Kinetics and mechanisms of the aminolysis of N-hydroxysuccinimide esters in aqueous buffers

Cline, Gary W.; Hanna, Samir B.

doi:10.1021/jo00250a031

Cited by 75 publications

(78 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The respective reactive polymers poly(N-hydroxy succinimide acrylate) (PNHSA) and poly(N-hydroxy succinimide methacrylate) (PNHSMA) can react with amines in a polymer analogous reaction (also called postpolymerization modification) under very mild reaction conditions, yielding functionalized polyacrylamide or polymethacrylamide derivates. [21][22][23][24] By combining reactive polymers with various amines, functional polymers are now accessible that could not be prepared by the direct polymerization of the respective acrylamide monomers. The conversion of polymeric activates esters with amines is usually quantitative and proceeds (usually) without any side reactions under mild conditions, such as stirring at room temperature.…”

Section: Polymeric Activated Estersmentioning

confidence: 99%

Synthesis of well‐defined polymeric activated esters

Théato

2008

J. Polym. Sci. A Polym. Chem.

277

260

View full text Add to dashboard Cite

Monomers bearing an activated ester group can be polymerized under various controlled polymerization techniques, such as ATRP, NMP, RAFT polymerization, or ROMP. Combining the functionalization of polymers via polymeric activated esters with these controlled polymerization techniques generate possibilities to realize highly functionalized polymer architectures. Within this highlight two different research areas of activated esters in polymer science will be discussed: (i) the preparation of defined reactive polymer architectures by controlled polymerization techniques and (ii) the preparation of defined reactive thin films. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6677–6687, 2008

show abstract

Section: Polymeric Activated Estersmentioning

confidence: 99%

Synthesis of well‐defined polymeric activated esters

Théato

2008

J. Polym. Sci. A Polym. Chem.

277

260

View full text Add to dashboard Cite

show abstract

“…24 These values will be used as fitting parameters in the following section. The estimated rate constants plotted against reciprocal temperature give the Figure S3, and the activation ΔH ‡ and ΔS ‡ are obtained from the slope and intercept of the plot on the basis of the equation ln(k deg T −1 ) = −ΔH ‡ (RT) −1 + ΔS ‡ R −1 + ln(κk B h −1 ).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Kinetic Study for AB-Type Coupling Reaction of Tetra-Arm Polymers

et al. 2011

View full text Add to dashboard Cite

The reaction rate for the polycondensation in the Tetra-PEG gel system, i.e., A−B type coupling reaction between mutually reactive two four-arm polymers, has been studied by ATR-IR spectroscopy. It was found that (1) the polycondensation kinetics of Tetra-PEG gel can be simply treated as a chemical reaction between mutually reactive end-groups in solution, (2) the reaction undergoes as a simple second-order reaction from beginning to end regardless of gelation threshold, and (3) the gelation mechanism was predicted from the thermodynamic enthalpy and entropy at the transition state estimated by temperature dependence of rate constants. The reson of smooth second-order kinetics is suspected to be that the meanfield approximation can be applied to the reactivity of terminal groups on Tetra-PEGs; i.e., the reactivity of terminal groups on Tetra-PEGs is not affected by the steric hindrance, substitution effet, and gelation threshold. ■ INTRODUCTIONGelation or cross-linking is one of the fundamental but key reactions in the production of polymeric materials. A variety of commercial products, namely rubbers, gels, paints, and adhesives, are made by way of gelation threshold, i.e., the onset of formation of infinitely large clusters. Hence, the understanding of the kinetics of network formation is of particular importance not only from basic science but also from industrial points of view.One of the simplest ways describing the cross-linking kinetics is to treat as a series of branching reactions. 1,2 Let us consider the AB-type polycondensation. When the mean-field approximation is applied to the reactivity of terminal functional group, the reaction rate equation is described as a simple diffusioncontrolled reaction rate equation.Here, C A (t), C B (t), and k are the concentrations of species A and B and reaction rate constant. It should be noted that k is constant from initiation to completion regardless of the gelation threshold because the mean-field approximation is applied to the reactivity of terminal functional group. The validity of this equation was tested and partly confirmed. For example, Yokoyama and Dusek et al. investigated the time variation of the number of cross-links on the polyurethane network formation. However, the reaction kinetics was not discussed in detail. 3,4 Rozenberg, Kambe, and Dusek et al. reported that the reaction rate constant fell down at the later stage of reaction between epoxides and amines. 5−8 These studies were on the polymer melt systems. As for the network formation of conventional chemical gels, Bates and Howard calculated the reaction rate constants for gelation reaction under assumption of third-order kinetics. 9 This reaction obeyed a third-order kinetics only at the early stage of gelation. In addition, Stepto et al. reported polycondensation reaction of low-molecular-weight precrusors around the gel point. 10,11 However, the reaction exponent or reaction rate constant was not predicted. As mentioned above, there are only a few experimental data fully supporting the eq 1....

