ELECTROANALYTICAL

t33EMlSmY AND INTERFACIAL ELEClROCHEMiSTRY Elsevier Sequoia_ S.A., Laus+me - hinted in The Netherlands

SHORT

COMMUNICATIONS

Studies on the composition some aminoacids

and stability of uranyl, vanadyl and titanous complexes

with

A number of papers on the metal complexes of amino acidsIb have appeared in the literature in recent years. These studies are mainly concerned with the determination of the stability constant of a complex by various electrometric methods, viz. potentiometry, pH-metry, polarography, etc. References to studies on the complexes of Cu, Zn, Fe, Ni, Co, Mn, Cd and other transition metals are available but no attempt has yet been made to investigate possible complex formation between VW+, uo$+ and Ti3+ ions with amino acids. The present communication deals with the behaviour of these ions towards some amino acids. Formation of 1 : 1 complexes has been indicated by conductometric titrations, and the stability constants of the complexes have been computed from the results of pH-metric titrations. acids such as glycine, fi-alanine, DL-or-alanine, L-asparagine, DL-serine, L-leucine, DL-valine and L-proline (B.D.H. biologically pure) were used for the experiments, and their solutions (0.01 M) were prepared in doubly-distilled water. Uranyl sulphate (B.D.H. AnalaR), and vanadyl sulphate (B.D.H.) were employed and solutions of these salts were analysed gravimetrically as the metal oxides5=6. An aqueous solution of titanium(W) chloride was prepared by dissolving crystals of TiCl, - 6 H,O in air-free doubly-distilled water, and the solution standardized. Fresh solutions were always prepared before use and kept covered with a layer of kerosene oil or toluene throughout the investigations to avoid oxidation. Carbonate-free KOH solution was used for pH-metric titrations. It was stored in a Pyrex- bottle fitted with a KOH tube for_ protection against atmospheric CO,. The solution was standardized by titrating with standard oxalic acid solution, and the strength was checked periodically before carrying out pH-metric titrations. The conductometric titrations were performed using a Philips conductivity bridge model PR 9500/90 and a dip type conductivity cell (cell constant 1.48). The pH-metric titrations were carried out with a direct reading EIL pH-meter model 23A using glass and calomel electrodes. All the titrations were carried out in a specially designed.celI, with p$.ovision for adding metal salt solutions from a burette, to a &-red oxygen-free system_
.Results and .discussion The, composition of the vanadyl, uranyl and titanous complexes with variqus Experimental Amino

acids was determined conductotietrically, The conductom&ric titrations were -:.reGersible_In all ca+a ratio of. 1 : 1 .(m_etaI : amino acid) was established_ Typical 1. curvek &..given in Fig 1. The pH-metric.titrations were performed triplicate for e&h akininn &id-.The titrations we& car&d out in the order : (li) apino acid (0.01 M), . - _ :, . .:_~. , _
amind

in.

-. .::3: &r&&~~~&eni.,24 ~. I . .Y_.: ..

_/

. _(1970) 46+4&j ,: .. . _ ._

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COMMUNICATIONS

465

3
71361211 -

3l2loo-

Volume

of

metnl

salt/ml

Fig. 1. Reverse conductometric titrations: (I) M/15 TiCI, added to 40 ml of M/300 DL-serine, (2) M/12 UO$O, added to 40 ml of M/240 DL-a-alanine, (3) M/15 VOSO, added to 40 ml of M/300 DL-valine.

0.8 0.6
0.4

-3.0

-4.0

--6.0

Curve Curve

A.C
B-

Fig. 2 Formation curves : (A) DL-valineyVOSO, serine-TiCIJ complex.

complex, (B) DL-a-alanine-U02S04

complex,

J. Electroanal. Chem., 24 (1970)

-.

.-

466.

-.

