4D Biofabrication: 3D Cell Patterning Using Shape‐Changing Films

A novel approach for fabrication of 3D cellular structures using new thermosensitive shape‐changing polymer films with photolithographically patterned surface—4D biofabrication is reported. The surface of shape‐changing polymer films is patterned to selectively adsorb cells in specific regions. The 2D cell pattern is converted to the 3D cell structure after temperature‐induced folding of the polymer films. This approach has a great potential in the field of tissue engineering and bioscaffolds fabrication.     

Half‐Cell and Full‐Cell Applications of Highly Stable and Binder‐Free Sodium Ion Batteries Based on Cu3P Nanowire Anodes

Sodium‐ion battery (SIB) is especially attractive in cost‐effective energy storage device as an alternative to lithium‐ion battery. Particularly, metal phosphides as potential anodes for SIBs have recently been demonstrated owing to their higher specific capacities compared with those of carbonaceous materials. Unfortunately, most reported metal phosphides consist of irregular particles ranged from several hundreds nanometers to tens of micrometers, thus delivering limited cyclic stability. This paper reports the sodium storage properties of additive‐free Cu₃P nanowire (CPNW) anode directly grown on copper current collector via an in situ growth followed by phosphidation method. Therefore, as a result of its structure features, CPNW anode demonstrates highly stable cycling ability with an ≈70% retention in capacity at the 260th cycle, whereas most reported metal phosphides have limited cycle numbers ranged between 30 and 150. Besides, the reaction mechanism between Cu₃P and Na is investigated by examining the intermediate products at different charge/discharge stages using ex situ X‐ray diffraction measurements. Furthermore, to explore the practical application of CPNW anode, a pouch‐type Na⁺ full cell consisting of CPNW anode and Na₃V₂(PO₄)₃ cathode is assembled and characterized. As a demonstration, a 10 cm × 10 cm light‐emmiting diode (LED) screen is successfully powered by the Na⁺ full cell.     

Organic D‐A‐π‐A Solar Cell Sensitizers with Improved Stability and Spectral Response

A novel concept “D‐A‐π‐A” organic sensitizer instead of traditional D‐π‐A ones is proposed. Remarkably, the incorporated low bandgap, strong electron‐withdrawing unit of benzothiadiazole shows several favorable characteristics in the areas of light‐harvesting and efficiency: i) optimized energy levels, resulting in a large responsive range of wavelengths into NIR region; ii) a very small blue‐shift in the absorption peak on thin TiO₂ films with respect to that in solution; iii) an improvement in the electron distribution of the donor unit to distinctly increase the photo‐stability of synthetic intermediates and final sensitizers. The stability and spectral response of indoline dye‐based DSSCs are improved by the strong electron‐withdrawing benzothiadizole unit in the conjugation bridge. The incident‐photon‐conversion efficiency of WS‐2 reaches nearly 850 nm with a power conversion efficiency as high as 8.7% in liquid electrolyte and 6.6% in ionic‐liquid electrolyte.     

Efficient and Ambient‐Air‐Stable Solar Cell with Highly Oriented 2D@3D Perovskites

3D organic–inorganic lead halide perovskites have shown great potential in efficient photovoltaic devices. However, the low stability of the 3D perovskite layer and random arrangement of the perovskite crystals hinder its commercialization road. Herein, a highly oriented 2D@3D ((AVA)₂PbI₄@MAPbI₃) perovskite structure combining the advantages of both 2D and 3D perovskite is fabricated through an in situ route. The highest power conversion efficiency (PCE) of 18.0% is observed from a 2D@3D perovskite solar cell (PSC), and it also shows significantly enhanced device stability under both inert (90% of initial PCE for 32 d) and ambient conditions (72% of initial PCE for 20 d) without encapsulation. The high efficiency of 18.0% and nearly twofold improvement of device stability in ambient compared with pure 3D PSCs confirm that such 2D@3D perovskite structure is an effective strategy for high performance and increasing stability and thus will enable the timely commercialization of PSCs.     

