Biomimetics, Vol. 7, Pages 221: States of Aggregation and Phase Transformation Behavior of Metallosurfactant Complexes by Hexacyanoferrate(II): Thermodynamic and Kinetic Investigation of ETR in Ionic Liquids and Liposome Vesicles

Scheme 1. The structure of surfactant–cobalt(III) complexes.

Scheme 1. The structure of surfactant–cobalt(III) complexes.

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Scheme 2. Electron transfer reaction of surfactant complexes by ferrocyanide ions. LL = ip, dpq and dpqc; A = Dodecylamine.

Scheme 2. Electron transfer reaction of surfactant complexes by ferrocyanide ions. LL = ip, dpq and dpqc; A = Dodecylamine.

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Figure 1. Plot of k against DPPC for cis-[Co(ip)2(C12H25NH2)2](ClO4)3 under various temperatures; cis-[Co(ip)2(C12H25NH2)2](ClO4)3 = 4 × 10−4 mol dm−3, μ = 1.0 mol dm−3, [Fe(CN)6]4− = 0.01 mol dm−3.

Figure 1. Plot of k against DPPC for cis-[Co(ip)2(C12H25NH2)2](ClO4)3 under various temperatures; cis-[Co(ip)2(C12H25NH2)2](ClO4)3 = 4 × 10−4 mol dm−3, μ = 1.0 mol dm−3, [Fe(CN)6]4− = 0.01 mol dm−3.

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Scheme 3. DDPC-mediated ETR of surfactant–cobalt(III) complexes.

Scheme 3. DDPC-mediated ETR of surfactant–cobalt(III) complexes.

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Figure 2. Plot of k against [BMIM]Br for cis-[Co(ip)2(C12H25NH2)2](ClO4)3 at various temperatures; cis-[Co(ip)2(C12H25NH2)2](ClO4)3 = 4 × 10−4 mol dm−3, μ = 1.0 mol dm−3, [Fe(CN)6]4− = 0.01 mol dm−3.

Figure 2. Plot of k against [BMIM]Br for cis-[Co(ip)2(C12H25NH2)2](ClO4)3 at various temperatures; cis-[Co(ip)2(C12H25NH2)2](ClO4)3 = 4 × 10−4 mol dm−3, μ = 1.0 mol dm−3, [Fe(CN)6]4− = 0.01 mol dm−3.

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Figure 3. Eyring plot for cis-[Co(ip)2(C12H25NH2)2](ClO4)3 in DPPC medium. [Complex] = 4 × 10−4 mol dm−3; [Fe2+] = 0.01 mol dm−3; [μ] = 1.0 mol dm−3.

Figure 3. Eyring plot for cis-[Co(ip)2(C12H25NH2)2](ClO4)3 in DPPC medium. [Complex] = 4 × 10−4 mol dm−3; [Fe2+] = 0.01 mol dm−3; [μ] = 1.0 mol dm−3.

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Figure 4. Eyring plot for cis-[Co(ip)2(C12H25NH2)2](ClO4)3 in [BMIM]Br medium. [Complex] = 4 × 10−4 mol dm−3; [Fe(CN)6]4− = 0.01 mol dm−3; [μ] = 1.0 mol dm−3.

Figure 4. Eyring plot for cis-[Co(ip)2(C12H25NH2)2](ClO4)3 in [BMIM]Br medium. [Complex] = 4 × 10−4 mol dm−3; [Fe(CN)6]4− = 0.01 mol dm−3; [μ] = 1.0 mol dm−3.

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Figure 5. Isokinetic plot of the activation parameters for the reduction of cis-[Co(ip)2(C12H25NH2)2](ClO4)3 by ion(II) in DPPC medium. [Complex] = 4 × 10−4 mol dm−3; [Fe2+] = 0.01 mol dm−3; [μ] = 1.0 mol dm−3. (Entropy and Enthalpy of activation is symbolized ΔS‡ and ΔH‡).

Figure 5. Isokinetic plot of the activation parameters for the reduction of cis-[Co(ip)2(C12H25NH2)2](ClO4)3 by ion(II) in DPPC medium. [Complex] = 4 × 10−4 mol dm−3; [Fe2+] = 0.01 mol dm−3; [μ] = 1.0 mol dm−3. (Entropy and Enthalpy of activation is symbolized ΔS‡ and ΔH‡).

