Catalytic hydrolysis of p‐nitrophenyl picolinate by copper(II) and zinc(II) complexes of N‐(2‐deoxy‐β‐D‐glucopyranosyl‐2‐salicylaldimino)

D‐glucosamine Schiff base N‐(2‐deoxy‐β‐D‐glucopyranosyl‐2‐salicylaldimino) and its Cu(II) and Zn(II) complexes were synthesized and characterized. The hydrolysis of p‐nitrophenyl picolinate (PNPP) catalyzed by ligand and complexes was investigated kinetically by observing the rates of the release of p‐nitrophenol in the aqueous buffers at 25°C and different pHs. The scheme for reaction acting mode involving a ternary complex composed of ligand, metal ion, and substrate was established and the reaction mechanisms were discussed by metal–hydroxyl and Lewis acid mechanisms. The experimental results indicated that the complexes, especially the Cu(II) complex, efficiently catalyzed the hydrolysis of PNPP. The catalytic reactivity of the Zn(II) complex was much smaller than the Cu(II) complex. The rate constant k_N showing the catalytic reactivity of the Cu(II) complex was determined to be 0.299 s^?1 (at pH 8.02) in the buffer. The pK_a of hydroxyl group of the ternary complex was determined to be 7.86 for the Cu(II) complex. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 345–350, 2002     

Hydrolysis of PNPP Catalyzed by Cu (II), Ni (II) Schiff Base Complexes in CTAB Micellar Solution

The kinetics of hydrolysis of p‐nitrophenyl picolinate(PNPP) catalyzed by metallomicelles formed from Cu (II), Ni (II) Schiff base complexes (CuL, NiL) and CTAB micelle were investigated in the pH range of 6.0–9.0 at 30°C. For the Cu (II) Schiff base complex CuL, the apparent rate constants (k _obsd) of PNPP hydrolysis initially increased with the increasing pH of reaction media, then fell off. For the Ni (II) Schiff base complex NiL, the k _obsd always increased with the increasing pH. The kinetic and thermodynamic parameters were calculated. The hydrolysis rate of PNPP catalyzed by Cu (II) complex was much larger than that by Ni (II) complex in CTAB micellar solution. The catalytic mechanism of the PNPP hydrolysis was discussed in detail, and the possibly active specie for the catalytic hydrolysis of PNPP was the monohydroxo metal complex.     

Metallomicellar Catalysis: Hydrolysis of PNPP Catalyzed by Copper(II), Zinc(II), Cerium(IV) Complexes with Long Alkyl Pyridine Ligands in CTAB Micellar Solution

A kind of new functional surfactant with substituted long alkyl pyridine was synthesized and its Ce(IV), Zn(II), and Cu(II) complexes were used as hydrolytic metalloenzyme models. The hydrolysis of p-nitrophenyl picolinate (PNPP) catalyzed by the metallomicelles in CTAB micellar solution was investigated at different pH and 30°C. Kinetic parameters of catalytic hydrolysis were obtained by employing the ternary complex kinetic model for metallomicellar catalysis. Effects of the structure of ligands and microenvironment of reaction on the hydrolytic reaction of PNPP have been discussed in detail. From the apparent rate constants (k _obsd ) of the catalytic hydrolysis of PNPP, it can be seen that the catalytic effect of complexes of ligand L² with long hydrocarbon chain was stronger than that of ligand L¹, and complex CuL² showed higher catalytic efficacy on the hydrolytic reaction than those of ZnL² and CeL². However, experiment results in this article showed that ZnL² and CeL² are more susceptible to environment than CuL². The catalytic mechanism was proposed, and the possibly active species for the catalytic hydrolysis of PNPP was determined to be the hydroxylated metal complex.     

