10.

Subramanian S., Ferreira M. M. C., Trsic M., “A STRUCTURE -ACTIVITY RELATIONSHIP STUDY OF NAPHTHOQUINONES AGAINST CARCINOSARCOMA WALKER 256”. Budapest, Hungary, 21-23/ 08/1997: CC'97 Conferentia Chemometrica, Book of Abstracts, Lec23 (1997). Oral L23 - Keynote Lecture.


           A STRUCTURE -ACTIVITY RELATIONSHIP STUDY OF
  NAPHTHOQUINONES AGAINST CARCINOSARCOMA WALKER 256

        Subramanian, Shayla1; Ferreira, Márcia M. C.2 and Trsic, Milan.3

  1 Departamento de Química, CCEN, Universidade Federal da Paraíba, João Pessoa,
                                            PB, 58051-900, Brasil
  2 Instituto de Química, Universidade Estadual  de Campinas, Campinas  SP, 13081-
                                                   970, Brasil
  3 Instituto de Química de São Carlos, Universidade  de São Paulo, 13560-970,  São
                                               Carlos, SP, Brasil

    Lapachol  and   its   analogues  are  known  to  possess  antitumor,  antibiotic  and
antimalarial  activities.  Lapachol   also   exhibits   antiinflammatory   and   antiulceric
action. It has been shown that this drug  is highly active  against Walker 256  (W256)
carcinosoma tumor in rats when parenterally or orally administered.

    MNDO-AM1  semi-emipirical  molecular orbital calculations  were  carried out  on
lapachol  and  several derivatives  of  1,4-naphthoquionones  in  order  to  investigate
possible relationships  between  electronic structural  parameters  and  activity against
Carcinosarcoma  W256  reported   in  the  literature. It  was  found  that, among the
calculated   electronic   indices,   the   HOMO   (highest  occupied  molecular  orbital)
coefficients (Sci2  i = 2s, 2px, 2py and 2pz) for carbon atoms of the side chain double
bond  have   a  significant   influence   in   this  activity,  while  the   LUMO  (lowest
unoccupied  molecular  orbital)  apparently  have  no  importance  on  it.

   Exploratory data analysis by Hierarchical Cluster (HCA) and Principal Component
Analysis  (PCA) for  autoscaled  data  consisting  of  26  samples  and  10  variables,
showed  a  clear  separation  of  active  compounds  from   the  inactive  ones.   PC1
discriminated between active/inactive compounds and PC2  discriminates a  small set
of inactive compounds. This analysis gives a strong evidence that the activity against
W256 involves a mechanism wherein  the quinone  acts as  a  reductor  through  the
participation of the p-electrons of the side-chain double bond. HCA  results  confirm
the PCA presented above, suggesting  that reasonable models might  be  constructed.
A classification study  with respect  to structure-activity using  the KNN  (K-Nearest
Neighbors)  and   SIMCA   (Soft  Independent  Modeling  of  Class  Analogy),   two
established  chemometric  methods  of   Pattern  Recognition,  have  been  used  for
modeling.  A  model  for   the  active  and   inactive  compounds   was  created  and
validated  using  26  samples  as  training  set  and  a  set  of 16 1,4-naphthoquinone
derivatives  was  used  as  a  test  to  predict  their  activity/inactivity.
 

                         Lec23