Stereolithography‐Based Hydrogel Microenvironments to Examine Cellular Interactions

A spatially organized three‐dimensional (3D) co‐culture of multiple cell types is required to recapitulate cellular interactions and microenvironments in complex tissues. Although there are limited reports for 3D patterning of cells and materials, approaches to examine functional interactions of 3D spatially patterned multiple cell types are lacking entirely. This is mostly due to difficulties in controlling the physical arrangement of cells in a 3D matrix and the physical properties of the cell‐encapsulating matrix, while keeping the cells alive and functional for extended periods of time. In this study, an automated maskless fabrication technique is combined with a tunable polymer blend to spatially organize primary hippocampus neurons (HNs) and skeletal muscle myoblast cells (MCs) in a 3D hydrogel matrix with tunable mechanical and degradation properties. The spatial organization of these multiple cell types revealed that the presence of MCs resulted in increased cholinergic functionality of the HNs, as quantified by their choline acetyltransferase activity. The presence of a factor alone is not sufficient, but its spatiotemporal control is necessary; a condition that is possibly true for many cellular interactions. Therefore, the system described here offers a different approach to examine such previously unknown interactions. The approach proposed in this study can be used to examine interactions between many different cell types and shift the 3D fabrication paradigm to a next level, which is to fabricate tissues that are not only viable but also functional.     

Molecularly Engineered Biodegradable Polymer Networks with a Wide Range of Stiffness for Bone and Peripheral Nerve Regeneration

To satisfy different mechanical requirements in hard and soft tissue replacements, a series of biodegradable and crosslinkable copolymers of poly(propylene fumarate)‐co‐polycaprolactone (PPF‐co‐PCL) are synthesized and employed to fabricate 2D disks and 3D scaffolds via photocrosslinking. Thermal properties such as the glass transition temperature (T_g) and melting temperature (T_m) of the PPF‐co‐PCL networks can be controlled efficiently by varying the PCL composition (φ_PCL). As a result, their mechanical properties vary significantly from hard and stiff materials to soft and flexible ones with increasing φ_PCL, making them attractive candidate materials for bone and peripheral nerve regeneration, respectively. Several PPF‐co‐PCL formulations are selected to perform in vitro cell studies using mouse pre‐osteoblastic MC3T3‐E1, rat Schwann cell precursor line (SPL201), and pheochromocytoma (PC12) cells, and in vivo animal testing in the rat femur bone defect model and in the rat sciatic nerve transection model. The formation of new bone in the porous bone scaffolds with a low φ_PCL and guided axon growth through the nerve conduits with a higher φ_PCL suggest that crosslinked PPF‐co‐PCLs have appropriate compatibility and functionality. Furthermore, the role of surface stiffness in modulating cellular behavior and functions is verified on the crosslinked PPF‐co‐PCL surfaces without any pretreatments.     

Modular Multifunctional Poly(ethylene glycol) Hydrogels for Stem Cell Differentiation

Synthetic polymers are employed to create highly defined microenvironments with controlled biochemical and biophysical properties for cell culture and tissue engineering. Chemical modification is required to input biological or chemical ligands, which often changes the fundamental structural properties of the material. Here, a simple modular biomaterial design strategy is reported that employs functional cyclodextrin nanobeads threaded onto poly(ethylene glycol) (PEG) polymer necklaces to form multifunctional hydrogels. Nanobeads with desired chemical or biological functionalities can be simply threaded onto the PEG chains to form hydrogels, creating an accessible platform for users. The design and synthesis of these multifunctional hydrogels are described, structure‐property relationships are elucidated, and applications ranging from stem cell culture and differentiation to tissue engineering are demonstrated.     

Obtaining Characteristic 4f–4f Luminescence from Rare Earth Organic Chelates

We report a study of a series of heavy rare earth tris‐8‐hydroxyquinolines (REQ₃s), using UV‐visible absorption spectroscopy, infrared absorption spectroscopy, and photoluminescence (PL) measurements. We show that the heavy REQ₃s are all chemically similar to each other and to aluminium tris‐8‐hydroxyquinoline, at least in terms of the ligand behavior. Characteristic rare earth 4f–4f luminescence is only observed for ErQ₃ and YbQ₃ due to the relatively low energy of the ligand triplet state. We show that a triplet transfer mechanism cannot be responsible for the observed Yb 4f–4f luminescence observed in YbQ₃. Instead, an internal chemiluminescent process is shown to be energetically favorable. The thin film PL spectra of all the heavy REQ₃s are dominated by triplet emission, except for that of ErQ₃, for which transfer to the Er³⁺ ion represents an efficient alternative. The PL spectra of powder samples, which would be expected to consist of approximately equal amounts of both isomers, are dominated by singlet emission. This is in contrast to the results from the thin films, and suggests that the isomer which predominates in the thin films has a much higher intersystem crossing rate than the other isomer.     

Controlled Polarizability of One‐Nanometer‐Thick Oxide Nanosheets for Tailored,High‐κ Nanodielectrics

An important challenge in current microelectronics research is the development of techniques for making smaller, higher‐performance electronic components. In this context, the fabrication and integration of ultrathin high‐κ dielectrics with good insulating properties is an important issue. Here, we report on a rational approach to produce high‐performance nanodielectrics using one‐nanometer‐thick oxide nanosheets as a building block. In titano niobate nanosheets (TiNbO₅, Ti₂NbO₇, Ti₅NbO₁₄), the octahedral distortion inherent to site‐engineering by Nb incorporation results in a giant molecular polarizability, and their multilayer nanofilms exhibit a high dielectric constant (160–320), the largest value seen so far in high‐κ nanofilms with thickness down to 10 nm. Furthermore, these superior high‐κ properties are fairly temperature‐independent with low leakage‐current density (<10^?7 A cm^?2). This work may provide a new recipe for designing nanodielectrics desirable for practical high‐κ devices.