We describe here a new method for labeling the defects of single-walled carbon nanotubes (SWNTs) using TiO2 nanoparticles as markers. SWNTs were prepared by chemical vapor deposition, and dilute nitric acid (2.6M) oxidation was used to introduce carboxylic acid groups at the defect sites. Characterization of the SWNTs using ultrastructural and spectroscopic analyses was carried out following introduction of TiO2 nanoparticles. The results indicated that TiO2 nanoparticles were chemically absorbed at SWNT defect sites via an ester-type linkage between carboxylic acid groups at the defect sites and hydroxyl groups at the surface of the TiO2 nanoparticles. In addition, the adsorption behavior of TiO2 nanoparticles on SWNTs was determined following oxidization of the SWNTs using different processes. The results indicated that gas-phase oxidation introduces very few defect sites as evidenced by the low adsorption density of TiO2 nanoparticles. Refluxing in dilute nitric acid can be considered as a mild oxidation for SWNTs, affecting only those defects already present and causing no further damage. In contrast, sonication of SWNTs in H2SO4/H2O2 increased the incidence of carboxylic acid groups, not only at original defect sites but also at newly created defect sites along the walls of SWNTs, resulting in a higher density of TiO2 nanoparticles. In conclusion, labeling of SWNT defect sites using TiO2 nanoparticles permits direct determination of the density, distribution, and location of the defects and offers new possibilities for the creation of heterojunctions between nanotubes and nanoparticles in the future.

We report herein a modified approach to the seed-mediated synthesis of large-diameter quasispherical gold nanoparticles by using 2-mercaptosuccinic acid (MSA) as a reducing agent in aqueous solution at room temperature. Simply through a one-step seeding growth approach, gold nanoparticles in the size range 30-150 nm were prepared from 15 nm gold seeds under the particular [HAuCl 4 ]:[MSA] ratio of 1:0.6. Particle diameters could be controlled by varying the ratio of [HAuCl 4 ]:[seeds]. The resultant gold nanoparticles are quasispherical with narrow size distributions (relative standard deviation, RSD < 10%) and high yields; other nanostructures (nanorods, triangles, or hexagonal nanoplates) are rarely found, although they are frequently observed during the seeding growth when using hydroxylamine or ascorbic acid as reducing agents. The presence of MSA, which is not only a reducing agent but also a capping agent, is believed to make a great contribution to the isotropic growth of gold seeds and the formation of such monodisperse quasispherical particles.

Natural materials are often compositionally and structurally heterogeneous for realizing particular functions. Inspired by nature, researchers have designed hybrid materials that possess properties beyond each of the components. Particularly, it remains a great challenge to realize site‐specific anisotropy, which widely exists in natural materials and is responsible for unique mechanical properties as well as physiological behaviors. Herein, the spontaneous formation of aligned graphene oxide (GO) flakes in sodium alginate (SA) matrix with locally controlled orientation via a direct‐ink‐writing printing process is reported. The GO flakes are spontaneously aligned in the SA matrix by shear force when being extruded and then arranged horizontally after drying on the substrate, forming a brick‐and‐mortar structure that could anisotropically contract or expand upon activation by heat, light, or water. By designing the printing pathways directed by finite element analysis, the orientation of GO flakes in the composite is locally controlled, which could further guide the composite to transform into versatile architectures. Particularly, the transformation is reversible when water vapor is applied as one of the stimuli. As a proof of concept, complex morphing architectures are experimentally demonstrated, which are in good consistency with the simulation results.

Many natural materials possess built-in structural variation, endowing them with superior performance. However, it is challenging to realize programmable structural variation in self-assembled synthetic materials since self-assembly processes usually generate uniform and ordered structures. Here, we report the formation of asymmetric microribbons composed of directionally self-assembled two-dimensional nanoflakes in a polymeric matrix during three-dimensional direct-ink printing. The printed ribbons with embedded structural variations show site-specific variance in their mechanical properties. Remarkably, the ribbons can spontaneously transform into ultrastretchable springs with controllable helical architecture upon stimulation. Such springs also exhibit superior nanoscale transport behavior as nanofluidic ionic conductors under even ultralarge tensile strains (>1,000%). Furthermore, to show possible real-world uses of such materials, we demonstrate in vivo neural recording and stimulation using such springs in a bullfrog animal model. Thus, such springs can be used as neural electrodes compatible with soft and dynamic biological tissues.

Poly(vinylidene fluoride) (PVDF) nanotubes were fabricated by melt-wetting into porous anodic aluminum oxide (AAO) templates with two different interfacial properties: one is pristine AAO, and the other is modified by FOTS (AAO-F). Their crystallization and melting behaviors are compared with those of a bulk sample. For the PVDF in AAO-F, the nonisothermal crystallization temperature is slightly lower than that of bulk, and the melting temperature is similar to that of bulk. For the PVDF in pristine AAO, when the pore diameter is 200 nm, the crystallization is induced by two kinds of nucleation: heterogeneous nucleation and interface-induced nucleation. On the contrary, in the AAO template with pore diameter smaller than 200 nm, only interface-induced nucleation occurs. The melting temperature of PVDF crystals in the pristine AAO is much higher than that of bulk which can be attributed to the presence of an interfacial layer of PVDF on the template inner surface. The interaction between PVDF and AAO template produces the interfacial layer. Such an interfacial layer plays an important role in enhancing the melting temperature of PVDF crystals. The higher melting peak is always observed when the PVDF is nonisothermally crystallized in the AAO template irrespective of the thermal erasing temperature suggesting the interfacial layer is very stable on the AAO template surface. If the PVDF nanostructures are released from AAO template, the higher melting peak disappears with the enhancement of thermal erasing temperature.

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