‫ﺗﻛﻭﻳﻥ ﺫﺍﺗﻲ‪:‬‬

‫ﺗﺄﻳﻥ ﺍﻷﺣﻣﺎﺽ ﺍﻷﻣﻳﻧﻳﺔ ﺍﻟﻣﺗﻌﺎﺩﻟﺔ‬

‫‪Ionisation des Acides aminés neutres‬‬

‫ﻣﻘﺗﻁﻑ ﻣﻥ ﻛﺗﺎﺏ ﻋﻠﻭﻡ ﺍﻟﺣﻳﺎﺓ‪ .‬ﺑﺭﻭﺗﻳﻧﺎﺕ ﻭ ﺃﻧﺯﻳﻣﺎﺕ‪ ،‬ﻡ‪ .‬ﺑﻌﺯﻳﺯ‪2013 ،‬‬

‫‪Extrait du livre Sciences de la vie. Protéines et Enzymes, M. Baaziz, 2013‬‬
‫‪http://www.takween.com/transition-secondaire-superieur/proteines-enzymes-sommaire.html‬‬
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‫ﻛﻣﺎ ﻳﻅﻬﺭ ﻓﻲ ﺍﻟﺭﺳﻡ ﺍﻟﺗﺎﻟﻲ‪ ،‬ﺗﻣﺗﺎﺯ ﺍﻷﺣﻣﺎﺽ ﺍﻷﻣﻳﻧﻳﺔ ﺍﻟﻣﺗﻌﺎﺩﻟﺔ ﺑﻐﻳﺎﺏ ﺃﻳﺔ ﺷﺣﻧﺔ ﻛﻬﺭﺑﺎﺋﻳﺔ ﻳﺣﻣﻠﻬﺎ ﺍﻟﺷﻖ‬
‫‪.R‬‬

‫ﻋﻧﺩ ﺩﺭﺟﺔ ﺍﻟﺣﻣﻭﺿﺔ ﺍﻟﻌﺎﻟﻳﺔ )‪ (pH = 1‬ﻳﻛﻭﻥ ﺍﻟﺣﻣﺽ ﺍﻷﻣﻳﻧﻲ ﻣﺷﺑﻌﺎ ﺗﻣﺎﻣﺎ ﺑﺎﻟﺑﺭﻭﺗﻭﻧﺎﺕ ﻭ ﻳﺣﻣﻝ ﺷﺣﻧﺔ‬
‫ﻛﻬﺭﺑﺎﺋﻳﺔ ﻣﻭﺟﺑﺔ )‪ .(+‬ﻋﻧﺩ ﺍﻹﺿﺎﻓﺔ ﺍﻟﺗﺩﺭﻳﺟﻳﺔ ﻟﻠﻘﺎﻋﺩﺓ‪ ،‬ﺗﺑﺩﺃ ﻣﺟﻣﻭﻋﺔ ﺍﻟﻛﺭﺑﻭﻛﺳﻳﻝ ﺍﻟﻣﺣﻣﻭﻟﺔ ﻓﻭﻕ ﺍﻟﻛﺎﺭﺑﻭﻥ‬
‫ﺃﻟﻔﺎ )‪ ،(Cα‬ﻭ ﻫﻲ ﺃﻛﺛﺭ ﺣﺎﻣﺿﻳﺔ‪ ،‬ﺑﻔﻘﺩ ﺑﺭﻭﺗﻭﻧﻬﺎ‪ ،‬ﺗﻠﻳﻬﺎ ﻣﺟﻣﻭﻋﺔ ﺍﻷﻣﻳﻥ‪.‬‬
‫ﺍﻧﻁﻼﻗﺎ ﻣﻥ ﺍﻻﺗﺯﺍﻥ ﺍﻷﻭﻝ )ﻗﺩﻑ ﺑﺭﻭﺗﻭﻥ ﺍﻟﻛﺎﺭﺑﻭﻛﺳﻳﻝ(‪ ،‬ﻳﻣﻛﻥ ﺍﺣﺗﺳﺎﺏ ﺛﺎﺑﺕ ﺍﻻﺗﺯﺍﻥ ‪) K1‬ﺛﺎﺑﺙ ﺍﻟﺗﻔﻛﻙ(‪،‬‬
‫ﺍﻟﺫﻱ ﻫﻭ‪:‬‬
‫)‪K1 = (H+) (A+)/( A+‬‬

