Self-Folding Graphene-Based Interface for Brain-Like Modular 3D Tissue (Adv. Funct. Mater. 37/2023)

Electrophysiology of 3D neuronal cultures is of rapidly growing importance for revealing cellular communications associated with neurodevelopment and neurological diseases in their brain-like 3D environment. Despite that the brain also exhibits an inherent modular architecture that is essential for cortical processing, it remains challenging to interface a modular network consisting of multiple 3D neuronal tissues. Here, a self-folding graphene-based electrode array is proposed that enables to reconstruct modular 3D neuronal tissue and investigate firing dynamics among moduli. A graphene-sandwiched parylene-C film self-folds into a cylindrical structure within which living cells can be encapsulated. Culture of encapsulated cells inside the folded graphene enables to spontaneously construct 3D cell aggregates and ensure firm contact between the graphene surface and encapsulated cells. As the inner graphene surface can be utilized as an electrode, the reliable cell–electrode contact allows for long-term electrical recording from multiple 3D aggregates. Additionally, the modular network consisting of multiple 3D aggregates exhibits richer firing patterns than a conventional homogenous 2D network, which demonstrates that the approach enables measurements of firing dynamics in complex 3D neuronal networks. The deformable graphene electrode will be a powerful platform for investigating complex cellular communications in brain-like 3D cultures.     

Spatial Control of Substitutional Dopants in Hexagonal Monolayer WS2: The Effect of Edge Termination

The ability to control the density and spatial distribution of substitutional dopants in semiconductors is crucial for achieving desired physicochemical properties. Substitutional doping with adjustable doping levels has been previously demonstrated in 2D transition metal dichalcogenides (TMDs); however, the spatial control of dopant distribution remains an open field. In this work, edge termination is demonstrated as an important characteristic of 2D TMD monocrystals that affects the distribution of substitutional dopants. Particularly, in chemical vapor deposition (CVD)-grown monolayer WS₂, it is found that a higher density of transition metal dopants is always incorporated in sulfur-terminated domains when compared to tungsten-terminated domains. Two representative examples demonstrate this spatial distribution control, including hexagonal iron- and vanadium-doped WS₂ monolayers. Density functional theory (DFT) calculations are further performed, indicating that the edge-dependent dopant distribution is due to a strong binding of tungsten atoms at tungsten-zigzag edges, resulting in the formation of open sites at sulfur-zigzag edges that enable preferential dopant incorporation. Based on these results, it is envisioned that edge termination in crystalline TMD monolayers can be utilized as a novel and effective knob for engineering the spatial distribution of substitutional dopants, leading to in-plane hetero-/multi-junctions that display fascinating electronic, optoelectronic, and magnetic properties.     

Mean molal activity coefficients of aqueous scandium chloride, nitrate, bromide and perchlorate solutions at 25.0°

The mean molal activity coefficients of aqueous scandium chloride, nitrate, bromide and perchlorate solutions were determined at 25.0° for dilute to saturated concentrations, together with the activities of water. In the dilute solutions of scandium halides, the activity coefficients were obtained from electromotive force measurements on galvanic cells, and the osmotic coefficients of all four solutions above 0.1 mol kg⁻¹ were determined from the isopiestic measurements. Least-squares equations were fitted to these coefficients, which were then used to calculate the mean molal activity coefficients and water activities. The relationships between these results and the corresponding activity data for other rare earth salts, and to the cation hydration and ionic interactions, are discussed. The results on scandium perchlorate solutions suggested that the inner-sphere hydration number of tervalent scandium ion may be seven.     

Ligand-Installed Nanocarriers toward Precision Therapy

Development of drug-delivery systems that selectively target neoplastic cells has been a major goal of nanomedicine. One major strategy for achieving this milestone is to install ligands on the surface of nanocarriers to enhance delivery to target tissues, as well as to enhance internalization of nanocarriers by target cells, which improves accuracy, efficacy, and ultimately enhances patient outcomes. Herein, recent advances regarding the development of ligand-installed nanocarriers are introduced and the effect of their design on biological performance is discussed. Besides academic achievements, progress on ligand-installed nanocarriers in clinical trials is presented, along with the challenges faced by these formulations. Lastly, the future perspectives of ligand-installed nanocarriers are discussed, with particular emphasis on their potential for emerging precision therapies.     