Spray‐Coated Silver Nanowires as Top Electrode Layer in Semitransparent P3HT:PCBM‐Based Organic Solar Cell Devices

Silver nanowire (Ag NW) thin films are investigated as top electrodes in semitransparent inverted organic solar cells. The performance of semitransparent poly(3‐hexylthiophene‐2,5‐diyl):[6,6]‐phenyl‐C61‐butyric acid methyl ester (P3HT:PCBM) organic solar cells with Ag NW top electrode layers is found to match very closely the performance of reference devices based on thermally evaporated, highly reflective metal silver top electrodes. The optical losses of the semitransparent electrodes are investigated in detail and analyzed in terms of transmission, scattering, and reflection losses. The impact on an external back reflector is shown to increase the light harvesting efficiency of optically thin devices. Further analysis of transparent devices under illumination from the indium tin oxide (ITO) backside and through the Ag NW front electrode open the possibility to gain deep insight into the vertical microstructure related devices performance. Overall, Ag NW top electrodes are established as a serious alternative to TCO based electrodes. Semitransparent devices with efficiencies of over η = 2.0% are realized.     

3D‐Printed Microrobotic Transporters with Recapitulated Stem Cell Niche for Programmable and Active Cell Delivery

Poor retention rate, low targeting accuracy, and spontaneous transformation of stem cells present major clinical barriers to the success of therapies based on stem cell transplantation. To improve the clinical outcome, efforts should focus on the active delivery of stem cells to the target tissue site within a controlled environment, increasing survival, and fate for effective tissue regeneration. Here, a remotely steerable microrobotic cell transporter is presented with a biophysically and biochemically recapitulated stem cell niche for directing stem cells towards a pre‐destined cell lineage. The magnetically actuated double‐helical cell microtransporters of 76 µm length and 20 µm inner cavity diameter are 3D printed where biological and mechanical information regarding the stem cell niche are encoded at the single‐cell level. Cell‐loaded microtransporters are mobilized inside confined microchannels along computer‐controlled trajectories under rotating magnetic fields. The mesenchymal stem cells are shown retaining their differentiation capacities to commit to the osteogenic lineage when stimulated inside the microswimmers in vitro. Such a microrobotic approach has the potential to enable the development of active microcarriers with embedded functionalities for controlled and precisely localized therapeutic cell delivery.     

Soluble Phenanthrenyl‐Imidazole‐Presenting Regioregular Poly(3‐octylthiophene) Copolymers Having Tunable Bandgaps for Solar Cell Applications

We have used Grignard metathesis polymerization to successfully synthesize a series of regioregular polythiophene copolymers that contain electron‐withdrawing and conjugated phenanthrenyl‐imidazole moieties as side chains. The introduction of the phenanthrenyl‐imidazole moieties onto the side chains of the regioregular polythiophenes increased their conjugation lengths and thermal stabilities and altered their bandgap structures. The bandgap energies, determined from the onset of optical absorption, could be tuned from 1.89 eV to 1.77 eV by controlling the number of phenanthrenyl‐imidazole moieties in the copolymers. Moreover, the observed quenching in the photoluminescence of these copolymers increases with the number of phenanthrenyl‐imidazole moieties in the copolymers, owing to the fast deactivation of the excited state by the electron‐transfer reaction. Both the lowered bandgap and fast charge transfer contribute to the much higher external quantum efficiency of the poly(3‐octylthiophene)‐side‐chain‐tethered phenanthrenyl‐imidazole than that of pure poly(3‐octylthiophene), leading to much higher short circuit current density. In particular, the short circuit current densities of the device containing the copolymer having 80 mol % phenanthrenyl‐imidazole, P82 , improved to 14.2 mA cm^–2 from 8.7 mA cm^–2 for the device of pure poly(3‐octylthiophene), P00 , an increase of 62 %. In addition, the maximum power conversion efficiency improves to 2.80 % for P82 from 1.22 % for P00 (pure P3OT ). Therefore, these results indicate that our polymers are promising polymer photovoltaic materials.     

Surface‐Modified Low‐Temperature Solid Oxide Fuel Cell

This paper reports both experimental and theoretical results of the role of surface modification on the oxygen reduction reaction in low‐temperature solid oxide fuel cells (LT‐SOFC). Epitaxial ultrathin films of yttria‐doped ceria (YDC) cathode interlayers (<10–130 nm) are grown by pulsed laser deposition (PLD) on single‐crystalline YSZ(100). Fuel cell current–voltage measurements and electrochemical impedance spectroscopy are performed in the temperature range of 350 °C ≈ 450 °C. Quantum mechanical simulations of oxygen incorporation energetics support the experimental results and indicate a low activation energy of only 0.07 eV for YDC, while the incorporation reaction on YSZ is activated by a significantly higher energy barrier of 0.38 eV. Due to enhanced oxygen incorporation at the modified Pt/YDC interface, the cathodic interface resistance is reduced by two‐fold, while fuel cell performance shows more than a two‐fold enhancement with the addition of an ultrathin YDC interlayer at the cathode side of an SOFC element. The results of this study open up opportunities for improving cell performance, particularly of LT‐SOFCs by adopting surface modification of YSZ surface with catalytically superior, ultrathin cathodic interlayers.     

