DNA liquid crystals with AIE effect toward humidity-indicating biomaterials.

In this study, by fabricating DNA doped with tetraphenylethene-containing ammonium surfactant, the resulting solvent-free DNA ionic complex could undergo a humidity-induced phase change that could be well tracked by the fluorescence signal of the surfactant. Taking advantage of the humidity-induced change in fluorescence, the reported ionic DNA complex could accurately indicate the humidity in real time.

Photoresponsive protamine ionic complex towards a smart hemostatic biomaterial.

Protamine (PA) is the only licensed antidote for reversing heparin anticoagulation by electrostatically binding with heparin. Efforts have been made on designing various heparin-scavengers, while, it remains a great challenge for gaining the external-stimuli responsive PA-release material. In this study, a generic strategy is developed for fabricating photoresponsive protein materials with the designed azobenzene-containing surfactant. For the first time, based on the isomerization of azobenzene, both cationic and anionic proteins could be phase change biomaterials which are capable of transiting to isotropic state under UV irradiation at room temperature. The formation of isotropic state could set the proteins free from the binding state, activating their intrinsic biological functions. Employing this mechanism, one smart PA material for inhibiting heparin is developed, which could effectively photo-modulate the heparin concentration by turning on-and-off the free state of PA from the binding state. With good biocompatibility, the PA material addresses photoresponsive hemostatic activity in biological studies, confirming its great potential clinical values. This work provides a new designing strategy for gaining photocontrollable hemostasis materials, also opening new opportunities for developing photoresponsive protein drugs and biomedical materials.

Photoresponsive heparin ionic complexes toward controllable therapeutic efficacy of anticoagulation.

Controllable heparin-release is of great importance and necessity for the precise anticoagulant regulation. Efforts have been made on designing heparin-releasing systems, while, it remains a great challenge for gaining the external-stimuli responsive heparin-release in either intravenous or catheter delivery. In this study, an azobenzene-containing ammonium surfactant is designed and synthesized for the fabrication of photoresponsive heparin ionic complexes through the electrostatic complexation with heparin. Under the assistance of photoinduced trans-cis isomerization of azobenzene, the obtained heparin materials perform reversible athermal phase transition between ordered crystalline and isotropic liquid state at room temperature. Compared to the ordered state, the formation of isotropic state can effectively improve the dissolving of heparin from ionic materials in aqueous condition, which realizes the photo-modulation on the concentration of free heparin molecules. With good biocompatibility, such a heparin-releasing system addresses photoresponsive anticoagulation in both in vitro and in vivo biological studies, confirming its great potential clinical values. This work provides a new designing strategy for gaining anticoagulant regulation by light, also opening new opportunities for the development of photoresponsive drugs and biomedical materials based on biomolecules.

Azobenzene-containing surfactant directs small features of DNA thermotropic liquid crystals via bottom-up and top-down strategies.

Compared to classical block copolymers, the self-assembly of small molecules shows an advantage in addressing small features. As a new type of solvent-free ionic complexes, azobenzene-containing DNA thermotropic liquid crystals (TLCs) form an assembly as block copolymers when using small DNA. However, the self-assembly behavior of such biomaterials has not been fully investigated. In this study, photoresponsive DNA TLCs are fabricated by employing an azobenzene-containing surfactant with double flexible chains. For these DNA TLCs, the self-assembly behavior of DNA and surfactants could be guided by the factors of the molar ratio of azobenzene-containing surfactant, dsDNA/ssDNA, and presence or absence of water, which addresses the bottom-up control on domain spacing of mesophase. Meanwhile, such DNA TLCs also gain top-down control on morphology via photoinduced phase change. This work would provide a strategy for regulating the small features of solvent-free biomaterials, facilitating the development of patterning templates based on photoresponsive biomaterials. STATEMENT OF SIGNIFICANCE: The relationship between nanostructure and function is attractive in the science of biomaterials. With biocompatibility and degradability, photoresponsive DNA materials in solutions have been widely studied in biological and medical areas, but they are still hard to obtain in a condensed state. The complex created with designed azobenzene-containing surfactants paves the way for obtaining condensed photoresponsive DNA materials. However, fine control of the small features of such biomaterials has not yet been achieved. In this study, we present a bottom-up strategy of controlling the small features of such DNA materials and, simultaneously, the top-down control of morphology via photoinduced phase change. This work provides a bi-directional approach to controlling the small features of condensed biomaterials.