Trimesoyl 1,3,5-tridimethyl malonate (TTDMM), trimesoyl 1,3,5-tridiethyl malonate (TTDEM), trimesoyl 1,3,5-tridipropyl malonate, trimesoyl 1,3,5-tridibutyl malonate, and trimesoyl 1,3,5-tridihexyl malonate first-generation dendrimers, a complete series of dialkyl malonate esters from methyl to hexyl, were synthesized by a divergent growth approach with about a 95% yield. TTDMM and TTDEM members of this series were characterized with 500-MHz NMR and Fourier transform infrared spectroscopy. The 7.469353 and 8.435395 m(2)/g surface areas and 700.1907- and 792.6436-nm pore-average diameters of TTDMM and TTDEM, respectively, implied that they could be used as prospective drug binders. Alkyl chains from methyl to hexyl of dialkyl malonate esters had enhanced interstitial spaces to trap the drugs and toxic heavy metals for their distribution and bioremediation, respectively. Thus, the dendrimers, silibinin (SB) complexes in a 1:1 ratio with acetone, were prepared and studied with Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic light scattering, scanning electron microcopy, and atomic force microscopy. The ultraviolet-visible spectroscopy at a 330-nm lamda max ((max)) showed about 5%/h SB released in phosphate buffered saline with 10% dimethyl sulfoxide. The objective was used to investigate the capacity of dialkyl malonate terminated dendrimers to encapsulate a maximum amount of SB and anticancer drugs and the in vitro releasing activity. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3537-3554, 2013