‫ﺑﺎﻟﻧﺳﺑﺔ ﻟﺣﻣﺽ ﻛﺭﺑﻭﻛﺳﻳﻠﻲ ‪10-4 M<K1<10-6 M :‬‬

‫ﺍﻋﺗﺑﺎﺭﺍ ﻟﻼﺗﺯﺍﻥ ﺍﻟﺛﺎﻧﻲ )ﻗﺩﻑ ﺑﺭﻭﺗﻭﻥ ﺍﻷﻣﻳﻥ(‪ ،‬ﻳﻣﻛﻥ ﺍﺣﺗﺳﺎﺏ ﺛﺎﺑﺙ ﺍﻻﺗﺯﺍﻥ ‪ ،K2‬ﻭﻫﻭ‪:‬‬
‫)‪K2 = (H+) (A-)/(A+‬‬

‫ﺑﺎﻟﻧﺳﺑﺔ ﻟﻸﻣﻳﻥ‪10-8 M<K2<10-10 M :‬‬

‫ﺑﺻﻔﺔ ﻋﺎﻣﺔ‪:‬‬

‫]ﺟﺯﻳﺊ ﻏﻳﺭ ﻣﻔﻛﻙ‪ ،‬ﺣﻣﺽ[ ‪] /‬ﺟﺯﻳﺊ ﻣﻔﻛﻙ‪ ،‬ﻗﺎﻋﺩﺓ[ )‪K = (H+‬‬

‫ﺗﺑﻘﻰ ﻧﺳﺑﺔ ﺍﻟﺟﺯﻳﺊ ﺍﻟﻣﻔﻛﻙ ﻭ ﺍﻟﻐﻳﺭ ﺍﻟﻣﻔﻛﻙ ﻣﺭﺗﺑﻁﺔ ﺑﺗﺭﻛﻳﺯ ﺍﻟﺑﺭﻭﺗﻭﻥ ‪) H+‬ﺍﻟﺫﻱ ﻳﻌﺑﺭ ﻋﻧﻪ ﺍﻟﺭﻗﻡ‬
‫ﺍﻟﻬﻳﺩﺭﻭﺟﻳﻧﻲ‪.(pH ،‬‬
‫ﻓﻲ ﺣﺎﻟﺔ ‪ ،pH = 7‬ﺃﻱ ‪ ،(H+) = 10-7‬ﺗﺻﺑﺢ ﺛﻭﺍﺑﺕ ﺍﻻﺗﺯﺍﻥ ‪ K1‬ﻭ ‪ K2‬ﻛﺎﻟﺗﺎﻟﻲ‪:‬‬

‫‪ -‬ﺣﺎﻟﺔ ‪:K1 = 10-5 M‬‬

‫‪ ،(A+)/( A+) = 10-5/10-7 = 100‬ﻟﻛﻝ ‪ 100‬ﺟﺯﻳﺊ ﻗﺎﻋﺩﻱ )‪ (A+‬ﻳﻭﺟﺩ ﺟﺯﻳﺊ ﺣﻣﺿﻲ ﻭﺍﺣﺩ )‪.(A+‬‬
 ‫‪ -‬ﺣﺎﻟﺔ ‪:K2 = 10-9 M‬‬

‫‪ ،(A-)/( A+) = 10-9/10-7 = 1/100‬ﻟﻛﻝ ﺟﺯﻳﺊ ﻗﺎﻋﺩﻱ )‪ (A-‬ﺗﻭﺟﺩ ‪ 100‬ﺟﺯﻳﺊ ﺣﻣﺿﻲ )‪.(A+‬‬

