Introduction

Involvement of sulphur chemistry in metabolic pathways Metal ion catalysis in living systems Participation of nanoparticles coordination of redox site of ligands, through space : Synergetic effect .Proposed work Oxidation of bioactive molecules such as Cysteine, Mercaptoethylamine,GSH etc. -Catalysis : Micronutrients such as Cu(II), Zn(II) etc. - Participation of nanoparticles

2-

Nature of oxident
Methylene blue [phenothiazine 5 ium, 3,7 bis (dimethylamino) chloride,MB]

Applications: Memory facilitation in dementia. Photocatalytic degradation on nanocomposites Photocatalytic reduct by TiO2 nanoclusters.
Degradation of DNA.

Oxidation of cystiene hydrochloride and 2-Mer captoethylamine hydrochloride by MB catalysed by Cu(II) in presence of Zn(II) in acidic medium.

Stoichiometry RSH : MB =2:1

Table I Synergetic Effect of Zn(II) on the rate [ZnII]X 105 M Extent of reaction k1/2 X 106 in about 45 min.(%) M1/2s-1 (A) 0.4 Nil 87 3.8 0.4 1.0 89 4.6 [Cys]= 3.0X10-2M, [MB]= 2.4X10-5 M, [HCl]= 5.0X10-3 M [KCl]= 2.0X10-6M, ethanol = 4%(v/v) ,Temp= 350c =5.018X10-3 M (B) 2.0 Nil 80 1.6 2.0 5.0 83 2.0 [2-ME]= 1.8X10-2M, [MB] =2.0X10-5 M], [H2SO4] = 2.5X10-5 M Temp= 350c, =7.508X10-2 M [CuII]X105 M

Table II Rate data at different [substrate]

[Cys] x 102 M
1.0 2.0 3.0 4.0 5.0 6.0

k1/2 x 106
M1/2 S-1 2.0 1.0 3.4

3.2 4.6 5.1 6.8 8.1

[2-ME] x 102 k0x 109 k1/2 x 106 M M-1 S-1 1.25 3.8 1.50 1.8
1.80 2.20 2.60 3.00 2.0 -

k1 x 104 M1/2 S-1

-

S-1

4.7 4.6 5.0

[MB]= 2.4X 10-5 M; [HCl]= 5.0X 10-3 M [CuII]= 4.0X 10-6 M; [ZnII]= 1.0X 10-5 M [KCI]= 2.0X 10-6 M; Ethanol= 4% (v/v) Temp.= 35 C; = 5.06X 10-3M

[MB]= 2.0X 10-5 M; [H2SO4]= 2.5X 10-2 M; [CuII]= 2.0X 10-5 M; [ZnII]= 5.0X 10-5 M; Temp.= 35 C; = 7.528X 10-2 M;

Table III Rate data at different [H+]

[HCl] x 103 k1/2 x 106 M M1/2 S-1 2.5 5.0 10.0 15.0 4.7 4.7 5.1 5.4 [H2SO4] x 102

M
1.7 2.0 2.5 3.3 23.3 27.6 30.1

k1/2 x 106 M1/2 S-1

24.7

20.0
30.0

5.8
6.7

6.7
9.1

8.1
6.7

[Cys]= 3.0X 10-2 M; [MB]= 2.4 X 10-5 M [Cu II]= 4.0X 10-6 M; [Zn II]= 1.0X 10-5 M [KCI]= 2.0X 10-6 M; Ethanol= 4% (v/v) Temp.= 35 C; = 0.03 M

[2-ME]= 1.8X 10-2 M; [MB]= 2.0 x 10-5 M [Cu II]= 2.0X 10-5 M; [Zn II]= 5.0X 10-5 M; Temp.= 35 C; = 0.2803 M

Table IV Rate data at different [CuSO4]

[Cu II] x 102 M M1/2 S-1 1.0 2.0 4.0 6.0 8.0 10.0 2.1 3.4 4.6 5.1 6.9 7.8 k1/2 x 106 [Cu II] x 105 k 0x 109 k1/2 x 106 k1 x 104 M M-1 S-1 M1/2 S-1 S-1 1.0 1.67 2.00 3.00 4.00 6.00 3.6 1.7 2.0 2.1 1.7 4.3 [HCl]= 4.8 -