Studies on the Kinetics and Mechanism of Hydrolysis of p-nitrophenyl Picolinate (PNPP) by Unsymmetrical bis-Schiff Base Complexes with Aza-crown Ether or Morpholino Pendants

Two novel unsymmetrical bis-Schiff base manganese(III) and cobalt(II) complexes with benzo-10-aza-crown ether pendants (MnL¹Cl, CoL¹), and their analogoues with morpholino pendants (MnL²Cl, CoL²), have been synthesized and employed as models to mimic hydrolase in p-nitrophenyl picolinate (PNPP). The kinetics and the mechanism of PNPP hydrolysis catalyzed by these complexes were investigated. A kinetic mathematical model of PNPP cleavage catalyzed by these complexes was proposed. The effects of the complexes structure and reactive temperature on the rate of catalytic PNPP hydrolysis have been also examined. The results showed that the rate for the catalytic PNPP hydrolysis increased following the increase in pH of the buffer solution; four complexes exhibited high activity in the catalytic PNPP hydrolysis. Compared with the crown-free analogoues MnL²Cl and CoL², the crowned Schiff base complexes (MnL¹Cl, CoL¹) exhibit a higher catalytic activity; the pseudo-first-order-rate (k_obs) for the PNPP hydrolysis catalyzed by the complex MnL¹Cl containing benzo-10-aza-crown ether is 1.04 × 10³ that of spontaneous hydrolysis of PNPP at pH = 7.00, [S] = 2.0×10⁻⁴ mol dm⁻³.     

PNPP Cleavage Catalyzed by Schiff Base Mn(III) Complexes Containing Polyether Side Chains in CTAB Micellar Solutions

Two Schiff base Mn(III) complexes containing polyether side chain were synthesized and characterized. The catalytic hydrolysis of p‐nitrophenyl picolinate (PNPP) by the two complexes in the buffered CTAB micellar solution in the pH range of 6.60–8.20 was investigated kinetically in this study. The influences of acidity, temperature, and structure of complex on the catalytic cleavage of PNPP were also studied. The mechanism of PNPP hydrolysis catalyzed by Schiff base manganese(III) complexes in CTAB micellar solution was proposed. The relative kinetic and thermodynamic parameters were determined. Comparied with the pseudo‐first‐order rate constant (k ₀) of PNPP spontaneous hydrolysis in water, the pseudo‐first‐order rate constants (k _obsd) of PNPP catalytic hydrolysis are 1.93×10³ fold for MnL¹ ₂Cl and 1.06×10³ fold for MnL² ₂Cl in CTAB micellar solution at pH=7.00, T=25°C, and [S]=2.0×10^?4mol · dm^?3, respectively. Furthermore, comparing the k _obsd of PNPP catalytic hydrolysis by metallomicelles with that of PNPP hydrolysis catalyzed only by metal complexes or CTAB micelle at the above‐mentioned condition, metallomicelles of MnL₂(L=L¹, L²) Cl/CTAB exhibit notable catalytic activities for promoting PNPP hydrolysis, and MnL¹ ₂Cl/CTAB system is superior in promoting cleavage of PNPP relative to MnL² ₂Cl/CTAB system under the same experimental conditions. The results indicate that the rate of PNPP catalytic cleavage is influenced by the structures of the two complexes, the acidity of reaction systems, and the solubilization of PNPP in CTAB micelles.     

Cobalt(II) Schiff Base Complexes Bearing Aza Crown Ether Pendants as Synthetic Hydrolase Catalyzing PNPP Hydrolysis

Two Co^II complexes with aza crown ether substituted salicylaldimine Schiff base, CoL¹ ₂ and CoL² ₂, have been synthesized and employed as models to mimic hydrolase in catalytic hydrolysis of a carboxylic ester. The specific change of u.v.–vis. absorption spectra of the hydrolytic reactive systems has been observed, which indicates that key intermediates are formed by PNPP and Co^II complexes. The kinetics and the mechanism of PNPP hydrolysis have been investigated. The kinetic mathematical model for PNPP cleavage catalyzed by the Co^II complexes has been proposed. The results show that, compared with the crown-free analogous CoL³ ₂, the bis(aza crown ether)s Co^II complexes CoL¹ ₂ and CoL² ₂ exhibit high activity in the PNPP catalytic hydrolysis; the rate of the PNPP hydrolysis catalyzed by the complexes increases with the increase of pH of the buffer solution; the pseudo-first-order rate constants (k _ob) of PNPP hydrolysis catalyzed by the complexes is 1000 times more than that of spontaneous hydrolysis of PNPP.     

