Structure-activity relationships and mode of action of 5-mercapto-substituted oligo- and polynucleotides as antitemplates inhibiting replication of human immunodeficiency virus type 1

Introduction of a reactive 5-mercapto group into some of the cytosine and/or uracil bases of various oligo- and polynucleotides by partial thiolation resulted in several potent inhibitors of the replication of human immunodeficiency virus type 1 (HIV-1) in primary human lymphocytes. These compounds exhibited little if any toxicity against uninfected peripheral blood mononuclear cells and showed 15 to 75 times higher antitemplate activity against a p66/p51 HIV-1 recombinant reverse transcriptase (RT) than against the DNA polymerase alpha from human lymphocytes. In contrast, the unthiolated oligo- and polynucleotides are void of antitemplate activity, and their apparent inhibitory effect on HIV-1 closely paralleled their toxicity for the cells. Partially thiolated poly(dC) (MPdC) was the most potent of all the compounds tested against HIV-1 in peripheral blood mononuclear cells (50% effective concentration, 1.8 micrograms/ml or 0.019 microM), while showing low cytotoxicity (greater than 100 micrograms/ml). The corresponding unmodified poly(dC) showed no anti-HIV-1 activity at 50 micrograms/ml but had pronounced cytotoxicity. MPdC was also a potent inhibitor of HIV-1 RT (50% inhibitory concentration, 0.30 micrograms/ml). The inhibitory activities of thiolated homooligo(dCs) against both HIV-1 replication and HIV-1 RT increased with increasing chain length. The heterooligonucleotides included in this study were designed as structural analogs of portions of the natural primer of HIV-1 RT, i.e., tRNA(3Lys). An 18-mer analog of the 3' terminus, complementary (antisense) to the primer-binding site of the HIV-1 genome, was attached to an oligo(dC) tail and 5-thiolated; this increased its activity and decreased its toxicity. This compound will serve as a new lead in the development of more effective antitemplates against HIV-1.

[1]  J. Sambrook,et al.  Molecular Cloning: A Laboratory Manual , 2001 .

[2]  E. Uhlmann,et al.  Antisense oligonucleotides: a new therapeutic principle , 1990 .

[3]  R. Schinazi,et al.  Combinations of 3'-azido-3'-deoxythymidine (zidovudine) and phosphonoformate (foscarnet) against human immunodeficiency virus type 1 and cytomegalovirus replication in vitro , 1989, Antimicrobial Agents and Chemotherapy.

[4]  S. Hughes,et al.  Comparison of inhibitory activities of various antiretroviral agents against particle-derived and recombinant human immunodeficiency virus type 1 reverse transcriptases , 1989, Antimicrobial Agents and Chemotherapy.

[5]  R. Schinazi,et al.  Combinations of isoprinosine and 3'-azido-3'-deoxythymidine in lymphocytes infected with human immunodeficiency virus type 1 , 1988, Antimicrobial Agents and Chemotherapy.

[6]  P. Zamecnik,et al.  Oligodeoxynucleoside phosphoramidates and phosphorothioates as inhibitors of human immunodeficiency virus. , 1988, Proceedings of the National Academy of Sciences of the United States of America.

[7]  R. Schinazi,et al.  Synthesis and antiviral activity of various 3'-azido analogues of pyrimidine deoxyribonucleosides against human immunodeficiency virus (HIV-1, HTLV-III/LAV). , 1988, Journal of medicinal chemistry.

[8]  P. Zamecnik,et al.  Inhibition of replication and expression of human T-cell lymphotropic virus type III in cultured cells by exogenous synthetic oligonucleotides complementary to viral RNA. , 1986, Proceedings of the National Academy of Sciences of the United States of America.

[9]  J. Minowada,et al.  Inhibition of DNA polymerase alpha from leukemic and normal human cells by partially thiolated human deoxyribonucleic acids. , 1985, Cancer biochemistry biophysics.

