Development of novel chimeric toxins for targeted therapy by genetic engineering


 

Principal Investigator : Janendra K Batra

Project Assistants
Purushottam Kumar (till Aug 2000)
Umesh Ahuja (till Dec 2000)

Ph D Students
Anita Goyal (till June 2000)
Deepak Gaur
Shveta
Divya Vijayan

Design and development of recombinant protein toxins for targeted therapy is the theme of research. Members of two families of ribonucleases namely (i) Aspergillus ribotoxins and (ii) human ribonucleases are being analyzed for structure-function relationships to understand their molecular mechanism of action with an aim to design knowledge-based chimeric toxins.

A.    Studies on the molecular mechanism of action of ribonucleolytic protein toxins

The objective of this study was to investigate structure-function relationship of Aspergillus ribotoxin restrictocin, human pancreatic ribonuclease (HPR), eosinophil cationic protein (ECP), and eosinophil-derived neurotoxin (EDN) to understand their mechanism of action.

The HPR mutants were further characterized for their interaction with the ribonuclease inhibitor (RI). The ribonuclease activity of the mutants, in the presence of RI, was quantitatively studied by assaying their activity on poly(C). At an enzyme concentration of 0.8 ng, and a RI concentration of 0.25 U, wt HPR, K7A and N71A showed 30% activity, whereas the mutants Q11A and E111A exhibited 60-80% activity. However, when the enzyme concentration was increased to 1.6 ng, all the four mutants showed full enzymatic activity in the presence of RI, whereas HPR exhibited only 50% activity. The double mutants Q11A:E111A and N71A:E111A, and the triple mutant K7A:N71A:E111A exhibited 60-95% activity at a concentration of 0.8 ng in the presence of 0.25U RI. However, the behavior of mutants K7:E111A, Q11A:N71A:E111A and K7A:Q11A:N71A:E111A in the presence of RI was found to be similar to that of wt HPR. These results suggest that the mutants – K7A, Q11A, N71A, E111A, Q11A:E111A, N71A:E111A and K7A:N71A:E111A are less sensitive to inhibition by RI than wt HPR. The inhibition constants (Ki) for the RI-HPR/mutant interactions were determined by measuring the steady state rate of poly(C) cleavage in the presence of RI. The Ki values for the seven mutants – K7A, Q11A, N71A, E111A, Q11A:E111A, N71A:E111A and K7A:N71A:E111A were 5-25 fold higher than that of wt HPR, indicating that the binding affinity of the mutants with RI had been reduced. In order to study the effect of these mutations on the interaction of HPR with the intracellular RI, their cytotoxic activity was assayed on U373 MG, J774.A1, K562, A431, and A549 cell lines. The HPR triple mutant K7A:N71A:E111A, which exhibited maximum resistance against RI, was found to be most cytotoxic. It displayed at least a 10-fold higher cytotoxic activity than HPR on the most sensitive cell line U373MG. The mutants Q11A and E111A were 2-3 fold more cytotoxic than wt HPR on all the cell lines studied. Similarly, the mutants N71A:E111A, Q11A:E111A, K7A and N71A exhibited higher cytotoxicity than HPR; however, they were not as potent as the mutants Q11A and E111A.

HPR exhibits significantly high ribonuclease activity on double stranded RNA, compared to RNase A. In the dimeric bovine seminal ribonuclease, that exhibits a 46- fold higher activity on dsRNA compared to RNase A, two glycine residues at positions 38 and 111 have been found to play an important role in the activity on dsRNA. In HPR, a glycine residue is present at position 38 only, whereas RNase A is devoid of any glycine residue at these positions. The present study was conducted to investigate the role of the glycine residue at position 38 and the effect of incorporating a glycine residue at position 111 on the activity of HPR on dsRNA. Five mutants of HPR-G38A, G38D, E111A, E111G and G38D; E111G were prepared by site directed mutagenesis. The mutants were expressed in E.coli and the proteins were purified to homogeneity. The CD spectra of the mutants G38A, G38D, E111A, E111G showed structural similarity with wt HPR; however, the secondary structure of the mutant G38D:E111G appeared to be altered. All the mutants exhibited RNase activity on the substrates Poly(C), yeast tRNA and cCMP similar to that of wt HPR. The activity of the mutants on double stranded RNA was studied by assaying their activity on poly(A).poly(U). The mutants G38D and G38D:E111G displayed a lower activity than wt HPR. The mutant E111G showed a higher activity on Poly(A).Poly(U). The mutants G38A and E111A exhibited a similar activity on dsRNA as wt HPR. The substitution of Gly38 to Ala (G38A) is a conservative mutation in which there is no significant change in the nature or charge of the side chain and thus produces no change in activity of HPR. However, the mutation of Gly38 to Asp (G38D), a residue present in RNase A, results in the loss of activity on duplex RNA. The substitution of Glu111 to Gly (E111G) results in an enhancement in the RNase activity on dsRNA. These results suggest that glycine at positions 38 plays an important role in the activity of HPR on dsRNA.

