Diagonalization of a certain operator in irreducible representations of the positive discrete series of the quantum algebra U_q(su(1,1)) is studied. Spectrum and eigenfunctions of this operator are found in an explicit form. These eigenfunctions, when normalized, constitute an orthonormal basis in the representation space. The initial U_q(su(1,1))-basis and the basis of eigenfunctions are interrelated by a matrix with entries, expressed in terms of big q-Laguerre polynomials. The unitarity of this connection matrix leads to an orthogonal system of functions, which are dual with respect to big q-Laguerre polynomials. This system of functions consists of two separate sets of functions, which can be expressed in terms of q-Meixner polynomials M_n(x;b,c;q) either with positive or negative values of the parameter b. The orthogonality property of these two sets of functions follows directly from the unitarity of the connection matrix. As a consequence, one obtains an orthogonality relation for q-Meixner polynomials M_n(x;b,c;q) with b<0. A biorthogonal system of functions (with respect to the scalar product in the representation space) is also derived.

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