SHORT

COMMUNI

CA-l-IONS

8PH 7-

*7-

6543L 4 3
0

6-

For an-ves F&r cum

A: B;CA, B; C

f%rcurms~~C

Fig.-3. pH-metric titrations: (A_ 4 C) DL-serine-TiC13. (A, B: C) DL-a-alanine-UO,SO,

DL-vztlhe-VOS04. TABLE
BY TWO

(A, .B, C)

1
LOG (&/tllOl 1-2) FOR VANADYL, URANYL AND TITANOUS AMINO ACIDS COMPLEXES OBTAINED

VALUES OF

METHODS

Amino

ads

Van&y1 s&hate Theoretical Graphical 6.90 9.80 8.70 xx 9.10 IO.30 7.50 8.65

Uranyi suiphate Theorerical 6.88 9.92 9.00 8.62 8.61 10.46 6.86 8.59 Graphical 6.85 9.90 9.00 8.65 8.60 10.45 6.90 8.60

Titanous chloride Theoreticai 7-25 9.72 8.53 8.52 8.55 10.08 7.60 8.12 Graphical
720 9.70 -

L-Asparagine j3-Alanine DL-a-Alanine Giycine L-Leucine L-Proline QL-Serine.

DL-Valine

6.95 9.77 8.75 xx 9.08 10.33 7.54 8.65

8.50 8.50 8.50 10.05 7.60 8.20

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CbmCATIONS

467, _

acid bound by. one atom of.the metal ion, vLere calculated &om the v&es of -log [SC] obtain&d by pJott_ing fi vs. -log [SC] (Fig. 2). [SC] is the concetitratjdn j., of tie free aniino~ ticid. The ~vaIues_oflog Kti for various amino acids evaluated fibm the formation curves, and those calculated are given b Tgble 1: The values of the overall stability constants log K, obtained froni the formation cuties (Fig. 2), are iri good agreement with those calculat&d. Uranyl suiphate, vanadyl suiphate and titanous ,chlo+de.form 1 : 1 complexes with various %rnino acids (L-asparagine, j?-al-e, DL-a-alanine, glycine, L-ieucine, L-proline, L-serine and DL-valine). In the vanadyl and titanous complexes the values. of log K, vary from. L-aspziragine (6.95, 7.25) to L-proline (10.33,. lO.CjS),whereas iti uranyl complexes the variation is from DL-serine (6.86) to L-proline (10.46). There does not seem to.be any correlation between the nature of the aminoacids and the K, values although, with a few exceptions, the latter decreases with increase in chain length of carbon atoms. The real nature of bonding in these complexes is a matter of speculation as no complex could be isolated in a sufficiently pure form.
amirio

due to the Vice Chancellor,A.M.U.Aligarh Fellowschip to one of us (0-F.).

Department of Chemistry, Aiigarh Muslim University, Aiigarh (India)

Acknowledgement Thanks are

for granting aResearch Omar Farooq A. U. Malik N. Ahmtid* S. M. F. Rahman

2599.

1 D. J. PERKIN, 2 J. B. GILBERT, 3 A. A. KHAN 4 A. ALBERT,

Biochem. f., 51 (1952) 487. 0. CLYDE AND J. 2. HEARON, J. Am. Chem. Sot.. 77 (1955) AND W. U. MALIK, J. Indian Chem. Sot., 40 (1963) 565.
AND

Biochem.

5 A. C.

GUMMING

J., 47 (1950) 53 i. S. A_ KAY, Quantitatioe

Chemical

Analysis, Analysis, Vol. VII,

Oliver and Boyd, London,

Vol. 1, D- van Nostrand,

IX edn., York,

1945, p. 367. 6 N. H. FURMAN (Ed.). Standard Methods VI edn., 1962, pm 1189. 7 J. W. MELLOR, Inorganic and Theoretical (Ed.), Standard Methods 8 N. H. FIJIAN VI edn., 1962, p_ 984.

of Chemical Chemistry, of Chemical

New

Analysis,

Longmans,. London, 1963, p. 74. Vol. I, _D. van Nostr~d, New York,

Received July 3rd, 1969

* Present addiess : Department

of Cheplistry, Louisiana State University, Baton Rou-ge, La. 70803, &J:+%. __