Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)In this work it is presented a facile and novel method for modification of bioglass surface based on (Ca-molten salt batry(2+)vertical bar Na-glass(+)) ion exchange by immersion in molten salt bath. This method allows changing selectively the chemical composition of a surface layer of glass, creating a new and more reactive bioglass in a shell that surrounds the unchanged bulk of the original BG45S5 bioglass (core-shell type system). The modified bioglass conserves the non-crystalline structure of BG45S5 bioglass and presents a significant increase of surface reactivity in comparison with BG45S5. Melt-derived bioactive glasses BG45S5 with the nominal composition of 46.1 mol% SiO2, 24.4 mol%Na2O, 26.9 mol%CaO, and 2.6 mol% P2O5 have been subjected to ion exchange at 480 degrees C in molten mixture of Ca(NO3)(2) and NaNO3 with molar ratio of 70:30 for different time periods ranging from to 60 min. The optimization studies by using XRF and XRD showed that ion exchange time of 30 min is enough to achieve higher changes on the glass surface without alters its non-crystalline structure. The chemical composition, morphology and structure of BG45S5 and bioglass with modified surface were studied by using several analytical techniques. FOR and O-1s XPS results showed that the modification of glass surface favors the formation of Si-O-NBO groups at the expense of Si-O-BO-Si bonds. Si-29 MAS-NMR studies showed that the connectivity of (Si)Q(n) species decreases from cross-linked (Si)Q(3) units to chain-like (Si)Q(2) units and finally to depolymerized (Si)Q(1) and (Si)Q(0) units after ion exchange. This result is consistent with the chemical model based on the enrichment with calcium ions of the bioglass surface such that the excess of positive charges is balanced by depolymerization of silicate network. The pH changes in the early steps of reaction of bioactive glasses BG45S5 and BG45Ca30, in deionized water or solutions buffered with HEPES were investigated. BG45Ca30 bioactive glass exhibited a significant increase in the pH during the early steps of the reaction compared to BG45S5. (C) 2016 Elsevier B.V. All rights reserved.728697Sao Paulo Research Foundation - FAPESP [2010/05394-9]Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)