We report the functionalization of cross-linked poly(divinylbenzene) (pDVB) microspheres using both thiol-ene chemistry and azide-alkyne click reactions. The RAFT technique was carried out to synthesize SH-functionalized poly(N-isopropylacrylamide) (pNIPAAm) and utilized to generate pNIPAAm surface-modified microspheres via thiol-ene modification. The accessible double bonds on the surface of the microspheres allow the direct coupling with thiol-end functionalized pNIPAAm. In a second approach, pDVB microspheres were grafted with poly(2-hydroxyethyl methacrylate) (pHEMA). For this purpose, the residual double bonds on the microspheres surface were used to attach azide groups via the thiol-ene approach of 1-azido-undecane-11-thiol. In a second step, alkyne endfunctionalized pHEMA was used to graft pHEMA to the azide-modified surface via click-chemistry (Huisgen 1,3-dipolar cycloaddition). The surface-sensitive characterization methods X-ray photoelectron spectroscopy, scanning-electron microscopy and FT-IR transmission spectroscopy were employed to characterize the successful surface modification of the microspheres. In addition, fluorescence microscopy confirms the presence of grafted pHEMA chains after labeling with Rhodamine B.

A combination of reversible addition fragmentation chain transfer (RAFT) polymerization and hetero Diels‐Alder (HDA) chemistry has been utilized to successfully generate functional core‐shell microspheres. Initially, precipitation polymerization in conjunction with the RAFT technique has been employed to synthesize divinylbenzene (DVB) microspheres with surface expressed RAFT groups. Subsequently, HDA cycloaddition has been performed under mild reaction conditions (50 °C, 24 h) with a diene‐functionalized poly(ε‐caprolactone) (PCL). While the successful grafting is immediately evident by optical inspection of the microspheres (color change from purple to white), X‐ray photoelectron spectroscopy (XPS), and attenuated total reflectance spectroscopy (ATR) were additionally employed to characterize the chemical composition and surface functionalization of the microspheres. Further, confocal microscopy was used to confirm the presence of grafted PCL chains after labeling them with rhodamine B.magnified image

The performance of solid substrates is not only governed by their molecular constitution, but is also critically influenced by their surface constitution at the solid/gas or solid/liquid interface. In here, we critically review the use of orthogonal chemical transformations (so‐called click chemistry) to achieve efficient surface modifications of materials ranging from gold and silica nanoparticles, polymeric films, and microspheres to fullerenes as well as carbon nanotubes. In addition, the functionalization of surfaces via click chemistry with biomolecules is explored. Although a large host of reactions fulfilling the click‐criteria exist, pericyclic reactions are most frequently employed for efficient surface modifications. The advent of the click chemistry concept has led—as evident from the current literature—to a paradigm shift in current approaches for materials modification: Away from unspecific and nonselective reactions to highly specific true surface engineering.

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The surface modification of divinylbenzene (DVB)‐based microspheres is performed via a combination of reversible addition fragmentation chain transfer (RAFT) polymerization and rapid hetero‐Diels–Alder (HDA) chemistry with the aim of quantifying the grafting densities achieved using this “grafting‐to” method. Two variants of the RAFT‐HDA concept are employed to achieve the functionalization of the microspheres. In the first approach, the microspheres are functionalized with a highly reactive diene, i.e., cyclopentadiene, and are subsequently reacted with polystyrene chains (number‐averaged molecular weight, Mn = 4200 g mol−1; polydispersity index, PDI = 1.12.) that carry a thiocarbonyl moiety functioning as a dienophile. The functionalization of the microspheres is achieved rapidly under ambient conditions, without the aid of an external catalyst. The surface grafting densities obtained are close to 1.2 × 1020 chains per gram of microspheres. In the second approach, the functionalization proceeds via the double bonds inherently available on the microspheres, which are reacted with poly(isobornyl acrylate) chains carrying a highly dienophilic thiocarbonyl functionality; two molecular weights (Mn = 6000 g mol−1, PDI = 1.25; Mn = 26 000 g mol−1, PDI = 1.26) are used. Due to the less reactive nature of the dienes in the second approach, functionalization is carried out at elevated temperatures (T = 60 °C) yet in the absence of a catalyst. In this case the surface grafting density is close to 7 chains nm−2 for Mn = 6000 g mol−1 and 4 chains nm−2 for Mn = 26 000 g mol−1, or 2.82 × 1019 and 1.38 × 1019 chains g−1, respectively. The characterization of the microspheres at various functionalization stages is performed via elemental analysis for the quantification of the grafting densities and attenuated total reflectance (ATR) IR spectroscopy as well as confocal microscopy for the analysis of the surface chemistry.