‫ﺇﺭﺗﻛﺎﺯﺍ ﻋﻠﻰ ﻣﻔﻬﻭﻡ ﺍﻟﺭﻗﻡ ﺍﻟﻬﻳﺩﺭﻭﺟﻳﻧﻲ )ﺍﻟﻠﻭﻏﺎﺭﻳﺗﻡ ﺍﻟﺳﺎﻟﺏ ﻟﺗﺭﻛﻳﺯ ﺇﻳﻭﻥ ﺍﻟﻬﻳﺩﺭﻭﺟﻳﻥ‪pH = -log10 ،‬‬
‫)‪ ،((H+‬ﻧﺳﺗﺧﻠﺹ‪:‬‬

‫ﻋﻧﺩ ﺣﺎﻟﺔ ﺗﻌﺎﺩﻝ ‪ pH‬ﻣﻊ ‪ ، pK‬ﻳﺻﺑﺢ ﺗﺭﻛﻳﺯ ﺍﻟﺟﺯﻳﺊ ﺍﻟﻣﻔﻛﻙ ﻳﺳﺎﻭﻱ ﺗﺭﻛﻳﺯ ﺍﻟﺟﺯﻳﺊ ﺍﻟﻐﻳﺭ ﺍﻟﻣﻔﻛﻙ‪ .‬ﻭ‬
‫ﻳﺳﻣﻰ ﻫﺫﺍ ﺍﻟﺭﻗﻡ ﺍﻟﻬﻳﺩﺭﻭﺟﻳﻧﻲ '‪ pH‬ﻧﺻﻑ ﺍﻟﺗﻔﻛﻙ' )‪ ،(pH de demi-dissociation‬ﻭ ﻫﻭ ﻳﻌﺑﺭ ﻋﻠﻰ‬
‫ﻗﻭﺓ ﺍﻟﺣﻣﺽ ﺃﻱ ﺳﻬﻭﻟﺔ ﺍﻟﺗﺟﺭﺩ ﻣﻥ ﺑﺭﻭﺗﻭﻧﻪ‪ .‬ﻣﺛﻼ‪ ،pK1< pK2 :‬ﻳﻌﻧﻲ ﺃﻥ ﺍﻟﺣﻣﺽ ‪ 1‬ﺃﻗﻭﻯ ﻣﻥ ﺍﻟﺣﻣﺽ‬
‫‪.2‬‬
‫‪ pH‬ﺗﻌﺎﺩﻝ ﺍﻟﺷﺣﻧﺔ ﺍﻟﻛﻬﺭﺑﺎﺋﻳﺔ )‪ (pH isoélectrique, pHi‬ﻟﻸﺣﻣﺎﺽ ﺍﻷﻣﻳﻧﻳﺔ‬