To study the mechanism of action of saporin, the putative active site residues, Y72, Y120, E176, R179 and W208 were mutated to alanine. Two additional invariant residues Y16 and R24, proposed to be playing a role in normal a-helical pattern of saporin were also mutated to alanine. The mutants were expressed in E.coli, and the proteins were purified to homogeneity. The CD-spectral analysis of mutants showed that except for Y16A, all the mutants retained the structure similar to saporin. The protein synthesis inhibitory activity of mutants was assessed in an in vitro translation assay. R24A and W208A showed similar activity as saporin, whereas mutation of Y16, Y72, Y120, E176 and R179 resulted in the loss of protein synthesis inhibitory activity. Mutants were also assessed for their specific 28S rRNA glycosylase activity. Saporin, R24A and W208A released the a-fragment from the 28S rRNA, on aniline treatment, at a concentration as low as 0.04mg/ml, whereas Y16A, Y72A, Y120A, E176A and R179A started showing a faint band only at 1mg/ml, indicating at least a 25-fold reduction in the activity due to these mutations. Y72A released a a-fragment after 5mg/ml The DNase-like activity of saporin and its mutants was studied on plasmid pBR322. At lower concentrations (0.25-1.0mg/ml of saporin/2mg of DNA) saporin changes the conformation of DNA, whereas at higher concentrations (2-3mg and more) it completely digests the DNA. Among the mutants R24A, Y120A, E176A and R179A were found to be as active as saporin. Y16A and W208A (upto 4mg did not completely digest the DNA, however these mutants converted the plasmid to relaxed circular/linear form. Y72A did not act on DNA at all upto 4mg The cytotoxic activity of saporin and its mutants was studied on J774A.1, HUT102, L929 and U937 cell lines. The mutants having both the glycosidase and the DNase-like activity were found to be cytotoxic. In order to study the mechanism of toxicity, cytotoxicity experiments were done in presence of Brefeldin A and ammonium chloride. BFA apparently does not affect the cytotoxicity of saporin on L929 and J774A.1 cells. The study demonstrates that (a) the residues Y72, Y120, E176 and R179 are crucially involved in the activity of saporin, (b) both the N-glycosidase and DNase activities are required for cytotoxicity and (c) these activities may be residing in different locations in the saporin molecule.

The genes for EDN and ECP were cloned in pVEX11, expressed in E.coli, and the proteins purified to homogeneity. On yeast tRNA, EDN was 200-fold more active than ECP. On poly(U), EDN was 50-100 fold more active than ECP, and on poly(C) ECP did not show any detectable activity. The protein synthesis inhibitory activity was assessed in an in vitro translation system. EDN was 30-fold more active than ECP. To study the mechanism of action of EDN, putative active site and substrate binding residues, based on sequence and structural homology to RNase A, were mutated to alanine by site-directed mutagenesis. These residues include W7, Q14, R36, N39, Q40, H82 and D112. The mutants were expressed in E.coli and purified to homogeneity. The mutants were assayed for ribonuclease activity on various substrates and for in vitro protein synthesis inhibitory activity. On the basis of various functional assays, residues Q14 and R36 appear to be crucially involved in the ribonucleolytic activity of EDN.

B.        Construction and evaluation of ribonuclease-based chimeric toxins

The objective in this project was the development of chimeric toxins with restrictocin and human pancreatic ribonuclease, and characterization of their in vitro and in vivo cytotoxic activity. Also, to design and engineer the chimeric toxins based on the knowledge from the structure-function analysis to improve their biological activity.

Our studies have shown that HPR can be engineered to generate variants with reduced sensitivity to the intracellular inhibitor, resulting in a significant enhancement in its cytotoxic activity. Bovine seminal ribonuclease, which is a dimeric RNase with a very low sensitivity towards the intracellular ribonuclease inhibitor, has been shown earlier to have a potent antitumour activity. We have employed recombinant techniques to generate a dimeric form of HPR in which two monomers of HPR are joined by a flexible peptide linker. The gene fusion was expressed in E.coli, and the recombinant protein was purified to homogeneity. The dimeric HPR was found to contain similar ribonucleolytic activity as that of HPR. However, compared to HPR the dimeric HPR was found to have a very potent cytotoxic activity on a variety of cell lines. It is currently being evaluated on cancers of neuronal origin, on which bovine seminal ribonuclease has been shown to be very highly active. The dimeric human pancreatic ribonuclease should be a useful toxin for the construction of immunotoxins with low immunogenicity.

To target human IL4 receptor, DNA coding for human IL4 was used to generate chimeric toxins IL4-restrictocin, IL4-spacer-restrictocin, restrictocin-IL4 and restrictocin-spacer-IL4. Chimeric toxins with saporin targeted at the IL4 receptor were also made containing the ligand at the amino and carboxy terminus of saporin. The chimeric toxins have been produced in E.coli and proteins have been purified to homogeneity. Various proteins are now being characterized for their cytotoxic activity on the target cell lines.