll) and Zn(ll) with

Ornithine, Citruline and arginine and reported the formation constants of

chelates containing 1:1 and 1:2 molar ratios of metal ion to mono-protonated

ligands. The stability order is:

Cu(ll) > Ni(ll) > Co(ll) > Mn(ll) > Ca(ll) > Mg(ll).

Maley and Mellor17

reported the stability constants for glycine, alanine, valine

and leucine complexes of copper, zinc, cobalt and manganese. However the

elaborate studies on the avidity of amino acids with trace metal ions was

conducted by Albert18

, wherein he computed the overall stability constant

(Ks) for the complex formation between amino acids having only two ionizing

groups like glycine, L-proline, DL-serine, DL-methionine, DL-tryptophan,

DL-phenylalanine, DL-norleucine, DL-valine, L-asparagine, β-alanine and

taurine with metal ions such as Cu2+

, Ni2+

, Zn2+

, Co2+

, Cd2+

, Fe2+

, Mn2+

, Mg2+

and Fe2+

.

Perkins19

determined the stability constants by using Potentiometric method in

which ratio of amino acid to metal was 2:1 for bivalent and 1:1 for univalent

metals. Group ll metal ions form complexes with very low stability constants

as compared to group 12 metals which form complexes with very high

stability constants. The order of stability was found to be Hg(ll) > Be(ll) >

Zn(ll) > Cd(ll). Perkin also investigated the effect of amino acids structure on

the stability of complexes formed with metals of group lll.

Studies on Tl (I), Pb (II) and Bi (III) complexes

167

Muenz20

determined the stability constants of the 1:1 and 2:1 complexes of

EDTA with Pb(ll), Mg(ll), Cd(ll), Cu(ll) and La(lll) by calculating the free

energies of complex formation by a method based on a electrostatic model

taking into account the covalent interactions. The results agreed well with

known experimental data. The decrease in the stability with successive ligand

addition and the chelate effects are only due to the action of repulsive forces

and excess free energy changes.

Berezina and co-workers21

reported the stability constants and thermodynamic

parameters of complex formation for MA+ and MA2 complexes were M

stands for Mn (ll) and A stands for serine, methionine, norvaline, tryptophan,

phenyl-β-alanine and α-alanine. The relative stabilities of the complexes were

discussed. The 1:2 complexes were formed only in the presence of the large

excess of amino acids in the solution.

Rangaraj and Ramanujan22

determined the stability constants of Uranyl

complexes with glycylglycine, DL-α-alanine, DL-valine, L-asparagine, α-

amino-butyric acid and DL-β-phenylalanine using pH titrations at 310C, 0.1M

(NaClO4) ionic strength and pH 1.7 to 3.5. Ionization constants were

determined for the ligands under the same experimental conditions; 1:1

complexes were formed in all the cases.

T. Kiss and co-workers

23 studied the stability constants of the mixed ligand

complexes of L-dopa, L-tyrosine,L-phenylalanine and dopamine with copper

(ll) and nickel (ll) ions and 2, 2‟-bipyridyl and 1,10-phenanthroline pH-

metrically at 250C and an ionic strength of 0.2 mol/dm

3 (KCl) . Spectral

studies were made to establish the binding mode of the ambidentate L-dopa in

the ternary complexes. In contrast with the aromatic (N,N) donar atoms, the

(O, O) binding mode of L-dopa is particularly favoured in its ternary systems

with copper (ll) and nickel (ll). Thus, even at physiological pH there is a very

considerable formation of (O, O)-bound mixed ligand complexes containing a

free amino acid side-chain. Numerous binary transition metal-L-dopa

Studies on Tl (I), Pb (II) and Bi (III) complexes

168

complexes and the ternary complexes formed with various ligands have been

evaluated from a coordination chemistry aspect, with regard to the possibility

of their therapeutic application in the treatment of Parkinson disease.

A. Corsini and E. J. Billo24

studied the stability of metal chelates of the rigid

ligands: 4-amino-5-hydroxyacridine and 4, 5-dihydroxyacridine and

compared results with existing data for several 2-substituted 8-

hydroxyquinoline. They have explained stability effects in terms of ring strain

and substituent steric hindrance.