Metallomicellar Catalysis. Catalytic Hydrolysis of p-Nitrophenyl Picolinate by bis-{N-(2-Deoxy-β-D-glucopyranosyl-2-[3-carboxyl-salicylaldimino])} M2 (II) (M = Cu,Zn, Co) in CTAB Micellar Solution

The hydrolysis of p-nitrophenyl picolinate (PNPP) catalyzed by the binuclear complexes bis-{N-(2-deoxy-β-D-glucopyranosyl-2-[3-carboxyl-salicylaldimino])} M₂ (II) (M = Cu, Zn, Co) was investigated kinetically by observing the rates of the release of p-nitrophenol in the presence of surfactant (hexadecyltrimethylammonium bromide CTAB at different pHs and 25°C. The scheme for binuclear complex metallomicelle catalyzed reaction acting mode involving a ternary complex composed of ligand, metal ion and substrate in micelle was established and the relative kinetic and thermodynamic parameters (k_N, K_s, pK_a) were obtained. The reaction is discussed in terms of a bifunctional catalytic mechanism.     

Catalytic hydrolysis of carboxylic acid esters by Cu(II) and Zn(II) complexes containing a tetracoordinate macrocyclic Schiff base ligand in Brij35 micellar solution

The macrocyclic Schiff base complexes of Cu(II) and Zn(II) in Brij35 micellar solution are investigated kinetically for the catalytic hydrolysis of p-nitrophenyl acetate (PNPA) and p-nitrophenyl picolinate (PNPP) at 30 °C. The results indicate that different mechanisms are operative for the two complexes in the hydrolysis of PNPA and PNPP. The Cu(II) complex can only catalyze the hydrolysis of PNPP by the mechanism which involves the nucleophilic attack of external hydroxide ion on the carbonyl, while the Zn(II) complex can accelerate the hydrolysis of both PNPP and PNPA, by way of the intramolecular nucleophilic attack of zinc-bound hydroxide ion on carbonyl for PNPP and the less effective intermolecular nucleophilic attack of zinc-bound hydroxide ion on carbonyl for PNPA, respectively. The catalytic activity of Zn(II) complex is close to or even higher than that of Cu(II) complex. The reason is discussed in details.     

氮杂冠醚或吗啉基取代的单Schiff碱配合物催化α-吡啶甲酸对硝基苯酯水解

两种含5-取代苯并-10-氮杂-15-冠-5的Schiff碱锰(III)、钴(II)配合物( , )及其吗啉基取代的类似物( , ) 用于催化α-吡啶甲酸对硝基苯酯(PNPP)水解。探讨了氮杂冠醚Schiff 碱配合物催化PNPP水解的动力学和机理;提出了配合物催化PNPP水解的动力学模型;考察了配合物结构、反应温度、缓冲溶液pH值等对PNPP水解反应的影响。结果表明,在25℃条件下随着缓冲溶液pH值的增大,催化PNPP水解速率提高;含取代苯并-10-氮杂-15-冠-5的Schiff碱配合物表现出更高的催化活性。根据阿累尼乌斯公式和不同温度下的表观一级常数求出水解反应的表观活化能。     

Comparative kinetics of carboxylic esters hydrolysis catalyzed by the zinc(II) complex of a macrocyclic Schiff base ligand

The comparative kinetic investigation of the hydrolysis of p-nitrophenyl picolinate (PNPP) and p-nitrophenyl acetate (PNPA) catalyzed by the tetracoordinate macrocyclic Schiff base complex of zinc(II) (1) at 30 °C is reported. The results indicate that the (1) catalyzed hydrolyses of PNPP and PNPA are acid-base catalytic processes and that the active species is the metal bound hydroxide ion, namely, ZnL—OH^–. (1) promoted hydrolysis of PNPP proceeds much faster than that of PNPA. At pH 7.51, the apparent second-order rate constants k _c for hydrolysis of PNPP and PNPA are 0.254 and 7.28 × 10^–3 mol^–1 dm³ s^–1, respectively. The difference in hydrolytic rates may be attributed to the difference of hydrolytic mechanisms by which the PNPP and PNPA operate. The reasons are discussed in detail.     

