Crosslinking ionic oligomers as conformable precursors to calcium carbonate.

Inorganic materials have essential roles in society, including in building construction, optical devices, mechanical engineering and as biomaterials1-4. However, the manufacture of inorganic materials is limited by classical crystallization5, which often produces powders rather than monoliths with continuous structures. Several precursors that enable non-classical crystallization-such as pre-nucleation clusters6-8, dense liquid droplets9,10, polymer-induced liquid precursor phases11-13 and nanoparticles14-have been proposed to improve the construction of inorganic materials, but the large-scale application of these precursors in monolith preparations is limited by availability and by practical considerations. Inspired by the processability of polymeric materials that can be manufactured by crosslinking monomers or oligomers15, here we demonstrate the construction of continuously structured inorganic materials by crosslinking ionic oligomers. Using calcium carbonate as a model, we obtain a large quantity of its oligomers (CaCO3)n with controllable molecular weights, in which triethylamine acts as a capping agent to stabilize the oligomers. The removal of triethylamine initiates crosslinking of the (CaCO3)n oligomers, and thus the rapid construction of pure monolithic calcium carbonate and even single crystals with a continuous internal structure. The fluid-like behaviour of the oligomer precursor enables it to be readily processed or moulded into shapes, even for materials with structural complexity and variable morphologies. The material construction strategy that we introduce here arises from a fusion of classic inorganic and polymer chemistry, and uses the same cross-linking process for the manufacture the materials.

The Cell-Isolation Capsules with Rod-Like Channels Ensure the Survival and Response of Cancer Cells to Their Microenvironment.

Current macrocapsules with semipermeable but immunoprotective polymeric membranes are attractive devices to achieve the purpose of immunoisolation, however, their ability to allow diffusion of essential nutrients and oxygen is limited, which leads to a low survival rate of encapsulated cells. Here, a novel method is reported by taking advantage of thermotropic liquid crystals, sodium laurylsulfonate (SDS) liquid crystals (LCs), and rod-like crystal fragments (LCFs) to develop engineered alginate hydrogels with rod-like channels. This cell-isolation capsule with an engineered alginate hydrogel-wall allows small molecules, large molecules, and bacteria to diffuse out from the capsules freely but immobilizes the encapsulated cells inside and prevents cells in the microenvironment from moving in. The encapsulated cells show a high survival rate with isolation of host immune cells and long-term growth with adequate nutrients and oxygen supply. In addition, by sharing and responding to the normal molecular and vesicular microenvironment (NMV microenvironment), encapsulated cancer cells display a transition from tumorous phenotypes to ductal features of normal epithelial cells. Thus, this device will be potentially useful for clinical application in cell therapy by secreting molecules and for establishment of patient-derived xenograft (PDX) models that are often difficult to achieve for certain types of tumors, such as prostate cancer.

Dual-emission hydrogel nanoparticles with linear and reversible luminescence-response to pH for intracellular fluorescent probes.

A type of dual-emission probe with highly recognizable luminescence-response to pH has been designed. For the prepared core-shell polymeric hydrogel nanoparticles probe (Eu(DBM)3Phen doped polystyrene (PS)-co-poly(N-isopropylacrylamide)(PNIPAM)/FITC), the red emission of inner encapsulated europium complexes Eu(DBM)3Phen is remained in the hydrophobic PS core and used as a stable reference signal. Comparingly, the green emission of outer electrostatic bonded fluorescent isothiocyanate (FITC) moieties on the hydrophilic PNIPAM shell is adjusted and acted linear and reversible luminescence-response to pH between 5.8 and 7.4 with an exact resolution of 0.1 units. As a remarkable and smart pH probe, the hydrogel nanoparticles show low biological toxicity and prolonged resistance to ions and photobleaching. Also, the probes have successfully discriminated the fluorescent imaging for cytoplasmic matrix based on different pH with minimum biologic background fluorescence. These dual-emission pH-sensitive hydrogel nanoparticles suggest potential applications in clinical medicine, such as cell imaging and disease diagnosis.

Repair of tooth enamel by a biomimetic mineralization frontier ensuring epitaxial growth.

The regeneration of tooth enamel, the hardest biological tissue, remains a considerable challenge because its complicated and well-aligned apatite structure has not been duplicated artificially. We herein reveal that a rationally designed material composed of calcium phosphate ion clusters can be used to produce a precursor layer to induce the epitaxial crystal growth of enamel apatite, which mimics the biomineralization crystalline-amorphous frontier of hard tissue development in nature. After repair, the damaged enamel can be recovered completely because its hierarchical structure and mechanical properties are identical to those of natural enamel. The suggested phase transformation-based epitaxial growth follows a promising strategy for enamel regeneration and, more generally, for biomimetic reproduction of materials with complicated structure.