The equilibria involved in the association of Cd2+

, Zn2+

and Pb2+

with

glycylglycine have been investigated polarographically (25oC) by K. Nag et

al25

. Studies have been made at pH < 4 (where C-terminal end of the glycine

residue take place) and at pH > 7 (where both the N-terminal amino group and

the carbonyl group of the peptide linkage occurs). The nature of binding was

found to depend on solution pH, in the lower range of pH, comparatively

weaker (1:1) complexes were report with Cd2+

and Pb2+

ions (that of Zn2+

could not be detected due to the overlapping hydrogen wave) whereas in the

higher range, more stable complexes (both 1:1 and 1:2) were formed for all

the metal ions. Stepwise formation constants were determined by DeFord and

Hume‟s method.

Flood and Loris26

have reported the equilibrium constant of glycine with

copper, nickel, cobalt, zinc, cadmium and mercury. The order of stability

among various metal complexes has been found to be: Hg(ll) > Cu(ll) > Ni(ll)

> Zn(ll) > Co(ll) > Cd(ll).

Karezynski and co-workers27

have determined stability constants of Cu(ll)

complexes with some amino acids and peptides by Bjerrum‟s method.

Computed values have been reported.

Masood and co-workers28

have investigated the complexing behavior of

Co(ll), Ni(ll), and Cu(ll) with S-containing amino acids by pH-metric

Studies on Tl (I), Pb (II) and Bi (III) complexes

169

technique in the temperature range of (25-40)0C. The thermodynamic

parameters have been evaluated and the effect of the transition metal ions on

the mode of ionization of the ligands is discussed.

Kabiruddin and Zubaida29

have used polarographic technique to study the

complexing behavior of Cd(ll) with some amino acids as the primary ligand

and 2, 2-bipyridyl as the secondary ligand. Dissociation constants of the

amino acids have been calculated and the stability constants of binary and

ternary complexes have been determined.

Nair and co-workers30

have determined the stability constants of

heterobinuclear complexes, formed in aqueous solution with the biologically

important ligands viz, L-dopa, dopamine and L-Histidine by Cu(ll)-Ni(ll),

Cu(ll)-Zn(ll) and Ni(ll)-Zn(ll) and L-Cysteine and D-pencillamine with Ni(ll)-

Zn(ll) by computation of pH titration data. A qualitative attempt has been

made on the comparison of the log β-values, to study the Irving-William‟s

order of stability. The higher stability of mixed metal complexes over the

mixed ligand system is also discussed.

Reddy and co-workers31

have studied the interaction of Zinc-cysteine-

histidine and related systems which act as good models for the Zinc centre in

TF lll A (Zn-Cysteine protein) and the stability data reported suggest S,N

coordination for Zn. These results further indicate that irrespective of slight

variation in the secondary ligands, the stability remains the same when similar

donor atoms are involved in metal bonding.

James D. Carr and D. G. Swartzfager32

studied the interactions of the alkali

metal ions: lithium. Sodium, potassium, and cesium with the dextro and meso

isomers of the ligands 2,3-diaminobutane-N,N,N‟,N‟ tetraacetic acid over an

extended pH range (1.5-13.5). The log KML, values of the 1:1 complexes with

the dextro isomer was reported as 5.25, 3.93, and 1.56 for lithum, sodium and

potassium respectively. For the meso isomer, the log KML values for lithum

and sodium were reported as 2.60 and 0.48 respectively. The values of the

Studies on Tl (I), Pb (II) and Bi (III) complexes

170

stability constants were shown to be directly related to the proton affinities of

the ligands used.

Sergeev and Korshunov33

determined the stability constants of uranium (lV)

with various amino acids spectrophotometrically. The spectra consist of two

individual peaks corresponding to U (lV) H2O and equimolar complexes of

corresponding lanthanides and actinides complexes. A linear dependence was

observed between stability constants of the complexes and the ionization

constants corresponding to the amino acids used.

Tovstopyat and co-workers34

determined the ionization constants of alanine,

norvaline, norleucine, aspartic acid and the stability constants of their

complexes with Cu(ll), Zn(ll), Ni(ll) and Co(ll) at 0oC, 10

oC,20

oC and 25

oC.