show abstract

“…The bifunctional cross-linking agents N-succinimidyl-3-(2-pyridy1dithio)-propionate (SPDP, from Pierce) and N-hydroxysuccinimidyl ester of iodoacetic acid (SIA, synthesized in crystalline form following the method described in [37]) were used for the production of HSA-monensin conjugates. Disulfide (HSA-SPDP-monensin) and thioether (HSA-SIAmonensin) cross-linked conjugates were synthesized according to previously published procedures [2,31.…”

Section: Hsa-monensin Conjugatesmentioning

confidence: 99%

Mechanisms involved in serum‐dependent inactivation of the immunotoxin enhancers monensin and carrier‐protein—monensin

Franceschi

Dosio

Anselmi

et al. 1994

European Journal of Biochemistry

View full text Add to dashboard Cite

The immunotoxin-enhancing properties of monensin and of human-serum-albumin-monensin conjugates are severely impaired in the presence of human serum. In this study we have therefore investigated the interaction between serum proteins and monensin leading to the inactivation of monensin function as immunotoxin potentiator. We found that the binding of monensin-specific mAb to thioether-cross-linked or disulfide-cross-linked protein-monensin conjugates is negatively affected by serum, as indicated by immunoenzymic (ELISA) and radioimmunobinding analysis. Size-exclusion chromatography of serum samples indicated that the greatest blocking effect is due to protein components of 40-90 kDa eluting as a broad peak (peak 4). Analysis of the proteins contained within peak 4 by ion-exchange chromatography followed by microsequencing revealed that the major components of peak no. 4 were transferrin, human serum albumin and immunoglobulin fragments. Investigations on the nature of the interactions between serum proteins and monensin leading to monensin inactivation were conducted by affinity chromatography of serum on immobilized human-serum-albumin-monensin conjugates, size-exclusion chromatography, SDSPAGE analysis of serum-treated human-serum-albumin-monensin conjugates, and evaluation of the stability of immobilized human-serum-albumin-bound '251-monensin following treatment with serum. Addition of esterase inhibitors (e.g. EDTA, 4-nitrophenyl phosphate) or prior treatment of the serum at 56°C partially reversed the serum effects observed. We conclude that serum proteins block the immunotoxin-enhancing effect of monensin and of human-serum-albumin-monensin conjugates by multiple mechanisms involving hydrophobic and covalent interactions and enzyme-mediated cleavage of protein-bound monensin.Hybrid molecules formed by mAbAigands chemically or genetically linked to toxins (immunotoxins) have been proposed as a new class of anti-tumor pharmacological reagents [l]. In particular, immunotoxins made with mAb linked to ricin A chain (RTA) have been extensively studied in vitro and in animal models [2-111, and their anti-tumor potential clinically evaluated [ 12-171. Although RTA-immunotoxins show high target-cell selectivity and low in vivo toxicity [12,13,[15][16][17], their cytotoxic potency is variable, depending on the internalization rate [18, 191, the intracellular distribution (11, 20-231, the target-cell type [24, 251 and other parameters. As a result, clinical trials conducted with RTA-immunotoxins have met with limited success [12-171. To increase the anti-target cell potency of RTA-immunotoxins, lysosomotropic amines (e.g. chloroquine, methylamine, ammonium chloride) or ionophores (e.g. monensin,Correspondence to M. Colombatti, Istituto di Immunologia e Malattie Infettive, Universiti di Verona, c/o Policlinico Borgo Roma, 1-37134 Verona, ItalyAbbreviations. HSA, human serum albumin; RIB, radioimmunobinding ; Tfn, transferrin; Nph-P, 4-nitrophenyl phosphate; RTA, rich toxin A chain; SPDP, N-succinimidyl-3-(2-pyridyl...

show abstract

Kinetics and mechanisms of the aminolysis of N-hydroxysuccinimide esters in aqueous buffers

Cited by 75 publications

References 0 publications

Synthesis of well‐defined polymeric activated esters

Synthesis of well‐defined polymeric activated esters

Kinetic Study for AB-Type Coupling Reaction of Tetra-Arm Polymers

Mechanisms involved in serum‐dependent inactivation of the immunotoxin enhancers monensin and carrier‐protein—monensin

Contact Info

Product

Resources

About