Metallomicellar Catalysis Hydrolysis of p-Nitrophenyl Picolinate Catalyzed by Copper(II), Nickel(II), and Zinc(II) Complexes of Long Alkyl Pyridine Ligands in Micellar Solution

The ternary complex kinetic model for metallomicellar catalysis has been proposed in this paper. The catalytic effects of bivalent metal ion (Cu(2+), Zn(2+), and Ni(2+)) complexes of long alkyl pyridine ligands upon the hydrolysis of p-nitrophenyl picolinate (PNPP) have been studied kinetically in aqueous buffer of pH ranging from 5.0 to 8.5 at 30 degrees C. The effect of pH on the reactivity is discussed. The results indicate that the metallomicelles formed by pyridine ligands promote the hydrolysis of PNPP, and the order is Cu(II) system>Ni(II) system>Zn(II) system. A stereochemical modification of the complex in the CTAB micelle is suggested as a likely explanation for the observed phenomena. Copyright 2000 Academic Press.     

Studies on Schiff Base Complexes with Aza-Crown Ether Pendants as Synthetic Hydrolases for p-Nitrophenyl Picolinate in Brij35 Surfactant Micellar Solution

Schiff base complexes with aza-crown ether pendants have been synthesized and employed as models for hydrolase enzymes by studying the kinetics of their hydrolysis reactions with p-nitrophenyl picolinate (PNPP) in Brij35 surfactant micellar solution. A kinetic model of PNPP cleavage catalyzed by these complexes is proposed. The effects of complex structures and reaction temperature on the rate of catalytic PNPP hydrolysis have also been examined. The rate increases with pH of the buffered Brij35 micellar solution under 25°C; all four complexes exhibited high activity in the catalytic PNPP hydrolysis. The catalytic activity of the phenyl-bridged Schiff base complex is larger than that of ethyl-bridged Schiff base complex for the same substituent and metal. The catalytic activity of manganese(III) complex is superior over cobalt(II) complex in catalyzing hydrolysis of PNPP under the same ligand. The pseudo-first-order rate for PNPP hydrolysis catalyzed by CoL¹ containing aza-crown ether is 2.96 × 10⁴ times that of spontaneous hydrolysis of PNPP in Brij35 surfactant micellar solution at pH = 7.60, [S] = 2.0 × 10^?4 mol dm^?3.     

CATALYTIC HYDROLYSIS OF P-NITROPHENYL PICOLNATE BY BIOXOCYLAM ZINC(II) COMPLEXES IN MICELLAR SOLUTION

The effects of dioxocyclam Zn³ ion complexes in micellar solution on ihe hydrolysis of PNPP have been investigated in this paper. Second order rate constants of Ihe hydrolysis of PNPP catalyzed by dio*ocyclam Zn²⁺ion complexes at various pH and the deprotonation constants of H₂ cooriinated to the dioxocyclam Zn²⁺ion complexes pKwere determined kinetically, and the catalytic mechanism was discussed. The results unexpectedly showed that the activation was much larger for Itpophilic ligand under miccllar condition than for bydrophilic ligands under non-miccllar conditions, indicating the dioxocyclam Zn²⁺ ion complex to be an excellent model of carbonic anhydnue.     

Studies on p-Nitrophenyl Picolinate Cleavage by Unsymmetrical Bis-Schiff Base Manganese(III) and Cobalt(II) Complexes in CTAB Surfactant Micellar Solution

The unsymmetrical bis-Schiff base manganese(III) and cobalt(II) complexes with either benzo-10-aza-crown ether pendants (MnL¹Cl, MnL²Cl) or morpholino pendant (MnL³Cl, CoL³) have been employed as models for hydrolase by studying the kinetics of their hydrolysis reactions with p-nitrophenyl picolinate (PNPP) in the buffered CTAB micellar solution. A kinetic model of PNPP cleavage catalyzed by these complexes is proposed. The effects of complex structures and reaction temperature on the rate of PNPP hydrolysis have been examined. All four complexes exhibit higher catalytic activity in the buffered CTAB micellar solution and the rate increases with pH of the buffered CTAB micellar solution under 25°C. The complexes containing a crown ether group exhibit higher catalytic activities than the free-crown analogues. The catalytic activity of manganese(III) complex is superiority over cobalt(II) complex in catalyzing hydrolysis of PNPP under the same ligand.     