The complexometric investigation was carried out potentiometrically. A

linear dependence was established between the stability constants of the metal

complexes, the corresponding acids and the temperature. The stability

constants in case of metal ions can be arranged in the order: Cu(ll) > Zn(ll) >

Ni(ll) > Co(ll). The stability of the complexes decrease with elongation of the

carbon chain of the amino acids and increase with their basicity. Ligands

protonation and Ni(ll) complex stability were determined pH-metrically at

25oC in 1M NaCl for 3-amino propionic acid, 3-amino butyric acid and 4-

amino butyric acid. Complex stability decrease as the number of CH2 group

between COOH and NH2 group increases.

G. S. Malik and co-workers35

reported the formation of mixed ligand

complexes of Ni(ll), Zn(ll), and Cd(ll) with 1,10-phenanthroline or 2,2‟-

bipyridyl in presence of Histidine. A study has been conducted pH-metrically.

The Stepwise formation of 1:1:1 mixed ligand complexes have been inferred

from the Potentiometric titration curves. The formation constants of the

resulting mixed ligand complexes have been calculated at 30oC (µ=0.1KNO3)

and the values have been found to be higher than the formation constant of

Studies on Tl (I), Pb (II) and Bi (III) complexes

171

1:2 and lower than those of 1:1 metal-His complexes. The order of stability in

terms of metal ions follows the order, Ni(ll) > Zn(ll) > Cd(ll).

Khyat and co-worker36

determined the stability constants for Pb(ll) complexes

of glycine, serine, aspartic acid and some peptides using electromeric method

in aqueous solution (25oC, 1.0 M NaClO4). The results are in accordance with

the tendency of Pb (ll) to form tetrahedral complexes rather than octahedral

ones.

Patil and Gurav37

studied polarographically Pb(ll) complexes of aminoacids (

asparagines, phenylalanine and tryptophan). The reducation of Pb2+

in

aminoacids at the DME was reversible and diffusion controlled. Lead forms

three complex species with asparagines and two complex species with

phenylalanine and tryptophan. They have also investigated Cd(ll) –

phenylalanine complexes by polarographic studies at three different

temperatures. The stability of (1:1), (1:2) and (1:3) – (metal: ligands)

complexes were calculated. The thermodynamics of the coordination

complexes were calculated from the temperature dependence and the

dissociation constant of phenylalanine was determined by the method of

Irving and Rassoti.

J.P. Manners et al.38

studied the stability of a number of thallium(I) complexes

by using Spectrophotometric and titration methods. The shifts of proton and

phosphorus nuclear resonances of ligands on binding to thallium(I) are

described. From these data inferences are drawn as to the strength and mode of

binding of thallium(I) to different ligand atoms. The importance of this work

for the study of potassium activated biological systems is stressed.

Karl Wieghardt et al.39

studied the Complexes of thallium(I) and (III) with the

1,4,7-triazacyclononane (L) ligands. Kinetics and mechanism of the reduction

of [L2Tl(III)]3+

is reported. Crystal structure of (N,N',N"-trimethyl-1,4,7-

triazacyclononane)thallium(I) hexafluorophosphate is reported in this study.

Studies on Tl (I), Pb (II) and Bi (III) complexes

172

Sasan Sharifi40

reported the stability constants of the complexes of TI(I) and

Cd(II) ions with dipeptides of glycyl-L-phenylalanine and L-

phenylalanylglycine in aqueous solution at 25 ºC and 0.1 mol dm-3

ionic

medium using a combination of potentiometric and spectrophotometric

techniques. Sodium perchlorate was used to maintain the ionic strength. The

composition of the complexes formed was determined and it was shown that

thallium(I) and cadmium(II) forms two mononuclear 1:1 species with the

ligands, of the type [Tl(HL)]+, TlL, [Cd(HL)]

2+ and [CdL]

+ in the pH range of

study (1.5-10.5), where L represents a fully dissociated ligand.

