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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

maduropeptin

• 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.

The dianion makes radicals

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

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

The precursor

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

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

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

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 =

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

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

k = (kb * T) exp(-DG) .

h RT

1.987 X 10-34 298EXP(-19.633)

CHANGE THIS@@

6,626 X 10-348.314-298

Rate constant first try

10+9 POWER

1.38×10−23 J K−1

298k EXP (-19.633)

J·s8.314-298

6.626×10−34

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

• • 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

• 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.

• 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.