‫ﺗﻔﻛﻙ ﺣﻣﺽ ﺃﻣﻳﻧﻲ ﻛﺎﻟﺟﻠﻳﺳﻳﻥ ﺍﻟﻣﺗﻣﻳﺯ ﺑﺎﻟﺛﻭﺍﺑﺕ ‪ K1‬ﻭ ‪ ،K2‬ﻳﻧﺗﺞ ﺃﺷﻛﺎﻻ ﻣﺧﺗﻠﻔﺔ ﻟﻠﺣﻣﺽ ﺍﻷﻣﻳﻧﻲ ﺣﺳﺏ‬
‫ﺍﻟﺷﺣﻧﺔ ﺍﻟﻛﻬﺭﺑﺎﺋﻳﺔ ﻟﻛﻝ ﺷﻛﻝ‪ .‬ﺗﺗﻐﻳﺭ ﺍﻟﺷﺣﻧﺔ ﺍﻟﻛﻬﺭﺑﺎﺋﻳﺔ ﺍﻟﺻﺎﻓﻳﺔ )‪ (Charge électrique nette‬ﻭﻓﻖ‬
‫ﺗﺭﻛﻳﺯﺍﺕ ﺃﺷﻛﺎﻝ ﺍﻟﺣﻣﺽ ﺍﻷﻣﻳﻧﻲ ﻭ ﻋﺩﺩ ﻭﻧﻭﻉ ﺍﻟﺷﺣﻧﺎﺕ ﺍﻟﻣﺣﻣﻭﻟﺔ ﻭ ﺍﻟﺗﻲ ﻳﺗﺣﻛﻡ ﻓﻳﻬﺎ ﻋﻧﺻﺭ ‪ .pH‬ﻫﻧﺎﻙ‬
‫‪ pH‬ﻣﻌﻳﻥ ﻳﻌﻁﻲ ﻟﻠﺣﻣﺽ ﺍﻷﻣﻳﻧﻲ ﺷﺣﻧﺔ ﻛﻬﺭﺑﺎﺋﻳﺔ ﺻﺎﻓﻳﺔ ﺗﺳﺎﻭﻱ ﺍﻟﺻﻔﺭ‪ .‬ﺇﻧﻪ ‪ pH‬ﺗﻌﺎﺩﻝ ﺍﻟﺷﺣﻧﺔ‬
‫ﺍﻟﻛﻬﺭﺑﺎﺋﻳﺔ ﺃﻭ ‪ pH‬ﺗﻌﺎﺩﻝ ﺍﻷﻳﻭﻥ ﺍﻟﺫﻱ ﻳﺭﻣﺯ ﻟﻪ ﺏ ‪) pHi‬ﺃﻭ ﻛﺫﻟﻙ ‪ .(PI‬ﻳﻠﻌﺏ ﻣﻔﻬﻭﻡ ‪ pHi‬ﺩﻭﺭﺍ ﻫﺎﻣﺎ ﻓﻲ‬
‫ﻣﻌﺭﻓﺔ ﺍﺗﺟﺎﻩ ﻫﺟﺭﺓ ﺍﻷﺣﻣﺎﺽ ﺍﻷﻣﻳﻧﻳﺔ ﻭ ﺍﻟﺑﺭﻭﺗﻳﻧﺎﺕ ﺃﺛﻧﺎء ﻋﻣﻠﻳﺔ ﻋﺯﻝ ﺍﻟﺟﺯﻳﺋﺎﺕ ﺑﺎﻟﻛﻬﺭﺗﻬﺟﻳﺭ‬
‫)‪ (Electrophorèse‬ﻋﻧﺩ ‪ pH‬ﻣﻌﻳﻥ‪.‬‬