García Bugarín M et al.41

reported formation constants for thallium(I)

complexes of DL-penicillamine (PenH2), N-acetyl-L-cysteine (AcyH2), and N-

acetyl-DL-penicillamine (ApeH2) in aqueous solution in 150 mmol dm-3 NaCl

medium at 370C by Potentiometric titrations using a glass electrode. Glycine

has been used as a model for simple amino acids. The experimental data may be

explained by the formation of the complexes T1(Pen)-, T1(Pen)H, T1(Acy)-,

and T1(Ape)- with logarithmic formation constants 3.60, 12.05, 2.27, and 2.45,

respectively. Analysis of the results obtained and comparison of complexing

ability of thallium(I) with that of dimethyl-thallium(III) seem to indicate that

thallium(I) toxicity does not directly stem from its interference with the

metabolism of sulphur-containing compounds.

Masoud Rafizadeh42

have reported synthesis, characterization and crystal

Structure of thallium (I) complex containing monodeprotonated 2,6-

Pyridinedicarboxylic acid. The reaction of an ethanolic solution of 2,6-

pyridinedicarboxylic acid (LH2) with TlNO3 in the presence of triethylamine

led to the coordination polymer [Tl(LH)]n. The complex was characterized by

elemental analysis, IR spectroscopy and single-crystal X-ray diffraction.

J. Karthikeyan et al.

43 studied a simple and selective complexometric method

for the determination of thallium in presence of other metal ions on the basis of

selective masking ability of ethanethiol towards thallium (III). Thallium present

Studies on Tl (I), Pb (II) and Bi (III) complexes

173

in a given sample solution is first complexed with a known excess of EDTA

and the surplus EDTA is titrated with standard zinc sulphate solution at pH 5-

6(hexamine) using xylenol orange as the indicator. A 0.3% aqueous solution of

ethanethiol is then added to displace EDTA from the Tl(III)-EDTA complex.

The released EDTA is titrated with standard zinc sulphate solution as before.

Reproducible and accurate results are obtained for 3.70 mg to 74.07 mg of

Tl(III) with relative error less than ± 0.44% and coefficient of variation not

more than 0.27%. The interference of various ions was studied and the method

was used for the analysis of thallium in its synthetic alloy mixtures and also in

complexes.

U. K. Misra44

studied thallium poisoning and its diverse manifestations and

found that there can be delay in diagnosis if clear history of poisoning is not

forthcoming. A 42 year old man presented on the third day of illness with

flaccid quadriparesis and paresthesia, which were confused with Guillain-Barré

syndrome. Because of associated loose motions, skin lesions, and liver and

kidney dysfunction arsenic poisoning was suspected. In the second week he

developed ophthalmoplegia, nystagmus, and neck tremor and later developed

alopecia, and then thallium poisoning was suspected. His serum thallium level

on the 18th day of illness was 40-980 μg/ml. When he was subjected to

haemodialysis, potassium supplementation, laxatives, and B complex

supplementation, he showed significant improvement after haemodialysis and

after three months he was able to walk with support. At six months of follow up

he became independent for activities of his daily living. Severe paresthesia,

ophthalmoplegia, cerebellar and extrapyramidal signs, and alopecia are highly

suggestive of thallium poisoning. Haemodialysis may be effective even in the

third week of poisoning.

Ouameur A Ahmed45

has reported that thallium (Tl) binds to the major and

minor grooves of B-DNA in the solid state. The aim of this study was to

examine the binding of Tl(I) cation with calf-thymus DNA in aqueous solution

Studies on Tl (I), Pb (II) and Bi (III) complexes

174

at physiological pH, using constant concentration of DNA (12.5 mM) and

varying concentrations of metal ions (0.5 to 20 mM). UV-visible and FTIR

spectroscopic methods were used to determine the cation binding site, the

binding constant and DNA structural variations in aqueous solution. Direct Tl

bindings to guanine and thymine were evident by major spectral changes of

DNA bases with overall binding constant of K = 1.40 x 10(4) M (-1) and little

perturbations of the backbone phosphate group. Both major and minor groove

bindings were observed with no alteration of the B-DNA conformation. At low

metal concentration (0.5 mM), the number of cations bound were 10 per 1000

nucleotides, while at higher cation concentration (10 mM), this increased to 30

cations per 1000 nucleotides.

Kemper and Bertram46

studied the ecotoxicological importance of TI(I) and

derived that its high acute toxicity on living organisms is comparable to that of

lead and mercury toxic heavy metals.

