The Kinetics of the Diazo Coupling Reaction.

Zollinger, Heinrich

doi:10.1021/cr60159a004

Cited by 26 publications

(8 citation statements)

References 22 publications

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“…(c) Activity Studies.-It was of interest to determine whether and to what extent the enhancement reaction between PNPDF and anti-DNP Ab produced a loss of Ab binding capacity; such a correlated loss of activity might be expected if the labeling reaction were indeed occurring in the active site. To a 1.25 X 10 ~5 m solution of anti-DNP Ab in sodium acetate 4 Diazonium reactions have been shown to follow secondorder kinetics (Zollinger, 1952(Zollinger, , 1953. The specific secondorder rate constant (k5, equation [2 ]) for the reaction of PNPDF and IV-chloracetyltyrosine calculated from our results is 1.2 X 10~2 M_1 sec-1 under these conditions.…”

Section: Experimental Methods and Resultsmentioning

confidence: 67%

Affinity Labeling of the Active Sites of Antibodies to the 2,4-Dinitrophenyl Hapten^*

Metzger¹,

Wofsy²,

Singer³

1963

Biochemistry

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The method of afkity labeling provides a general method for attaching a covalently bound label to the active sites of antibody and enzyme molecules. Previous studies with antibodies directed to the benzenearsonate hapten were entirely in accord with the predictions of the method. In the present studies, antibodies to the 2,4dinitrophenyl (DNP) hapten were investigated. The labeling reagent p-nitrophenyldiawnium fluoborate was found to react irreversibly with an excess of the unproteded antibody: (a) at a much more rapid rate than with the antibody whose active sites were protected with an excess of N-DNP-e-aminocaproic acid; (b) to give a product with stentially a pure azotyrosine spectrum; (c) at a rate which was first-order in the concentration of the reversible complex formed initially between the reagent and the antibody s i t s , in accord with the mechanism proposed for affinity labeling; and (d) to produce a loss of antibody binding sites corresponding closely to the number of azotyrosine groups formed. Related but less extensive studies were carried out with DNP-diazonium and p(carboxy)-benzenediazonium fluoborates and with other reagents. The results closely follow the predictions of the method, and provide strong evidence that a tyrosine residue is present in anti-DNP antibody sites. The results also indicate that there is a broad distribution of rates a t which the antibody sites are labeled, and therefore that the sites are heterogeneous. These studies provide the basis for an attempt to isolate and analyze labeled peptide

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Section: Experimental Methods and Resultsmentioning

confidence: 67%

Affinity Labeling of the Active Sites of Antibodies to the 2,4-Dinitrophenyl Hapten^*

Metzger¹,

Wofsy²,

Singer³

1963

Biochemistry

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“…It is interpreted as being an inherent property of the nucleophiles and is related to the solvation energies of the nucleophiles. Ritchie concluded that the transition states of these cation-anion combination reactions are very close in structure to that of the onesolvent-separated ion pair, and that two factors are important in determining the relative rates of reaction with the four nucleophiles mentioned: (1) desolvation energy of the anion; (2) effective ionic radii of the cation and anion, which determine Coulombic attraction.…”

Section: Reactions With Nucleophiles At the ß Nitrogenmentioning

confidence: 99%

“…N,N-Diphenylhydroxylamine and NaNC>2 are good nucleophiles and form good (i.e., relatively stable) homolytic leaving groups, namely diphenyl nitroxide [(CeHs^NO•] + H+, and nitrogen dioxide, respectively. These products • in (2) are also more efficient "gegen-radicals" for the oxidation of the arylcyclohexadienyl radical 5, the intermediate of the subsequent homolytic aromatic substitution 7, H Ar Ar than those which are formed without such additives or with aroyl peroxides as radical sources. This becomes evident from the increased yield of biphenyl products as well as from a comparison of kinetic hydrogen isotope effects of arylations carried out with aroyl peroxides (kn/ku = 6.6)46 with those for nitrite-assisted arylations in DMSO (kH/kD = 1.01 to 2.36)47 and in "classical" (i.e., heterogenous phase) Gomberg-Bachmann and acylarylnitrosamine4 •48 reactions.…”

Section: Reactions With Nucleophiles At the ß Nitrogenmentioning

confidence: 99%

“…I thank Dr. E. Haselbach (University of Basle) for stimulating discussions and Dr. J. R. Penton (ETHZ) for his help in the preparation of the English manuscript of this paper. For the support of our own work reported here, acknowledgment is made to the Swiss National Foundation for Scientific Research, Projects Received February 2,1973 Sulfoximine1 chemistry began in 1950, when Whitehead and Bentley discovered that the sulfoximine of methionine is the agent responsible for the toxicity of wheat flour treated with nitrogen trichloride.2 Such treatment had been widely practiced for many years.…”

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confidence: 98%

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Reactivity and stability of arenediazonium ions

Zollinger¹

1973

Acc. Chem. Res.

179

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“…Sodium nitrate at 4 M decreases the rate 19 per cent. Zollinger (163) has published a review of data on kinetics of diazo coupling reac tions.…”

Section: Ij2dbi'2'mentioning

confidence: 99%

Reaction Kinetics

Taube¹

1953

Annu. Rev. Phys. Chem.

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The Kinetics of the Diazo Coupling Reaction.

Cited by 26 publications

References 22 publications

Affinity Labeling of the Active Sites of Antibodies to the 2,4-Dinitrophenyl Hapten^*

Affinity Labeling of the Active Sites of Antibodies to the 2,4-Dinitrophenyl Hapten^*

Reactivity and stability of arenediazonium ions

Reaction Kinetics

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The Kinetics of the Diazo Coupling Reaction.

Cited by 26 publications

References 22 publications

Affinity Labeling of the Active Sites of Antibodies to the 2,4-Dinitrophenyl Hapten*

Affinity Labeling of the Active Sites of Antibodies to the 2,4-Dinitrophenyl Hapten*

Reactivity and stability of arenediazonium ions

Reaction Kinetics

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Product

Resources

About

Affinity Labeling of the Active Sites of Antibodies to the 2,4-Dinitrophenyl Hapten^*

Affinity Labeling of the Active Sites of Antibodies to the 2,4-Dinitrophenyl Hapten^*