Silk Protein Composite Bioinks and Their 3D Scaffolds and In Vitro Characterization

This paper describes the use of silk protein, including fibroin and sericin, from an alkaline solution of Ca(OH)2 for the clean degumming of silk, which is neutralized by sulfuric acid to create calcium salt precipitation. The whole sericin (WS) can not only be recycled, but completely degummed silk fibroin (SF) is also obtained in this process. The inner layers of sericin (ILS) were also prepared from the degummed silk in boiling water by 120 °C water treatment. When the three silk proteins (SPs) were individually grafted with glycidyl methacrylate (GMA), three grafted silk proteins (G-SF, G-WS, G-ILS) were obtained. After adding I2959 (a photoinitiator), the SP bioinks were prepared with phosphate buffer (PBS) and subsequently bioprinted into various SP scaffolds with a 3D network structure. The compressive strength of the SF/ILS (20%) scaffold added to G-ILS was 45% higher than that of the SF scaffold alone. The thermal decomposition temperatures of the SF/WS (10%) and SF/ILS (20%) scaffolds, mainly composed of a β-sheet structures, were 3 °C and 2 °C higher than that of the SF scaffold alone, respectively. The swelling properties and resistance to protease hydrolysis of the SP scaffolds containing sericin were improved. The bovine insulin release rates reached 61% and 56% after 5 days. The L929 cells adhered, stretched, and proliferated well on the SP composite scaffold. Thus, the SP bioinks obtained could be used to print different types of SP composite scaffolds adapted to a variety of applications, including cells, drugs, tissues, etc. The techniques described here provide potential new applications for the recycling and utilization of sericin, which is a waste product of silk processing.

Nanofiber/hydrogel core–shell scaffolds with three-dimensional multilayer patterned structure for accelerating diabetic wound healing

Impaired angiogenesis is one of the predominant reasons for non-healing diabetic wounds. Herein, a nanofiber/hydrogel core–shell scaffold with three-dimensional (3D) multilayer patterned structure (3D-PT-P/GM) was introduced for promoting diabetic wound healing with improved angiogenesis. The results showed that the 3D-PT-P/GM scaffolds possessed multilayered structure with interlayer spacing of about 15–80 μm, and the hexagonal micropatterned structures were uniformly distributed on the surface of each layer. The nanofibers in the scaffold exhibited distinct core–shell structures with Gelatin methacryloyl (GelMA) hydrogel as the shell and Poly (d, l-lactic acid) (PDLLA) as the core. The results showed that the porosity, water retention time and water vapor permeability of the 3D-PT-P/GM scaffolds increased to 1.6 times, 21 times, and 1.9 times than that of the two-dimensional (2D) PDLLA nanofibrous scaffolds, respectively. The in vitro studies showed that the 3D-PT-P/GM scaffolds could significantly promote cell adhesion, proliferation, infiltration and migration throughout the scaffolds, and the expression of cellular communication protein-related genes, as well as angiogenesis-related genes in the same group, was remarkably upregulated. The in vivo results further demonstrated that the 3D-PT-P/GM scaffolds could not only effectively absorb exudate and provide a moist environment for the wound sites, but also significantly promote the formation of a 3D network of capillaries. As a result, the healing of diabetic wounds was accelerated with enhanced angiogenesis, granulation tissue formation, and collagen deposition. These results indicate that nanofiber/hydrogel core–shell scaffolds with 3D multilayer patterned structures could provide a new strategy for facilitating chronic wound healing. Graphical Abstract

Large-Scale Preparation of Low-Cost Nonfullerene Acceptors for Stable and Efficient Organic Solar Cells

Despite the development of nonfullerene acceptors (NFAs) that have made a breakthrough in the photovoltaic performance, large-scale preparation of NFAs that is prerequisite for commercial application has never been explored. Herein, we designed two dodecacyclic all-fused-ring electron acceptors, F11 and F13, and develop a whole set of synthetic procedures, achieving unprecedented scalable preparation of NFAs in the lab at a 10-g scale notably within one day. The single-crystal structures of F11 reveals the 3D network packing. F11 and F13 display the lowest costs among reported NFAs, even comparable with the classical donor material, P3HT. By matching a medium-bandgap polymer donor, F13 delivers power conversion efficiencies of over 13%, which is an efficiency record for non-INCN acceptors. Benefiting from the intrinsically high stability, OSCs based on F11 and F13 show device stability superior to the typical ITIC- and Y6-based OSCs as evidenced by the tiny burn-in losses. The current work presents a first example for large-scale preparation of low-cost NFAs with good efficiency and high device stability, which is significant for OSC commercialization in near future.

3D Visualization of Bamboo Node’s Vascular Bundle

The vascular bundle is an important structural unit that determines the growth and properties of bamboo. A high-resolution X-ray microtomography (μCT) was used to observe and reconstruct a three-dimensional (3D) morphometry model of the vascular bundle of the Qiongzhuea tumidinoda node due to its advantages of quick, nondestructive, and accurate testing of plant internal structure. The results showed that the morphology of vascular bundles varied significantly in the axial direction. In the cross-section, the number of axial vascular bundles reached a maximum at the lower end of the sheath scar, and the minimum of it was at the middle of the diaphragm. The frequency of axial vascular bundles decreased from the lower end of the node to the nodal ridge, and subsequently increased until the upper end of the bamboo node. The proportion of parenchyma, fibers, and conducting tissue was 65.7%, 30.5%, and 3.8%, respectively. The conducting tissues were intertwined to form a complex 3D network structure, with a connectivity of 94.77%. The conducting tissue with the largest volume accounted for 60.26% of the total volume of the conducting tissue. The 3D-distribution pattern of the conducting tissue of the node and that of the fibers were similar, but their thickness changed in the opposite pattern. This study revealed the 3D morphometry of the conducting tissue and fibers of the bamboo node, the reconstruction of the skeleton made the morphology more intuitive. Quantitative indicators such as the 3D volume, proportion, and connectivity of each type of tissue was obtained, the bamboo node was enlarged mainly caused by the particularly developed fibers. This work laid the foundation for a better understanding of the mechanical properties and water transportation of bamboo and revealed the mystery of bamboo node shedding of Q. tumidinoda.