Tser-Sheng Lin47

used an ion-exchange separation technique followed by

analysis with atomic absorption spectroscopy to study the chemical forms and

distribution of thallium in Lakes Michigan, Huron, and Erie. The dominant

thallium forms found in water samples were analyzed by the oxidized Tl(III)

which comprised 68 ± 6% of the total dissolved thallium contrary to

thermodynamic prediction that Tl(I) is favored in natural waters. An overall

decline of thallium concentration from Lake Michigan to Lake Erie was

observed which may be related to rapid scavenging removal from the water

column.

Favari L.48

studied the capacity of thallium to substitute for K+ (potassium) in

activation of (Na+, K

+)-ATPase of liver plasma membranes of the rat and the

results indicate that T1+ can replace K

+ in the activation of the (Na

+, K

+)-

ATPase of liver plasma membranes. In the presence of Na+, similar activation is

obtained with T1+ concentrations only 1/10 of those of K+. In all other aspects,

the (Na+, K

+)- ATPases and (Na

+,T1

+)-ATPases were found to be identical.

Studies on Tl (I), Pb (II) and Bi (III) complexes

175

Cheam et al.49

have reported that thallium concentrations in the Great Lakes

waters are generally higher than those of cadmium and occasionally exceed the

levels in some contaminated area, by the human activities and urban

development. High concentrations of thallium recently found in lake trout from

the Great lakes suggest that the risk of thallium poisoning from fish

consumption may be higher than is generally recognized.

Tangfu Xiao et al.50

illustrate a real environment concern and draw attention to

the fact that natural processes can mobilize thallium, a highly toxic metal,

which may enter the food chain as a hidden health killer with severe health

impacts on local human population. Natural processes may be exacerbated by

human activities such as mining and farming and may cause enrichment of Tl in

the environment.

Yu-Tai-Tsai et al.51

reported that central nervous system is affected in acute

thallium intoxication. Neurologically the patients suffered from confusion,

disorientation and hallucination in the acute stage, followed by anxiety,

depression, and lack of attention and memory impairment in addition to

periphery neuropathy.

Pwi Pau52

studied a case of acute thallium poisioning in a 67-year old Chinese

woman with acute pain in the chest, abdomen and lower limbs. The diagnosis

was not made until alopecia developed. If detoxification therapy is not

commenced within 72 hours, the tissue-bound thallium may cause prolonged

neurological damage.

Bardwell DA et al.53

, crystallographically characterized the complexes of [TIL]

and [PbL2], where L-is the potentially tetradentate ligand bis[3-(2-pyridyl)-

pyrazolyl]dihydroborate containing two N,N'-bidentate chelating arms linked

by a-BH2-fragment. In [TIL] the Tl(I) is coordinated by one tetradentate

chelating ligand L-, whose four N donor atoms are approximately coplanar. The

Tl(I) ion lies similar at 1.4 Angstrom out of this plane, and the stereochemically

active lone pair is assumed to occupy the vacant axial site of the square

Studies on Tl (I), Pb (II) and Bi (III) complexes

176

pyramid. The Tl-N(pyridyl) bonds (2.96-3.17 Angstrom) are considerably

longer than the Tl-N(pyrazolyl) bonds (2.61-2.69 Angstrom). The molecules lie

in a stack along the Tl ... Tl axis. In [PbL2] there are seven Pb-N bonds in the

range 2.588-2.817 Angstrom, which are considered as 'normal' Pb-N

interactions, and one much longer interaction (3.055 Angstrom) to a pyridyl N

atom which, although rather remote, is still oriented towards the metal. The

metal ions therefore '7 + 1'-coordinate from two tetradentate chelating ligands.

V. V. Skopenko and co-workers54

isolated series of TI(I) oximate complexes

with 1, 10-phenanthroline and the coordination modes of ligands in these

complexes were investigated from IR spectra.

R. S. Saxena and co-workers55

studied polarographically the complexation of

thallium(I) by ethylthioglycolate (ETG). The reduction of Tl+ in

ethylthioglycolate solution has been found to be reversible and diffusion

controlled involving a one electron transfer process. Potential vs. concentration

data at 0·5M ionic strength are interpreted on the basis of the formation of three

complex species TIA, TIA2− and TlA3

2−. The logarithms of the stability

constants of these complexes are 1·74, 2·00 and 3·25 at 20°C and 1·70, 1·95 and

3·20 at 30°C, respectively. The values of ΔG, ΔH and ΔS at 30°C have also

been calculated.

