SummaryA new series of polymerizable methacrylated anthraquinone dyes has been synthesized by nucleophilic aromatic substitution reactions and subsequent methacrylation. Thereby, green 5,8-bis(4-(2-methacryloxyethyl)phenylamino)-1,4-dihydroxyanthraquinone (2), blue 1,4-bis(4-((2-methacryloxyethyl)oxy)phenylamino)anthraquinone (6) and red 1-((2-methacryloxy-1,1-dimethylethyl)amino)anthraquinone (12), as well as 1-((1,3-dimethacryloxy-2-methylpropan-2-yl)amino)anthraquinone (15) were obtained. By mixing of these brilliant dyes in different ratios and concentrations, a broad color spectrum can be generated. After methacrylation, the monomeric dyes can be covalently emplaced into several copolymers. Due to two polymerizable functionalities, they can act as cross-linking agents. Thus, diffusion out of the polymer can be avoided, which increases the physiological compatibility and makes the dyes promising compounds for medical applications, such as iris implants.

SummaryThe release of anthraquinone dyes from β-cyclodextrin modified, hyperbranched polyethylenimine (PEI-CD) was investigated. 5,8-Dichloro-1,4-dihydroxyanthraquinone (AQ-OH) was enclosed simply by ionic attraction between the phenolate groups of AQ-OH and the protonated amino groups of polyethylenimine (PEI). Additionally, the adamantyl moieties of 1,4-bis-N-adamantylaminoanthraquinone (AQ-Ada) were encapsulated by the cavity of CD modified PEI. Due to these different types of interaction, the dyes can be controllably released from the CD-cavity (AQ-Ada) by temperature variation or from salt encapsulation by pH variation (AQ-OH), as monitored by UV–vis spectroscopy.

Two anthraquinone dyes, 5,8-di-N -adamantylamino-1,4-dihydroxyanthraquinone (AQ-OH) and 1,4-di-N -adamantylaminoanthraquinone (AQ-H), are synthesized. The combination of AQ-OH and AQ-H with hyperbranched polyethylenimine (PEI) bearing covalently attached β -cyclodextrin spontaneously formed host-guest complexes with hydrodynamic diameters of about 260 nm. Even enlarged structures of the trifunctional AQ-H were observed via DLS. Repeated measurements show that their assembly and disassembly is reversible with a critical point at 26 ° C and therefore switchable via temperature. Also superstructures up to 100 μ m were detected via TEM, cryo-TEM-, and SEM. Hence, a smart colored network of switchable size consisting of a supramolecular approach involving an organic dye is described.[+] These authors contributed equally to this work. decomplexation behavior offers many ways to deliver active components, e.g., proteins, dyes, and anti-tumor drugs [ 7 ] to their specifi c destination and avoid undesired release. [ 8 ] Thus, using multifunctional guest molecules, networks and extended structures can be employed. [ 9 ] The adamantyl group is a very suitable guest for β -CD and inclusion phenomena with various β -CD-containing polymers are well described. [ 10 ] However, up to now such hyperbranched systems with covalently attached β -CD where not yet subjected to interact with adamantyl-modifi ed dye molecules. These compounds were synthesized as model substances for examining the different complexation behavior of adamantyl and anthraquinone moieties coexisting in one molecule. Anthraquinone dyes are readily available, easy to modify, thus versatile in color and functionality. [ 11 ] Some derivates interact with a wide range of proteins. [ 12 ] The unsubstituted quinoid rings show good inclusion properties regarding β -CD. [ 13 ] However, equilibrium constants for complexation of β -CD with anthraquinone derivatives are much lower than with adamantyl guests. [ 11 ] This characteristic can be used to create smart materials bearing various guests which can be activated or deactivated by stimuli-responsive behavior.In this present work we describe results about the supramolecular aggregation of di-adamantyl containing anthraquinone dyes with hyperbranched PEI bearing covalently attached β -CD moieties.