Determination of acidic dissociation constants of L-phenylalanyl-glycine and L-alanyl-L-alanine in water using ab initio methods

Year 2014, Volume: 42 Issue: 2, 263 - 274, 01.06.2014

Farhoush Kiani Mahmoud Tajbakhsh Fereydoon Ashrafi Nesa Shafiei Azar Bahadori Fardad Koohyar

Abstract

The acid dissociation constant is one of the fundamental properties of organic molecules. In this study, den- sity functional theory DFT calculations with B3LYP combined with 6-31+G d basis set were applied for determination of acidic dissociation constants of L-phenylalanyl-glycine and L-alanyl-L-alanine. An ab initio procedure for accurately calculating aqueous-phase pKa values of the L-phenylalanyl-glycine and L-alanyl- L-alanine is presented. Formation of intermolecular hydrogen bonds between the existent species and water has been analyzed using Tomasi’s method. In this way, it was determined that in alkaline aqueous solutions the cation, anion, and neutral species of L-phenylalanyl-glycine and L-alanyl-L-alanine are solvated with some molecules of water. Furthermore, the correlation between the pKa values of these dipeptides was investigated theoretically, and a comparable agreement was found with the experimental results.

Keywords

Acidity constant, L-phenylalanyl-glycine, L-alanyl-L-alanine, solvation free energy, ab initio methods

L-fenilalanil-gilisin ve L-alanil-L-alaninin sudaki asidik ayrışma sabitlerinin ab initio yöntemleri ile belirlenmesi

Abstract

A sidik ayrışma sabiti organik bileşiklerin en temel özelliklerinden birisidir. Bu çalışmada, yoğunluk fonksiyon teori DFT hesaplamaları 6-31+G d ile B3LYP birleştirilmiş temel setler L-fenilalanil-glisin ve L-alanil-Lalaninin asidik ayrışma sabitlerinin belirlenmesinde uygulanmıştır. L-fenilalanil-glisin ve L-alanil-L-alaninin sulufaz pK değeri hesaplamaları için ab initio yöntemi sunulmuştur. Mevcut türler ve su arasında oluşan moleküller arası hidrojen bağlarının oluşumu Tomasi yöntemi kullanılarak analiz edilmiştir. Bu şekilde, su molekülleri ile solvate olmuş L-fenilalanil-glisin ve L-alanil-L-alaninin katyonu, anyon ve nötr türleri bazik sulu çözeltilerde belirlenmiştir. Ayrıca, bu dipeptidlerin pKa değerleri arasındaki ilişki teorik olarak incelenmiş ve kıyaslanabilir uyumlu deneysel sonuçlar bulunmuştur

Keywords

Asitlik sabiti, L-fenilalanil-glisin, L-alanil-L-alanin, çözünme serbest enerjisi, ab initio yöntemleri

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