p‐Nitrophenyl Picolinate Cleavage by Unsymmetrical Bis‐Schiff Base Manganese(III) and Cobalt(II) Complexes with Aza‐Crown Ether or Morpholino Pendants

The unsymmetrical bis‐Schiff base manganese(III) and cobalt(II) complexes with either benzo‐10‐aza‐crown ether pendants (MnL¹Cl, MnL²Cl) or morpholino pendant (MnL³Cl, CoL³) have been employed as models for hydrolase by studying the kinetics of their hydrolysis reactions with p‐nitrophenyl picolinate (PNPP). A kinetic model of PNPP cleavage catalyzed by these complexes is proposed. The effects of complex structures and reaction temperature on the rate of PNPP hydrolysis have been examined. All four complexes exhibit high catalytic activity and the rate increases with pH under 25°C. The complexes of ligands containing a crown ether group exhibit higher catalytic activities than the non‐crown analogues. The catalytic activity of the complexes follows the order Mn(III)>Co(II) under the same ligands.     

Studies on PNPP Hydrolysis Catalyzed by Schiff Base Cobalt（Ⅱ） Complexes

Two cobalt（Ⅱ） complexes of the Schiff base with morpholino or aza-crown ether pendants, CoL^1 and CoL^2, as mimic hydrolytic metalloenzyme, were used in catalytic hydrolysis of carboxylic ester （PNPP）. The analysis of specific absorption spectra of the hydrolytic reaction systems indicates that key intermediates, made up of PNPP and Co（Ⅱ） complexes, have been formed in reaction processes of the PNPP catalytic hydrolysis. The mechanism of PNPP catalytic hydrolysis has been proposed based on the analytic result of specific absorption spectrum. A kinetic mathematical model, applied to the calculation of the kinetic parameter of PNPP catalytic hydrolysis, has been established based on the mechanism proposed. The acid effect of buffer solution, structural effect of the complexes, and effect of temperature on the rate of PNPP hydrolysis catalyzed by the complexes have been also discussed.     

Metallomicelle catalysis: Hydrolysis of p‐nitrophenyl picolinate induced by Schiff base Co(II) complexes in a Gemini surfactant micellar solution

Two Schiff base cobalt(II) complexes containing crowned substituents have been synthesized and employed to promote the hydrolysis of p‐nitrophenyl picolinate (PNPP) in a buffered micellar solution formed by a cationic Gemini surfactant, bis(hexadecyldimethylammonium)hexane bromide (G(hex)C16, 2Br^?) over a pH range of 6.50–8.50. In comparison, the reactivity of PNPP hydrolysis catalyzed by the same catalysts in the other micellar system, formed by a conventional single‐chain analogue, that is, hexadecyltrimethylammonium bromide (CTAB), has also been evaluated under a selected condition. The results clearly reveal that the two metallomicelles made of the aforementioned Co(II) complexes and the G(hex)C16 are both efficient for catalyzing PNPP hydrolysis with about 3 orders of magnitude in rate acceleration compared with the background rate of PNPP spontaneous hydrolysis. Moreover, the rates of PNPP hydrolysis catalyzed by the two cobalt(II) complexes in G(hex)C16 micelles are about 2 times higher than in CTAB micelles, correspondingly. In addition, observations show that steric hindrance of substituents of the two complexes is also one of the major influencing factors in the PNPP hydrolytic reaction. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 672–680, 2007     

On the Kinetics of Heterogeneous Free Radical Crosslinking Polymerization1)