[10]  P. Chandra,et al.  Inhibitors of retroviral DNA polymerase: their implication in the treatment of AIDS. , 1985, Cancer research.

[11]  M. Kung,et al.  Plasma clearance and tissue distribution of partially thiolated polycytidylic acid and its degradation products in rodents. , 1984, Cancer research.

[12]  J. Aradi,et al.  Enzymatic synthesis of polyuridylic acid containing modified bases. , 1980, Nucleic acids research.

[13]  R. Fiel,et al.  Structural characterization of partially thiolated poly(cytidylic acid). , 1979, Biochemistry.

[14]  H. Preisler,et al.  Effects of partially thiolated polycytidylic acid on the clonogenicity of murine leukemic stem cells. , 1979, Cancer research.

[15]  M. Kung,et al.  Oligonucleotides containing modified bases. I. Inhibition of DNA and RNA polymerases by partially thiolated oligocytidylic acids. , 1976, Biochemical and biophysical research communications.

[16]  M. Kung,et al.  Action of partially thiolated polynucleotides on the DNA polymerase alpha from regenerating rat liver. , 1976, Cancer research.

[17]  P. Chandra,et al.  POLYNUCLEOTIDES CONTAINING 5‐MERCAPTO‐SUBSTITUTED PYRIMIDINES: INHIBITION OF VIRAL DNA POLYMERASES AND THE BIOLOGICAL IMPLICATION * , 1975, Annals of the New York Academy of Sciences.

[18]  A. Mikulski,et al.  Inhibition of DNA-dependent RNA polymerase with partially thiolated polynucleotides. , 1973, Biochimica et biophysica acta.

[19]  F. Eckstein,et al.  Polynucleotides containing 2'-chloro-2'-deoxyribose. , 1972, Biochemistry.

[20]  F. Kenney,et al.  Inhibition of the DNA polymerase of Rauscher leukemia virus by single-stranded polyribonucleotides. , 1971, Proceedings of the National Academy of Sciences of the United States of America.

[21]  T. Kalman,et al.  The reaction of 5-bromouracil derivatives with sulfur nucleophiles, and a novel synthetic route to 5-sulfur-substituted uracils and nucleotides. , 1970, The Journal of organic chemistry.

[22]  T. Kalman,et al.  The autoxidation of 5-mercaptouracil and 5-mercaptodeoxyuridine. , 1967, Journal of the American Chemical Society.

[23]  D. Hoard,et al.  CONVERSION OF MONO- AND OLIGODEOXYRIBONUCLEOTIDES TO 5-TRIPHOSPHATES. , 1965, Journal of the American Chemical Society.

[24]  J. F. Codington,et al.  Nucleosides. XVIII. Synthesis of 2'-Fluorothymidine, 2'-Fluorodeoxyuridine, and Other 2'-Halogeno-2'-Deoxy Nucleosides1,2 , 1964 .

[25]  T. Chou,et al.  Quantitative analysis of dose-effect relationships: the combined effects of multiple drugs or enzyme inhibitors. , 1984, Advances in enzyme regulation.

[26]  Ho Yk,et al.  Inhibition of DNA polymerase-alpha from rat hepatoma with a series of new synthetic polynucleotides. , 1983 .

[27]  Y. Ho,et al.  CHEMICAL AND ENZYMATIC METHODS IN THE SYNTHESIS OF MODIFIED POLYNUCLEOTIDES , 1978 .

[28]  M. Stephenson,et al.  Inhibition of Rous sarcoma virus replication and cell transformation by a specific oligodeoxynucleotide. , 1978, Proceedings of the National Academy of Sciences of the United States of America.

[29]  T. Bardos Antimetabolites: molecular design and mode of action. , 1974, Topics in current chemistry.

[30]  M. Yoshikawa,et al.  A novel method for phosphorylation of nucleosides to 5'-nucleotides. , 1967, Tetrahedron letters.