‫ﺇﺣﺗﺳﺎﺏ ‪ pHi‬ﻟﻸﺣﻣﺎﺽ ﺍﻷﻣﻳﻧﻳﺔ ﺍﻟﻣﺗﻌﺎﺩﻟﺔ‪.‬‬

‫ﺗﺳﺎﻭﻱ ﻗﻳﻣﺔ ‪ pHi‬ﻣﻌﺩﻝ ﻗﻳﻣﺗﻲ ‪ pK‬ﻟﻠﺷﻛﻠﻳﻥ ﻣﻥ ﺍﻟﺣﻣﺽ ﺍﻷﻣﻳﻧﻲ ﺍﻟﻠﺫﻳﻥ ﻳﺣﻳﻁﺎ ﺍﻟﺷﻛﻝ ﺫﻭ ﺍﻟﺷﺣﻧﺔ‬
‫ﺍﻟﻛﻬﺭﺑﺎﺋﻳﺔ ﺍﻟﻣﺳﺎﻭﻳﺔ ﻟﻠﺻﻔﺭ )ﺗﺗﻭﻓﺭ ﻓﻲ ﺣﺎﻟﺔ ‪ .(pH = pHi‬ﻫﻛﺫﺍ ﺗﺻﺑﺢ ﻗﻳﻣﺔ ‪ ،pHi‬ﻟﻠﺟﻠﻳﺳﻳﻥ ‪ 5,97‬ﺗﻣﺛﻝ‬
‫ﻣﻌﺩﻝ ‪ (2,34) pK1‬ﻭ ‪ .(9,60) pK2‬ﻋﻧﺩ ﻧﻘﻁﺔ ‪ ،pH = pHi‬ﻳﻛﻭﻥ ﺍﻟﺣﻣﺽ ﺍﻷﻣﻳﻧﻲ ﻓﻲ ﺷﻛﻝ ‪A+‬‬
 ‫)‪ .(100%‬ﻋﻧﺩ ﻧﻘﻁﺔ ‪ ،pK1‬ﻳﻛﻭﻥ ﺍﻟﺣﻣﺽ ﺍﻷﻣﻳﻧﻲ ﻓﻲ ﺷﻛﻝ ‪ (50%) A+‬ﻭ ‪.(50%) A+‬‬
‫ﻋﻧﺩ ‪ ،pH = pK2‬ﻳﻛﻭﻥ ﺍﻟﺣﻣﺽ ﺍﻷﻣﻳﻧﻲ ﻓﻲ ﺷﻛﻝ ‪ (50%) A+‬ﻭ ‪.(50%) A-‬‬
‫ﻣﻧﺣﻧﻰ ﻣﻌﺎﻳﺭﺓ ﺍﻷﺣﻣﺎﺽ ﺍﻷﻣﻳﻧﻳﺔ ﺍﻟﻣﺗﻌﺎﺩﻟﺔ )‪.(Acides aminés neutres‬‬

‫ﺗﻬﺩﻑ ﻣﻌﺎﻳﺭﺓ )‪ (Titrage, Titration‬ﺍﻷﺣﻣﺎﺽ ﺍﻷﻣﻳﻧﻳﺔ ﺇﻟﻰ ﻣﻌﺭﻓﺔ ﺛﻭﺍﺑﺕ ‪ pK‬ﻷﺷﻛﺎﻝ ﺍﻟﺣﻣﺽ‬
‫ﺍﻷﻣﻳﻧﻲ ﺍﻟﻣﺗﺄﻳﻥ ﺑﻌﺩ ﺇﺿﺎﻓﺔ ﺗﺭﺍﻛﻳﺯ ﻗﻳﺎﺳﻳﺔ ﻣﻌﻳﻧﺔ ﻣﻥ ﻗﺎﻋﺩﺓ )‪ ،NaOH‬ﻣﺛﻼ( ﺃﻭ ﺣﻣﺽ ) ‪ ،HCl‬ﻣﺛﻼ(‬
‫ﻣﻊ ﻣﺭﺍﻗﺑﺔ ﺗﻐﻳﺭ ‪.pH‬‬
‫ﻣﻧﺣﻧﻰ ﻣﻌﺎﻳﺭﺓ ﺍﻟﺟﻠﻳﺳﻳﻥ‬
‫ﻳﺗﻣﻳﺯﺍﻟﺟﻠﻳﺳﻳﻥ ﺑﺷﻖ ‪ R‬ﺑﺳﻳﻁ )ﻳﺳﺎﻭﻱ ‪ (H‬ﻭ ﻫﻭ ﺣﻣﺽ ﺃﻣﻳﻧﻲ ﺫﻭ ﻭﻅﻳﻔﺗﻳﻥ ﻣﺗﺄﻳﻧﺗﻳﻥ )ﺍﻷﻣﻳﻥ ﻭ‬
‫ﺍﻟﻛﺎﺭﺑﻭﻛﺳﻳﻝ(‪ .‬ﺃﺛﻧﺎء ﺍﻟﺗﺻﺎﻋﺩ ﺍﻟﺗﺩﺭﻳﺟﻲ ﻝ ‪ pH‬ﺑﺈﺿﺎﻓﺔ ﻗﺎﻋﺩﺓ )ﻣﺛﻝ ‪ ،(NaOH‬ﻳﺑﺩﺃ ﺗﻔﻛﻙ ﺍﻟﻭﻅﺎﺋﻑ‬
‫ﺑﺎﻟﻭﻅﻳﻔﺔ ﺍﻷﻛﺑﺭ ﺣﻣﻭﺿﺔ‪ ،‬ﺃﻱ ‪ pK‬ﺍﻟﻣﻧﺧﻔﺽ )ﺗﺗﺟﻠﻰ ﻗﻭﺓ ﺍﻟﺣﻣﻭﺿﺔ ﻓﻲ ﺳﻬﻭﻟﺔ ﺍﻟﺗﺟﺭﺩ ﻣﻥ ﺍﻟﺑﺭﻭﺗﻭﻥ ‪(H+‬‬
‫ﻭ ﻫﻲ ﻭﻅﻳﻔﺔ ‪ COOH‬ﺃﻟﻔﺎ ﻟﻠﺣﻣﺽ ﺍﻷﻣﻳﻧﻲ‪ .‬ﻳﻣﺛﻝ ﺍﻟﺭﺳﻡ ﺍﻟﺗﺎﻟﻲ ﻣﻧﺣﻧﻰ ﻣﻌﺎﻳﺭﺓ ﺍﻟﺟﻠﻳﺳﻳﻥ‪.‬‬

