This document discusses nine-membered enediyne chromophores which are characterized by nine-membered rings containing two triple bonds separated by a double bond. These bacterial products are highly toxic to DNA and used as antitumor agents. The document focuses on the enediyne Mark 45, analyzing its thermochemistry and using ratios to calculate changes in Gibbs free energy, enthalpy, and entropy for its forward reaction. It also calculates a rate constant for the reaction and discusses the biological importance of nine-membered enediyne natural products.

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4. Definition of Enediyne
• 1. Noun. Any of a class of bacterial products
characterized by nine- or ten-membered rings
containing two triple bonds separated by a
double bond, many of which are highly toxic
to DNA and used as antitumour agents. ¹

5. maduropeptin

6. • This paper will discuss that the 10 member and nine
members ring in enediyne chromophores c 1027
• The primary mechanism utilized by nine member
enediyne producing organisms of interest the most
biologically relevant species is the enediyne diradical.
•
• The mode of action of nine membered enediynes,
which is generally accepted is the ability to produce
single stranded or double stranded DNAlesions, this
short paper will look at c1027, and the common me
thechism which includes only three species mark 42,
mark 45 amd mark 48.

7. The dianion makes radicals

8. The dianion makes radicals
• Number of atoms: 21
• Molecular multiplicity: 2
• Molecular charge: 0
• Dipole moment (Debye): 0.68
•
• E(Hartree) = -453.9810242
• E(kcal/mol) = -284877.63

9. The dianion makes radicals
• ---Thermochemistry at 298.15 K---
• ZPE (Hartree/molecule) = 0.197373
• ZPE (kcal/mol) = 123.854
• E (kcal/mol) = 128.504
• H (kcal/mol) = 129.096
• G (kcal/mol) = 102.874
• S (cal/mol-K) = 87.950

10. The precursor

11. Mark 45 precursor
MARK 45
---Thermochemistry at 298.15 K---
ZPE (Hartree/molecule) = 0.197373
ZPE (kcal/mol) = 123.854
E (kcal/mol) = 128.504
H (kcal/mol) = 129.096
G (kcal/mol) = 102.874
S (cal/mol-K) = 87.95

12. Mark 45 precursor
•
• ---Thermochemistry at 298.15 K---
• ZPE (Hartree/molecule) = 0.197373
• ZPE (kcal/mol) = 123.864
• E (kcal/mol) = 128.504
• H (kcal/mol) = 129.906
• G (kcal/mol) = 102.874
• S (cal/mol-K) = 90.441

13. Mark 45 precursor
• Number of atoms: 21
• Molecular multiplicity: 2
• Molecular charge: 0
• Dipole moment (Debye): 0.68
•
• E(Hartree) = -453.9810242
• E(kcal/mol) = -284877.63

14. Use of ratio for forward reaction
• DG DH
• Reactant == G (kcal/mol) = 102.874
129.096
• Mark 45
• Product == = H(kcal/mol) = 83.241
108.341
• Mark 45 anion
• DG===83.241/102.874==
•
• DH====108.341/129.096 =

15. MARK 45 MARK 45 DECREMENTED
---Thermochemistry at 298.15 K--- ---Thermochemistry at 298.15 K---
ZPE (Hartree/molecule) = 0.197373 ZPE (Hartree/molecule) =
0.16513
4
ZPE (kcal/mol) = 123.854 ZPE (kcal/mol) =
103.62
3
E (kcal/mol) = 128.504 E (kcal/mol) =
107.74
8
H (kcal/mol) = 129.096 H (kcal/mol) =
108.34
1
G (kcal/mol) = 102.874 G (kcal/mol) = 83.241
S (cal/mol-K) = 87.95 S (cal/mol-K) = 84.185

16. Change is delta G: 20.231
DELTA'S
DELTA ZPE (kcal/mol) = 123.854 103.623 20.231
DELTA E (kcal/mol) = 128.504 107.748 20.756
DELTA H (kcal/mol) = 129.096 108.341 20.755
DELTA G (kcal/mol) = 102.874 83.241 19.633
DELTA S (cal/mol-K) = 87.95 84.185 3.765

17. k = (kb * T) exp(-DG).
h RT
1.987 X 10-34 298EXP
(-
19.633)
CHANGE
THIS@@
6,626 X 10-34
8.314-
298

18. Rate constant first try
10+9 POWER
1.38×10−23
J K−1
298k EXP (-19.633)
J·s
8.314-298
6.626×10−34

19. biological importance of plants
•
• begin from "the nine -membered chromoprotein
family of enediynee has steadily grown of if 12th
of thing that up and chief
• the antroquinone bridge repeats it self in the
three molecules
• lets remove it using Maestro and make
calculations on Mark 45, mark 45 ANION , an
mark 48, lets assume a solvent free system. lets
use MP2, RHF/6-311G, and B3YL

20. •
• look at the 3 species as transition states-they
are actually-a family all nine national
products is having a common remember
system
• bicyclo[7.3.0] dodecjadiynene

21. • lnK_{eq}=frac{-Delta {G^o}}{RT},
•
• If there is a decrease in Gibbs free energy from one
state to another, this transformation is spontaneous
and the lower energy state is more stable. A highly
strained, higher energy molecular conformation will
spontaneously convert to the lower energy molecular
conformation.
• Examples of the anti and gauche conformations of
butane.
• Examples of the anti and gauche conformations of
butane.

22. • the nine natural pru thatcts are that's: necarzinostatin, kedarcidin,
c-1027 fifth with, an maduropeptin and N 1199A2
•
• Although old all the known nine membered enediynes that contain
a common bicyclo[7.3.0] dodecjadiynene chromphore, only five
have complete structures
•
• Recently humorous crytpic gene clusters encoding enediyne
biosynthesis in a variety ofactinycetes have neen unvieled, subjects
thingthat these organismshave the potential to produce
uncharacterized enediynes.
•
• The latter finng may significantly increase the pool of nine
membered enediynes in the years to come.