Manipulating the chemical affinity and kinetics of 3D silica particle network via the phase-separation technique

We developed a simple and versatile technique for a particle’s self-organizing-network based on a non-solvent induced micro-phase separation (NIPS). When a good solvent vaporizes from a particle dispersion in a ternary solution including the polymer, good solvent and non-solvent, the suspension is separated into the polymer network and non-solvent phase. If the affinity between the particles and polymer is sufficient enough, the particles are entrapped in the polymer network and particle network can be achieved. To expand this technique to particles with various physical properties, the surface of the particles was identified using the Hansen dispersibility parameter (HDP). From a comparison of the HDP of the unmodified and modified silica, an NH₂ group is suitable for entrapment of the silica by cellulose acetate as the polymer. However, with an increase in number of the silica particles, entrapment of the silica in the polymer was prevented. Control of the phase separation rate by the lowering temperature leaded to entrapment of silica particles in the polymer network. The proposed technique is effective not only for spherical oxide particles, but also for non-oxides, various shapes and structures. Depending on particle characteristics, functional films and bulk materials for thermal insulation, light diffusion, and electro conductivity can be obtained.     

Deep-ultraviolet Raman microspectroscopy: characterization of wide-gap semiconductors

We have developed a high-throughput deep-ultraviolet (DUV) Raman microspectrometer with excitation from a continuous wave (cw) laser operated at 244 nm that enables us to characterize thin surface layers of wide-gap semiconductors. This spectrometer system consists of a filter spectrometer for the rejection of stray light and a high-dispersion spectrograph combined with a liquid nitrogen cooled charge-coupled device (CCD) detector and extends the low-frequency limit of the observable spectral range down to 170 cm(-1). In the microscope we use a Cassegrain reflective objective for the collection of the scattered light and an off-axis mirror for introduction of the excitation laser light. DUV Raman spectroscopy has been applied for studying wide-gap semiconductors including SiC and AlGaN epitaxial films and shallow implanted layers of these materials. Raman spectra of various crystals have also been measured for examining the performance of this system. Resonance enhancement of Raman bands has been observed for several semiconductors, and the results are discussed.     

Structural change of water with solutes and temperature up to 100 degrees C in aqueous solutions as revealed by attenuated total reflectance infrared spectroscopy

The attenuated total reflectance infrared (ATR-IR) spectra of several aqueous solutions have been measured by using a newly developed heatable rod-type ATR cell. The OH stretching bands showed systematic change with increasing solute concentrations and these changes can be explained by four different OH components based on curve-fitting results. NaCl solutions show longer H-bond distance character, while carbonate solutions present shorter ones. The Na2CO3 1 M solution conserves this shorter H-bond nature up to 100 degrees C. On the other hand, the loose nature of NaCl solutions becomes less pronounced at higher temperatures because of the dissociation of pure water clusters. These in situ observations of water structures are generally in agreement with the expected nature of fluids within the earth.     

Control of the coating layer thickness of TiO2–SiO2 core–shell hybrid particles by liquid phase deposition

This paper describes control of the coating layer thickness and the crystallite size of the core–shell hybrid particles by controlling the process parameter. The core–shell hybrid particles were prepared using liquid phase deposition (LPD). We confirmed that the homogeneous coating was attained from the result of the zeta potential and the transmission electron microscope (TEM) observation. Furthermore, the coating layer microstructure was estimated using Brunauer–Emmett–Teller (BET) method. The obtained coating layer of titania was estimated using the band gap energy. Results indicate that the blue shift of the band gap energy signifies that the physical property of the hybrid particles was controlled by the coating layer thickness and the crystallite size, which are determined by the processing parameters.     

The functional role of CrkII in actin cytoskeleton organization and mitogenesis

Crk is a member of a family of adapter proteins predominantly composed of Src homology 2 and 3 domains, whose role in signaling pathways is presently unclear. Using an in situ electroporation system which permits the introduction of glutathione S-transferase (GST) fusion proteins into cells, we found that c-CrkII bound to p130(cas), but not to paxillin in serum-starved rat-1 fibroblasts overexpressing the human insulin receptor (HIRc cells) in vivo. 17 nM insulin stimulation dissociated the binding of c-CrkII to p130(cas), whereas 13 nM insulin-like growth factor-I, 16 nM epidermal growth factor (EGF), and 10% serum each showed little or no effect. We found that stress fiber formation is consistent with a change in the p130(cas).c-CrkII interactions before and after growth factor stimulation. Microinjection of either GST-Crk-SH2 or -Crk-(N)SH3 domains, or anti-Crk antibody each inhibited stress fiber formation before and after insulin-like growth factor-I, EGF, and serum stimulation. Insulin stimulation by itself caused stress fiber breakdown and there was no additive effect of microinjection. Microinjection of anti-p130(cas) antibody also blocked stress fiber formation in quiescent cells. Microinjection of the Crk-inhibitory reagents also inhibited DNA synthesis after insulin-like growth factor-I, EGF, and serum stimulation, but not after insulin. These data suggest that the complex containing p130(cas).c-CrkII may play a crucial role in actin cytoskeleton organization and in anchorage-dependent DNA synthesis.