‫ﺗﻌﺗﺑﺭ ﻣﻧﻁﻘﺗﻲ ﻣﻧﺣﻧﻰ ﻣﻌﺎﻳﺭﺓ ﺍﻟﺟﻠﻳﺳﻳﻥ ﺍﻟﻣﺗﻣﻳﺯﺗﺎﻥ ﺑﺗﻐﻳﺭ ﻁﻔﻳﻑ ﻓﻲ ‪ pH‬ﺭﻏﻡ ﺇﺿﺎﻓﺔ ﺍﻟﻘﺎﻋﺩﺓ‪ ،‬ﻣﻧﻁﻘﺗﻳﻥ‬
‫ﻣﻧﻅﻣﺗﻳﻥ )‪ .(zones tampons‬ﻭ ﻫﻲ ﺗﻭﺟﺩ ﺣﻭﻝ ﻧﻘﺎﻁ ‪) pK‬ﻣﻧﺎﻁﻖ ﻧﺻﻑ ﺗﻔﻛﻙ ﻣﺟﻣﻭﻋﺎﺕ‬
‫ﺍﻟﻛﺭﺑﻭﻛﺳﻳﻝ ﻭ ﺍﻷﻣﻳﻥ‪ .(zones de demi-dissociation ،‬ﻟﻛﻝ ﺍﻷﺣﻣﺎﺽ ﺍﻷﻣﻳﻧﻳﺔ ﻗﺩﺭﺓ ﻋﻠﻰ ﺍﻟﻌﻣﻝ‬
‫ﻛﻣﺣﺎﻟﻳﻝ ﻣﻧﻅﻣﺔ )‪ (solutions tampons‬ﻭ ﺗﻛﻭﻥ ﻗﺩﺭﺗﻬﺎ ﻋﻠﻰ ﺍﻟﺗﻧﻅﻳﻡ ﺃﻋﻠﻰ ﻋﻧﺩﻣﺎ ﻳﻛﻭﻥ ﺗﺭﻛﻳﺯ‬
‫ﻭﺍﻫﺏ ﺍﻟﺑﺭﻭﺗﻭﻥ ﻳﺳﺎﻭﻱ ﺗﺭﻛﻳﺯ ﻣﺳﺗﻘﺑﻝ ﺍﻟﺑﺭﻭﺗﻭﻥ‪.‬‬

‫ﻓﻳﺩﻳﻭ‪https://youtu.be/FRksDQQh2rM :‬‬