'*!#2&.)2 '!)!*+, !"!#$%& '!()() '!)!*+, ,”+- %*.+!/ ,'!&0 '!!1 -2&!3 ,$!40+, !#24#!4 ,,”+02 2"2 '!.!#2&.)2 '!+2&#1 :'!*+, /6#7)26 2, 82&#1 "”0-& * (,”+0) Ribosymes (! #&, ,!+2&#1 '!!.!#.6 '!+-42+2 (9()$& -23) 02.*!#.6" ()() * Chemical reactions and energy changes reactants If energy of reactants is greater than energy of products, energy is give out (released) during the reaction: EXERGONIC !"#$%&'( products If energy of reactants is less than energy of products, energy is taken in (absorbed) during the reaction: ENDERGONIC !"#$%)*( reactants INCREASING ENERGY ”!"#$%$&"'()”* +"#,$& $!5&!.6, %!!40+, * 1%7)-#23+) * #!37 0%, * Km 2 Vmax * '!!%201% '!&"3) * '!!0./2#,2 Energy is released to the surroundings products products Energy is absorbed from the surroundings reactants Reaction profile Reaction profiles transition state following the course of a one-step exergonic chemical reaction (or activated complex) e n e r g y bonds breaking activation energy, Ea reactants bonds forming exergonic reaction e n er g y reactants exergonic reaction products Course of reaction Reaction profiles following the course of a one-step endergonic chemical reaction products e n er g y products Click for endergonic exergonic reaction reactants Replay Close window ”!"#$%$&"'()”* +"#,$& $!5&!.6, %!!40+, * 1%7)-#23+) * #!37 0%, * Km 2 Vmax * '!!%201% '!&"3) * '!!0./2#,2 1%7) -#23+) %),%$ 1%7) -#23+) %),%$ (...'!)37#) ATP O O P O O O P O P O N O O P O O P O O H H OH H H O N NH N N O O GTP NH2 N O N O O O P O NH2 O O- H H OH H H H N H ATPase: ATP GTP X ADP + Pi Nitrogen fixation All living organisms need nitrogen • Nucleotides • Amino acids • Other bio-molecules But, although earth atmosphere is 78% N2 most organisms can not use it, and need fixed nitrogen - NH3, NO3, Urea etc. 3&26) 86+1# %2026) $(2#( !)!" 8('2!" .('-, !-! $(3)) %!/1! (-1 * .$-( !#2-!4& 86+1$) 18%" Haber-Bosch 9!#$%& 052!) * Fixed nitrogen can come from a three sources Fixed nitrogen can come from a three sources • Fertilizers • Fertilizers • Decaying bio-material • Biological Nitrogen Fixation • Decaying bio-material • Biological #( %2!367 Nitrogen Fixation !3&. 8(- - /2)02% rhizobium Nostoc Fixed nitrogen can come from a three sources • Fertilizers +"",-$. +"/0"".* 1/(. 2$*"/ • Decaying bio-material • Biological Nitrogen Fixation Azotobacter Trichodesmium 2 3 N2+3H2->2NH Fritz Haber (Nobel 1918) and Carl Bosch (1/2 nobel 1931) Haber-Bosch process: Mix gaseous H2 and N2 under: * high temperature (~500oC) * high pressure (~250 atmospheres, ~351kPa) * In the presence of a catalyst (porous iron prepared by reducing magnetite, Fe3O4). (N2->NH3) $!+2),# 86+1 02*!1 !)0%2/6, 9!#$% ,2$ !42#2!& 86+1 32&!6 kJ/mol 92.4 !$!40+, 001() $"2)+ $!40+, %)0& (NH3) 052%$( 822!" (N2-2 H2) '!.0./&2/$) 0%2! ?!"#3() !*3! 45 %5 4"36 2$0& ') • Only by bacteria (both archaea and eubacteria) • It is done by the nitrogenase multi-protein complex (NifH, D and K). A large protein hetro-oligomer • Although energetically favorable, it is bib-energetically expensive due to the very stable triple N N bond N2+10H++8e-+16ATP -> 2NH4++ H2+16ADP* *) As measure in-vitro • Other triple bond substrates cyanide (H!C N), azide (N3; both to NH3), and acetylene (HC CH) among others evolutionary origin? • The complex contain multiple metal centers, Fe-S, Mo etc. Also alternative complexes 2 3 N2+3H2->2NH Fritz Haber (Nobel 1918) and Carl Bosch (1/2 nobel 1931) Haber-Bosch process: Mix gaseous H2 and N2 under: * high temperature (~500oC) * high pressure (~250 atmospheres, ~351kPa) * In the presence of a catalyst (porous iron prepared by reducing magnetite, Fe3O4). Biological nitrogen fixation: * 1 atm * ~ room temperature * Catalyst? = enzyme - Nitrogenase !" #$%$&'( #$($)*" $+,&*"- #'./(- 1/2 N2->N e n e r g y activation energy, Ea 3/2 H2->3H N+3H>NH3 reactants %20)# ,'2!$# 82"+ 061+ *+420.!+$ /6#7)26( 2#( $#237$ 82+4+) ,%2&0 .020& !0)4# ,# exergonic reaction 1/2 N2, 3/2 H2 NH3 Course of reaction '!)!*+,$ 9!, *, ”?$* %, '!(23“ ”!"#$%$&"'()”* +"#,$& $!5&!.6, %!!40+, * 2,0 - '!)37#) 1%7)-#23+) * (*+420.!+ #!37 0%, * Km 2 Vmax * '!!%201% '!&"3) * '!!0./2#,2 '!*2*!# - .0./&2/ 86!#42-!.77 (cleft) ”36(”& ,5)+ '!*2*!# #( #!37$ 0%,$ +"'() 352 52 ,”1 - #!37$ 0%,# &# 2)!( 82+4+) $#237$ #( '!*2*!# +"'$'"% %, !%$2-! 1$(#(& '!!.40+, '!#26!( %!.)!*+, $!56,0# !#)!/ 425! Enzyme + Substrate ⇌ ES ! E + Product 352 52 ,”1 - #!37$ 0%,# &# 2)!( E + S ⇌ ES ! E + P