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Figure 6. Isokinetic plot of the activation parameters for the reduction of cis-[Co(ip)2(C12H25NH2)2](ClO4)3 by ion(II) in [BMIM]Br medium. [Complex] = 4 × 10−4 mol dm−3; [Fe(CN)6]4− = 0.01 mol dm−3; [μ] = 1.0 mol dm−3. (Entropy and Enthalpy of activation is symbolized ΔS‡ and ΔH‡).

Figure 6. Isokinetic plot of the activation parameters for the reduction of cis-[Co(ip)2(C12H25NH2)2](ClO4)3 by ion(II) in [BMIM]Br medium. [Complex] = 4 × 10−4 mol dm−3; [Fe(CN)6]4− = 0.01 mol dm−3; [μ] = 1.0 mol dm−3. (Entropy and Enthalpy of activation is symbolized ΔS‡ and ΔH‡).

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Table 1. Second-order rate constants for the reduction of cobalt(III) complex ion by Fe2+ in DPPC medium under various temperatures; cis-[Co(ip)2(C12H25NH2)2](ClO4)3 = 4 × 10−4 mol dm−3, μ = 1.0 mol dm−3, [Fe(CN)6]4− = 0.01 mol dm−3.

Table 1. Second-order rate constants for the reduction of cobalt(III) complex ion by Fe2+ in DPPC medium under various temperatures; cis-[Co(ip)2(C12H25NH2)2](ClO4)3 = 4 × 10−4 mol dm−3, μ = 1.0 mol dm−3, [Fe(CN)6]4− = 0.01 mol dm−3.

[DPPC] × 105
(mol dm−3)k × 102, dm3 mol−1 s−1 298 K303 K308 K323 K328 K333 K2.015.015.215.516.416.817.33.014.715.015.417.017.518.04.014.014.415.017.217.818.25.013.513.914.117.718.318.76.012.713.013.418.318.619.17.011.311.712.518.719.119.5

Table 2. Second-order rate constants for the reduction of cobalt(III) complex ion by Fe2+ in the presence of [BMIM]Br under various temperatures; cis-[Co(ip)2(C12H25NH2)2](ClO4)3 = 4 × 10−4 mol dm−3, μ = 1.0 mol dm−3, [Fe(CN)6]4− = 0.01 mol dm−3.

Table 2. Second-order rate constants for the reduction of cobalt(III) complex ion by Fe2+ in the presence of [BMIM]Br under various temperatures; cis-[Co(ip)2(C12H25NH2)2](ClO4)3 = 4 × 10−4 mol dm−3, μ = 1.0 mol dm−3, [Fe(CN)6]4− = 0.01 mol dm−3.

[(BMIM)Br] × 103, mol dm−3k × 102, dm−3 mol−1 s−1 298 K303 K308 K313 K318 K323 K1.44.04.26.58.914.723.01.65.25.57.712.020.627.41.86.17.48.525.531.533.72.06.59.415.528.634.855.42.210.515.221.332.145.363.72.411.420.224.235.258.277.22.611.621.225.636.259.680.4

Table 3. Activation parameters for the reduction of cis-[Co(ip)2(C12H25NH2)2](ClO4)3, μ = 1.0 moldm−3 in DPPC medium.

Table 3. Activation parameters for the reduction of cis-[Co(ip)2(C12H25NH2)2](ClO4)3, μ = 1.0 moldm−3 in DPPC medium.

[DPPC] × 105
(mol dm−3)∆H‡−∆S‡2.00.14218.23.00.37212.14.00.67204.35.00.99195.76.01.38185.67.02.03168.4

Table 4. Activation parameters for the reduction of cis-[Co(ip)2(C12H25NH2)2](ClO4)3, μ = 1.0 moldm−3 in [BMIM]Br medium.

Table 4. Activation parameters for the reduction of cis-[Co(ip)2(C12H25NH2)2](ClO4)3, μ = 1.0 moldm−3 in [BMIM]Br medium.

[(BMIM)Br]× 103,
mol dm−3∆H‡−∆S‡1.46.6250.21.66.5649.71.86.5742.12.06.6735.02.26.7934.72.47.2624.22.67.967.3

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