A 3D Lead Iodide Hybrid Based on a 2D Perovskite Subnetwork

Lead halide perovskites have emerged as promising materials for various optoelectronic applications. For photovoltaics, the reference compound is the 3D perovskite (MA)PbI3 (MA+ = methylammonium). However, this material suffers from instabilities towards humidity or light. This makes the search of new stable 3D lead halide materials very relevant. A strategy is the use of intermediate size cations instead of MA, which are not suitable to form the 3D ABX3 perovskites or 2D perovskites. Here, we report on a novel 3D metal halide hybrid material based on the intermediate size cation hydroxypropylammonium (HPA+), (HPA)6(MA)Pb5I17. We will see that extending the carbon chain length from two CH2 units (in the hydroxylethylammonium cation, HEA+) to three (HPA+) precludes the formation of a perovskite network as found in the lead and iodide deficient perovskite (HEA,MA)1+xPbxI3−x. In (HPA)6(MA)Pb5I17 the 3D lead halide network results from a 2D perovskite subnetworks linked by a PbI6 octahedra sharing its faces. DFT calculations confirm the direct band gap and reveal the peculiar band structure of this 3D network. On one hand the valence band has a 1D nature involving the p orbitals of the halide. On the other, the conduction band possesses a clear 2D character involving hybridization between the p orbitals of the metal and the halide.

Hybrid Supercapacitor Electrode Materials via Molecular Imprinting of Nitrogenous Ligands and Iron Complexes into Carbon Support

Novel hybrid supercapacitor materials were made by the covalent immobilization of nitrogenous ligands onto the surface of commercial carbon support (Vulcan XC-72), then coordinated to iron. The covalent attachment of the nitrogenous ligands allows for the controlled deposition of nitrogen functionalities on the surface of the carbon. The supercapacitor tests in acidic media showed significant growth of the capacitance as a result of the nitrogenous ligands on the support. Notably, the increase of the capacitance values directly correlates with the molecular loading on the surface. Following coordination of the iron to the ligands on the surface further elevated the capacitance via Faradaic reactions of the metal center. Remarkably, the overall capacitance of materials significantly increased after the course of long-term cycling tests (ca. 110% or higher). At the beginning of durability studies, a small decline in capacitance was observed, due to some extent of molecular decomposition on the surface of the electrode. However, the intense cycling further propagates a steady growth of the overall capacitance. This could be attributed to the process of polymerization of physisorbed molecules/ radicals that result in the formation of a 3D network structure that eventually boosts the overall capacitance and charge storage of the electrode.

A Simple Approach to Control the Physical and Chemical Features of Custom-Synthesized N-Doped Carbon Nanotubes and the Extent of Their Network Formation in Polymers: The Importance of Catalyst to Substrate Ratio

This study intends to reveal the significance of the catalyst to substrate ratio (C/S) on the structural and electrical features of the carbon nanotubes and their polymeric nanocomposites. Here, nitrogen-doped carbon nanotube (N-MWNT) was synthesized via a chemical vapor deposition (CVD) method using three ratios (by weight) of iron (Fe) catalyst to aluminum oxide (Al2O3) substrate, i.e.,1/9, 1/4, and 2/3, by changing the Fe concentration, i.e., 10, 20, and 40 wt.% Fe. Therefore, the synthesized N-MWNT are labelled as (N-MWNTs)10, (N-MWNTs)20, and (N-MWNTs)40. TEM, XPS, Raman spectroscopy, and TGA characterizations revealed that C/S ratio has a significant impact on the physical and chemical properties of the nanotubes. For instance, by increasing the Fe catalyst from 10 to 40 wt.%, carbon purity increased from 60 to 90 wt.% and the length of the nanotubes increased from 1.2 to 2.6 µm. Interestingly, regarding nanotube morphology, at the highest C/S ratio, the N-MWNTs displayed an open-channel structure, while at the lowest catalyst concentration the nanotubes featured a bamboo-like structure. Afterwards, the network characteristics of the N-MWNTs in a polyvinylidene fluoride (PVDF) matrix were studied using imaging techniques, AC electrical conductivity, and linear and nonlinear rheological measurements. The nanocomposites were prepared via a melt-mixing method at various loadings of the synthesized N-MWNTs. The rheological results confirmed that (N-MWNTs)10, at 0.5–2.0 wt.%, did not form any substantial network through the PVDF matrix, thereby exhibiting an electrically insulative behavior, even at a higher concentration of 3.0 wt.%. Although the optical microscopy, TEM, and rheological results confirmed that both (N-MWNTs)20 and (N-MWNTs)40 established a continuous 3D network within the PVDF matrix, (N-MWNTs)40/PVDF nanocomposites exhibited approximately one order of magnitude higher electrical conductivity. The higher electrical conductivity of (N-MWNTs)40/PVDF nanocomposites is attributed to the intrinsic chemical features of (N-MWNTs)40, such as nitrogen content and nitrogen bonding types.