Controlled Synthesis of Shell Cross-Linked Helical Poly(phenylborate isocyanide) Nanoparticles with H2O2/Redox Dual Responsiveness and Their Application in Antitumor Drug Delivery.

To mimic the helical structure and function of biopolymers, shell cross-linked nanoparticle (P4) composed of left-handed helical poly(phenylborate isocyanide) in core and hydrophilic polyisocyanide in shell was prepared. The phenylborate in the core and the disulfide bonds in the cross-linkage render the nanoparticle with excellent dual stimuli-responsiveness to glutathione (GSH) and H2O2. Nevertheless, it has good stability in normal physiological conditions. Because of the helicity and borate pendants of the core, such nanoparticle has high capacity for anticancer drug loading, for example, the loading capacity of doxorubicin (DOX) was up to 68%. Moreover, the DOX-loaded DOX@P4 showed excellent tumor cell penetration potency and fast drug release. More than 78% of murine breast cancer cell (4T1) can be killed within 48 h, supporting this material with great potential in antitumor drug nanocarriers.

Synthesis and Characterization of Dual Stimuli-Sensitive Biodegradable Polyurethane Soft Hydrogels for 3D Cell-Laden Bioprinting.

Three-dimensional bioprinting serves as an attractive platform to fabricate customized tissue-engineered substitutes from biomaterials and cells for the repair or replacement of injured tissues and organs. A common challenge for 3D bioprinting materials is that the structures printed from the biodegradable polymer hydrogels tend to collapse because of the poor mechanical stability. In this study, dual stimuli-responsive biodegradable polyurethane (PU) dispersions (PUA2 and PUA3) were synthesized from an eco-friendly waterborne process. Acrylate group was introduced in the PU chain end to serve as a photosensitive moiety for UV-induced cross-linking and improvement of the printability, while mixed oligodiols in the soft segment remained to be the thermosensitive moiety. The photo/thermal-induced morphological changes of PU nanoparticles were verified by dynamic light scattering, small-angle X-ray scattering, and rheological measurement of the dispersions. It was observed that these PU nanoparticles became more rod-like in shape after UV treatment and formed compact packing structures upon further heating. With the thermosensitive properties, these UV-cured PU dispersions underwent rapid thermal gelation with gel moduli in the range 0.5-2 kPa near body temperature. The rheological properties of the PU hydrogels including dynamic viscoelasticity, creep recovery, and shear thinning behavior at 37 °C were favorable for processing by microextrusion-based 3D printing and could be easily mixed with cells before printing to produce cell-laden constructs. The dual-responsive hydrogel constructs demonstrated higher resolution and shape fidelity as well as better cell viability and proliferation than the thermoresponsive control. Moreover, the softer hydrogel (PUA3) with a low modulus (<1 kPa) could offer neural stem cells a tofu-like, stable, and inductive 3D microenvironment to proliferate and differentiate. We expect that the photo/thermoresponsive biodegradable polyurethane ink may offer unique rheological properties to contribute toward the custom-made bioprinting of soft tissues.

Carbon-Quantum-Dots-Loaded Mesoporous Silica Nanocarriers with pH-Switchable Zwitterionic Surface and Enzyme-Responsive Pore-Cap for Targeted Imaging and Drug Delivery to Tumor.

Mesoporous silica nanocarriers with pH-switchable antifouling zwitterionic surface, enzyme responsive drug release properties and blue fluorescence are reported. Prolonged circulation in the blood system with zero premature release as well as efficient cellular uptake and intracellular drug release in tumor tissue are achieved.