Abstract

In this paper, two oximato complexes, mononuclear [Cu(Hdmg)₂] and binuclear [Cu₂(Hdmg)₂(H₂dmg)]ClO₄ · H₂O (H₂dmg: dimethylglyoxime), were synthesized and characterized. Hydrolyses of carboxyl acid esters, p‐nitrophenyl picolinate (PNPP) and p‐nitrophenyl acetate (PNPA), catalyzed by these two complexes were investigated in different micellar systems in the pH range from 6.58–8.65 at 25°C. The results obtained indicate that these two complexes exhibit good catalytic function. It also appears that both complexes accelerate the hydrolytic cleavage of PNPP and PNPA in cationic CTAB micellar solution faster than that in nonionic Brij35 micellar solution, which may be due to the different coordinating ability of substrates to complexes and electrostatic interaction between micelles and complexes. For binuclear Cu(II), the rate constant (k _N) for the hydrolysis of PNPA is about two times larger than that for PNPP in CTAB micellar solution, while in Brij35 micellar solution, the k _N values for PNPA and PNPP are roughly the same. This small difference may be ascribed to the configurations of intermediates formed during the reaction and electrostatic interaction between micelles and reactants.     

Kinetics and mechanism of promoted hydrolysis of 4‐nitrophenyl acetate by zinc(II)‐tripod: Different roles of mononuclear and trinuclear species

Coordination studies on Zn(II) complexes of 1,3,5‐tri(2,5‐diazahexyl)benzene (L) show that by comparison with the non‐deprotonation of complex ZnL in a 1:1 system, the three‐dimensional complexiaton decreases the pK_a of the Zn‐bound water molecule, that is, pK_a = 7.47 for trinulclear complex Zn₃L in a 3:1 metal–ligand ratio. These two types of zinc(II) complexes have been examined as catalysts for the hydrolysis of 4‐nitrophenyl acetate (NA) in 10% (v/v) CH₃CN at 298 K, I = 0.10 mol dm^?3 KNO₃ at pH range 6.5–8.2 and 8.5–10, respectively. Kinetic studies show that the second‐order rate constants of NA‐hydrolysis catalyzed by complexes ZnL, Zn₃L, and Zn₃LH_?1 are 0.021, 0.0082, and 0.342 mol^?1 dm³ s^?1, respectively. In all the cases, the pH‐dependent observed first‐order rate constant, k_obs, shows sigmoidal pH–rate profile. The 1:1 complex ZnL–H₂O undergoes NA hydrolysis by direct rate‐determining hydrolysis to produce 4‐nitrophenol(ate) (NP^?) and ZnL(OOCCH₃); while in the 3:1 system the oxygen atom of acetic group forms a H‐bond with the Zn(II)‐bound water of the second branch of tripod indicating that the polynuclear centers are associated and bi‐functional. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 41–48 2004     

PNPP Hydrolysis Catalyzed by Manganese(III) Complexes with Crowned Salicylaldimine Schiff Base Ligand

Four manganese(III) complexes (MnL¹Cl, MnL²Cl, MnL⁴₂Cl, MnL⁵₂Cl) with a crowned salicylaldimine Schiff base ligand have been synthesized and employed as models to mimic hydrolase in the hydrolysis of p-nitrophenyl picolinate (PNPP). The kinetics and mechanism of catalytic PNPP hydrolysis have been investigated. The kinetic mathematical model of PNPP cleavage catalyzed by these complexes has been proposed. The effects of the ligand structure and crown ether ring in complexes, and the reactive temperature on the rate of catalytic PNPP hydrolysis have been also examined. The results show that compared with the crown-free analogous MnL³Cl and MnL⁶₂Cl, the crowned Schiff base manganese(III) complexes, MnL¹Cl, MnL²Cl, MnL⁴₂Cl and MnL⁵₂Cl, exhibit more high catalytic activity, which follow the order: MnL¹Cl >MnL²Cl >MnL⁴₂Cl >MnL⁵₂Cl >MnL³Cl >MnL⁶₂Cl; the pseudo-first-order-rate (k_obs) for the PNPP hydrolysis catalyzed by the complex MnL¹Cl containing three crown ether rings is highest among six complexes and is 1.81 times that of MnL³Cl, 1.49 × 10³ times that of spontaneous hydrolysis of PNPP, respectively, at pH = 7.00, [S] = 2.0 × 10⁻⁴ mol dm⁻³.