3D Printed Stem‐Cell Derived Neural Progenitors Generate Spinal Cord Scaffolds

A bioengineered spinal cord is fabricated via extrusion‐based multimaterial 3D bioprinting, in which clusters of induced pluripotent stem cell (iPSC)‐derived spinal neuronal progenitor cells (sNPCs) and oligodendrocyte progenitor cells (OPCs) are placed in precise positions within 3D printed biocompatible scaffolds during assembly. The location of a cluster of cells, of a single type or multiple types, is controlled using a point‐dispensing printing method with a 200 µm center‐to‐center spacing within 150 µm wide channels. The bioprinted sNPCs differentiate and extend axons throughout microscale scaffold channels, and the activity of these neuronal networks is confirmed by physiological spontaneous calcium flux studies. Successful bioprinting of OPCs in combination with sNPCs demonstrates a multicellular neural tissue engineering approach, where the ability to direct the patterning and combination of transplanted neuronal and glial cells can be beneficial in rebuilding functional axonal connections across areas of central nervous system (CNS) tissue damage. This platform can be used to prepare novel biomimetic, hydrogel‐based scaffolds modeling complex CNS tissue architecture in vitro and harnessed to develop new clinical approaches to treat neurological diseases, including spinal cord injury.     

Tissue Engineered Bio‐Blood‐Vessels Constructed Using a Tissue‐Specific Bioink and 3D Coaxial Cell Printing Technique: A Novel Therapy for Ischemic Disease

Endothelial progenitor cells (EPCs) are a promising cell source for the treatment of several ischemic diseases for their potentials in neovascularization. However, the application of EPCs in cell‐based therapy has shown low therapeutic efficacy due to hostile tissue conditions after ischemia. In this study, a bio‐blood‐vessel (BBV) is developed, which is produced using a novel hybrid bioink (a mixture of vascular‐tissue‐derived decellularized extracellular matrix (VdECM) and alginate) and a versatile 3D coaxial cell printing method for delivering EPC and proangiogenic drugs (atorvastatin) to the ischemic injury sites. The hybrid bioink not only provides a favorable environment to promote the proliferation, differentiation, and neovascularization of EPCs but also enables a direct fabrication of tubular BBV. By controlling the printing parameters, the printing method allows to construct BBVs in desired dimensions, carrying both EPCs and atorvastatin‐loaded poly(lactic‐co‐glycolic) acid microspheres. The therapeutic efficacy of cell/drug‐laden BBVs is evaluated in an ischemia model at nude mouse hind limb, which exhibits enhanced survival and differentiation of EPCs, increased rate of neovascularization, and remarkable salvage of ischemic limbs. These outcomes suggest that the 3D‐printed ECM‐mediated cell/drug implantation can be a new therapeutic approach for the treatment of various ischemic diseases.     

Inverted‐Colloidal‐Crystal Hydrogel Matrices as Three‐Dimensional Cell Scaffolds

Successful engineering of functional tissues requires the development of three‐dimensional (3D) scaffolds that can provide an optimum microenvironment for tissue growth and regeneration. A new class of 3D scaffolds with a high degree of organization and unique topography is fabricated from polyacrylamide hydrogel. The hydrogel matrix is molded by inverted colloidal crystals made from 104 μm poly(methyl methacrylate) spheres. The topography of the scaffold can be described as hexagonally packed 97 μm spherical cavities interconnected by a network of channels. The scale of the long‐range ordering of the cavities exceeds several millimeters. In contrast to analogous material in the bulk, hydrogel shaped as an inverted opal exhibits much higher swelling ratios; its swelling kinetics is an order of magnitude faster as well. The engineered scaffold possesses desirable mechanical and optical properties that can facilitate tissue regeneration while allowing for continuous high‐resolution optical monitoring of cell proliferation and cell–cell interaction within the scaffold. The scaffold biocompatibility as well as cellular growth and infiltration within the scaffold were observed for two distinct human cell lines which were seeded on the scaffold and were tracked microscopically up to a depth of 250 μm within the scaffold for a duration of up to five weeks. Ease of production, a unique 3D structure, biocompatibility, and optical transparency make this new type of hydrogel scaffold suitable for most challenging tasks in tissue engineering.