E. Lada and co-workers56

studied the complexation of thallium(I) by 18-crown-

6, dibenzo-18-crown-6 and dicyclohexyl-18-crown-6 (cis-anti-cis isomer) in

methanol and N, N- dimethylformamide by Polarographic technique.

Deeb Marji and co-workers57

studied the complexation reactions between Ag+

and Tl+ ions with 15-crown-5 (15C5) and phenyl-aza-15-crown-5(PhA15C5)

Conductometrically in 90%acetonitrile-water and 50% acetonitrile - water

mixed solvents at temperatures of 293, 298, 303 and 308 K. The stability

constants of the resulting 1:1 complexes were determined, indicating that the

Tl+ complexes are more stable than the Ag

+ complexes. The enthalpy and

entropy of crown complexation reactions were determined from the temperature

Studies on Tl (I), Pb (II) and Bi (III) complexes

177

dependence of the complexation constants. The enthalpy and entropy changes

depend on solvent composition and the T∆S0 –∆H

0 plot shows a good linear

correlation, indicating the existence of entropy –enthalpy compensation in the

crown complexation reactions.

J. R. Hudman and co-workers58

investigated of some complexes of thallium (I)

and thallium (III) with nitrogen donor ligands. Some new vibrational

spectroscopic data are given for Tl (chelate)X3 where chelate = 2.2′bipyridyl;

1.10 phenanthroline or di-2-pyridylamine and X = Cl or Br. The new

complexes Tl (tripyam) X3 (tripyam = tri-2-pyridylamine, X = Cl or Br) are

reported together with a new series of compounds [Tl (chelate)X3 D.M.F.]

(chelate = as above or bidentate tri-2-pyridylamine, X = Cl or Br, DMF =

dimethyl-formamide). Chemical and spectroscopic reasoning lead to a

preference for a polymeric as opposed to a dimeric structure for [TI (chelate)

X3]. New data (1H n.m.r. and i.r.) are reported for [Tl (phen)2]Y (Y = NO3

− or

ClO4) and [Tl(bipy)2]ClO4. The stereochemical environment of the thallium (I)

cation is considered to be close to tetrahedral.

Ludolph et al.59

reported that human occupation of TI (I) may affect the nervous

system following inhalation. Thirty-six workers involved in cement production

for 5-44 years (mean of 22.9) exhibited paresthesia, numbness of toes and

fingers, the burning feet phenomenon and muscle cramps etc.

Davis et al.60

reported that cardiovascular damage in humans after ingestion of a

single estimated lethal dose of 54-110 mg thallium/kg, (thallium nitrate). There

was extensive damage of the myocardium with myofiber thinning,

accumulation of lipid droplets, myocardial necrosis and inflammatory reaction.

In human, acute ingestion of thallium sulfate caused gastroenteritis, diarrhea or

constipation; vomiting and abdominal pain was studied by Grunfeld and

Hinostroza61

. Ding-nan62

reported the gastrointestinal disturbances of thallium

in 189 cases due to thallium poisoning which occurred in China from 1960 to

1977.

Studies on Tl (I), Pb (II) and Bi (III) complexes

178

Khyat and co-worker63

reported the stability constants for Pb (ll) complexes of

glycine, serine, aspartic acid and some peptides by electrometric method in

aqueous solution at 25oC, 1.0 M NaClO4. The results are in accordance with the

tendency of Pb(ll) to be tetrahedral rather than octahedral.

Pb(ll) complexes of aminoacids: asparagines, phenylalanine and tryptophan

were studied polarographically by Patil and Gurav64

. The reducation of Pb2+

in

aminoacids at the DME was reversible and diffusion controlled. Lead forms

three complex species with asparagines and two complex species with

phenylalanine and tryptophan each. They have also investigated Cd(ll) –

phenylalanine complexes by polarographic studies at three different

temperatures. The stability of (1:1), (1:2) and (1:3) – (metal: ligands)

complexes were calculated. The thermodynamics of the coordination

complexes were calculated from the temperature dependence and the

dissociation constant of phenylalanine by Irving and Rassoti method.