8.00 [Cys]= 3.0 x 10-2 M,[MB]= 2.4 x 10-5 M [2-ME]= 1.8X 10-2 M; 5.0X 10-3 M; [Zn II]= 1.0X 10-5 M [MB]= 2.0 x 10-5 M; [H2SO4]= 2.5X 10 -2M; [KCI]= 2.0X 10-6 M; Ethanol= 4% (v/v) [Zn II] = 5.0X 10-5 M; Temp. = 35 C; = 0.03M Temp. = 35 c, =7.580X 10-2 M;

Other Kinetic features

Effect of addition of Zn(II): Rate increases and attains a limiting value Effect of addition of the product: Nil Effect of variation of : Erratic behaviour Effect of variation of D: rate increases on increasing D Activation Parameters: Cys 2-ME H* 42.6kJ 38.3kJ S* -210.0J -231.4J G* 106.2 kJ 70.1kJ

TEM

TEM images of reaction system in presence of Cu (II).

TEM images of reaction system in presence of Cu(II) and Zn(II).

Electron diffraction

Electron diffraction pattern of reaction system in presence of Cu(II).

Electron diffraction pattern of reaction system in presence of Cu (II) and Zn (II).

Table I Synergetic Effect of Zn(II) on the rate

[CuII]X105 M (A)

0.4 Nil 87 0.4 1.0 89 [Cys]= 3.0X10-2M, [MB]= 2.4X10-5 M, [HCl]= 5.0X10-3 M [KCl]= 2.0X10-6M, ethanol = 4%(v/v) ,Temp= 350c =5.018X10-3 M

[ZnII]X 105 M Extent of eaction k1/2 X 106 in about 45 min.(%) M1/2s-1

3.8 4.6

(B) 2.0

Nil 80 2.0 5.0 83 [2-ME]= 1.8X10-2M, [MB] =2.0X10-5 M], [H2SO4] = 2.5X10-5 M Temp= 350c, =7.508X10-2 M

1.6 2.0

blank

Rate expression

Table V Rate data obtained for the oxidation of cysteine, 2-Me and TSA by MB in presence of Cu(II) and Zn(II) in acidic medium
Metal ion acting as catalyst * Cu(II) Zn(II) Cu(II)+ Zn(II) * Cu(II) Zn(II) Cu(II)+Zn(II) Substrate employed Cysteine Cysteine Cysteine 2-ME 2-ME 2-ME Rate constant k1/2=3.8 x 10-6 M-1/2s-1 No influence k1/2=4.6 x 10-6 M-1/2s-1 k1/2=1.6 x 10-6 M-1/2s-1 No influence k1/2=2.0 x 10-6 M-1/2s-1

Cu(II) Zn(II) Cu(II)+Zn(II)

TSA TSA TSA

k 3/2=3. 6 x 10-1 M-1/2s-1 No influence k3/2=2.4 x 10-1 M-1/2s-1

Oxidation of Mercaptosuccinic acid by MB catalyzed by Cu(II) in acidic medium Salient Features

(i) Stoichiometry: 2:1 (ii) Order in MB: 1/2 (iii) Order in TMA: 1/2 (iv) Effect of variation of [MB]o : Rate increases and attains a limiting value. (v) Effect of variation of : Rate decreases on adding KCl,NaCl No change on adding KNO3 (vi) Effect of variation of D: Rate decreases on decreasing D

 (vii) Effect of variation of [H+]: Nil, But at lower[H+] (ca.< 2.0 x 10-2M ); order in MB becomes zero. (viii) Effect of equilibration of Cu(II) with other ingredients : Rate increases on increasing thr time of equilibration (ix) Effect of addition of the product: Nil (x) temperature dependence: In temperature range 20o-30oC; Anti-Arrhenius behaviour Beyond 30oC ; No change in k1/2

Activation Parameters
H* S* G* -21.0kJmol-1 -419.5JK-1mol-1 108.1 kJmol-1