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Polymers of high linear charge density but carrying not more than one charged group in the repeat unit, like the conventional vinylic polyelectrolytes, are well characterized and widely used in biotechnology and medicine, e.g. for separations of multi component proteins systems or delivery of cargo nucleic acids to the cell. The information on polyelectrolytes of higher charge density, specifically possessing two ionic or ionogenic groups in the repeat unit is rather scant. Meanwhile, there are grounds for believing that such “supercharged” polyelectrolytes are prone to bind efficiently with oppositely charged polymers, in particular proteins, enzymes and nucleic acids yielding (bio)polylectrolyte complexes. In the current work, a convenient approach for preparing of the supercharged polycations has been developed. Generally, the method is based on treatment by Menshutkin reaction of primary, secondary or tertiary amino groups of the polyamines with alkylation agent containing in the molecule pH-insensitive positively charged quaternized ammonium group.