Barrio et al.65

reported the stability constants of Pb(ll) and Zn(ll) complexes

with several amino acids by Potentiometric method. This method gives not only

the apparent stability constants of ML type complex but also the acid constants

of MLHx type complex. A hanging drop Zn or Pb amalgam electrode was used

as the indicator electrode of pZn and pPb respectively.

Muenz et al.66

reported the stability constants of the EDTA 1:1 and 2:1

complexes of Pb(ll), Mg(ll), Cd(ll), Cu(ll) and La(lll) by calculating the free

energies of complex formation by a method based on a electrostatic model

taking into account the covalent interactions. The results agreed well with

known experimental data. The decrease in the stability with successive ligand

addition and the chelate effects are only due to the action of repulsive forces

and free excess energy changes.

Gina Branica and co-workers67

studied the interactions between Pb(II) and

ascorbic acid by polarography and voltammetry. The following techniques were

applied: sampled polarography, differential pulse anodic stripping voltammetry,

Studies on Tl (I), Pb (II) and Bi (III) complexes

179

and square-wave voltammetry. Measurements were performed in perchlorate

aqueous solutions under physiological ionic strength (0.15 mol dm–3

).

Electrochemical reaction of the lead(II) ascorbate complex was studied in

various electrolyte compositions to find the optimal measurement conditions for

determination of the corresponding stability constants [Pb2+

] = 4 x 10–7

mol dm–

3, pH = 5.5; total concentration of ascorbic acid between 10–5 and 10–1 mol

dm–3

). Determination of stability constants of labile lead (II) ascorbate

complexes was based on the DeFord-Hume methodology, and they were

calculated from the dependence of the shift of Pb (II) peak potential on the free

ascorbate ion concentration. The computed stability constants were: log 1 =

9.3 and log β2 = 18.0.

Lin-Fu68

reported on ten cases of lead colic in children. It took twelve years

before a lead paint in the children‟s houses was identified as the source of the

poison and it was also reported that plumbism and that child were at particular

risk through the route from houses dust, to hand, to mouth.

Waldemar Grzybowski69

studied the complexation of cadmium and lead with

humic substances by differential pulse anodic stripping voltammetry and a

standard addition technique. The titration was done for humic substances of

different molecular weight that had been isolated from seawater and

subsequently redissolved in organic-free seawater. The different molecular

weight fractions were obtained by ultrafiltration using 1000 D (Dalton), 5000 D

and 10,000 D pore size filters. Comparison of calculated stability constants

suggests that the strengths of lead complexes in the analysed fractions are

similar and that of cadmium is complexed by the fraction smaller than 1000 D.

Neil Burford and co-workers70

studied Electrospray ionization mass spectra of

lead(II) nitrate–amino acid mixtures enable unequivocal identification of lead

complexes for each of the essential amino acids and a valine complex is

reported as the first crystallographically characterized lead–amino acid

complex.

Studies on Tl (I), Pb (II) and Bi (III) complexes

180

B. B. Tewari71

studied the quantitative indication of a complex formation comes

from the estimation of the stability or formation constants characterizing the

equilibria corresponding to the successive addition of ligands. The binary

equilibria of Pb(II)–methylcysteine and also mixed equilibria Pb(II)–

methylcysteine–penicillamine were studied by paper electrophoretic technique.

Manuel A. V72

studied the molar heat capacity and the standard molar

enthalpies of formation of the crystalline of bis(glycinate)lead(II), Pb(gly)2;

bis(DL-alaninate)lead(II), Pb(DL-ala)2; bis(DL-valinate)lead(II), Pb(DL-val)2;

bis(DL-valinate)cadmium(II), Cd(DL-val)2 and bis(DL-valinate)zinc(II),

Zn(DL-val)2, were determined, at T = 298.15 K, by differential scanning

calorimetry method.

Glen G. Briand and co-workers73

isolated the cysteinate and thiolactate

complexes of Bi(lll) by using the technique of electrospray ionization mass

spectrometry. The thiophilic nature of bismuth implicates sulfur centres as

likely site for interaction. This feature has been exploited to identify, isolate and

characterized complexes of bismuth with thiolate-carboxylate bifunctional

ligands.

Hongzhe Sun et al.74-75

reported the interaction of Bismuth complexes with

Metallothionein (ll) by UV titration and ICP (Induced couple plasma)-AAS

method. They also studied the role of Bi(lll) compounds in medicine, its

biological relevance and pharmacology as bismuth compounds are most

commonly used for treating gastrointestinal disorders.

Neil Burford et al.76

characterized the complexes of glutathione with As(lll),

Sb(lll), Cd(ll), Hg(ll), Tl(l), Pb(ll) or Bi(lll) by electrospray ionization mass

spectrometry in the gas phase.

Jeffrey R. Eveland77

prepared the bismuth(III) chloride-ether complexes,

BiCl3·diglyme (I), BiCl3·diethylcarbitol (II) and BiCl3·3THF (III). Compounds I

and II form dimers in the solid state and exhibit distorted pentagonal

Studies on Tl (I), Pb (II) and Bi (III) complexes

181

bipyramidal coordination around the bismuth centers, while complex III is

monomeric in the crystal lattice and shows approximate octahedral coordination

for bismuth.

D. E. Mahony78

reported that bismuth subsalicylate (BSS), the active ingredient

of Pepto-Bismol, has been used for many years to treat various disorders of the

gastrointestinal tract. By using mass spectrometry and the agar dilution method,

he determined that insoluble BSS interacts with certain dietary components and

organic substrates to produce water-soluble products with activity against

Clostridium difficile.

N. N. Golovnev et al.79-80

reported the stability constants of the bismuth(III),

indium(III), lead(II), and cadmium(II) monocomplexes with selenourea and

thiourea by using spectrophotometric method at the ionic strength 1 (0.5 mol/L

HClO4 + NaClO4) or 2 (1 mol/L HClO4 + NaClO4) and 276 and 298 K. For all

metals, the stability constants (β1) of the complexes with selenourea were

higher than the complexes with thiourea and changed in the series Bi3+

> Cd2+

≈

In3+

> Pb2+

. They also reported the stability constants of monocomplexes of

cysteine (H2Cys) and thiosemicarbazide with bismuth(III) at 288, 313 and 333

K in 0.5 M HClO4 at an ionic strength of 2(NaClO4) were determined by

spectrophotometry.

R. R. Jia and co-workers81

isolated the complexes of the aspartic acid with the

bismuth triiodide by a direct solid–solid reaction at room temperature. The

formula of the complex is MI3[OOCCH2CH(NH2)CO]2.5.2.5H2O (M=Sb, Bi).

The complex may be a dimer with bridge structure.

Stoltenberg et al.82 studied that bismuth may be transported retrogradely in both

sensory and motor axons if their ends are exposed to bismuth ions and gets

accumulated in neurons and glia cells in the brain regions.

Rao et al.83

and Sun et al.84

noted that trivalent bismuth nitrate and colloidal

bismuth subcitrate display protein-specific binding. The workers investigated

Studies on Tl (I), Pb (II) and Bi (III) complexes

182

the distribution of bismuth in the body. Bismuth is distributed via blood to the

spleen, liver, brain, heart, skeletal muscle, and, in particular, the kidney,

resulting in the manifestation of bismuth toxicity in vivo85

.

Having noted from the literature survey that inspite of high avidity of Tl(I),

Pb(ll) and Bi(lll) for bioligands, no appreciable research work has been done on

interaction of these metal ions with the bioligands, we intended to investigate

and report the interacting mode of Tl(I), Pb(ll) and Bi(lll) metal ions with some

biologically important ligands by employing Potentiometric and

Conductometric techniques. Besides that, isolation and characterization of

complexes of the concerned metal ions with some sulfur containing bioligands

has been reported. The aim of the present investigation was to study the

complexing behavior of the bioligands with the selected heavy metal ions

namely, TI(I), Pb(II) and Bi(III) to quantify the strength of bonding in terms of

both the stepwise as well as overall formation constants of the resulting

complexes with chelating agent, using Bjerrum‟s method86

as modified by

Albert in aqueous phase87

and ∆G0

value were calculated using the relation

∆Go= -2.303 RT log Ks at 25

oC.

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