Highly Interfacial Active Gemini Surfactants as Simple and Versatile Emulsifiers for Stabilizing, Lubricating and Structuring Liquids.

To date, locking the shape of liquids into non-equilibrium states usually relies on jamming nanoparticle surfactants at an oil/water interface. Here we show that a synthetic water-soluble zwitterionic Gemini surfactant can serve as an alternative to nanoparticle surfactants for stabilizing, structuring and additionally lubricating liquids. By having a high binding energy comparable to amphiphilic nanoparticles at the paraffin oil/water interface, the surfactant can attain near-zero interfacial tensions and ultrahigh surface coverages after spontaneous adsorption. Owing to the strong association between neighboring surfactant molecules, closely packed monolayers with high mechanical elasticity can be generated at the oil/water interface, thus allowing the surfactant to produce not only ultra-stable emulsions but also structured liquids with various geometries by using extrusion printing and 3D printing techniques. By undergoing tribochemical reactions at its sulfonic terminus, the surfactant can endow the resultant emulsions with favorable lubricity even under high load-bearing conditions. Our study may provide new insights into creating complex liquid devices and new-generation lubricants capable of combining the characteristics of both liquid and solid lubricants.

Tough, Transparent, and Slippery PVA Hydrogel Led by Syneresis.

Slippery and transparent polyvinyl alcohol (PVA) hydrogels with mechanical robustness exhibit broad applications in artificial biological soft tissues, flexible wearable electronics, and implantable biomedical devices. Most of the current PVA hydrogels, however, are unable to integrate these features, which compromises its performance in biological and engineering applications. To achieve such purpose, herein, a novel tactic is proposed, salting-out-after-syneresis of PVA, to realize a mechanically robust and highly transparent slippery PVA hydrogel. The syneresis of PVA sol is first conducted to form highly dense and transparent PVA polymer networks, then the salting-out effect tunes the aggregation of the polymer chains to rapidly induce the phase separation and crystallization. The resultant hydrogels show the transparency up to 98% in the visible region, the tribological coefficient down to 0.0081, and the excellent mechanical properties with strength, modulus, and toughness of 26.72 ± 1.05, 6.66 ± 0.29 MPa, and 55.21 ± 1.62 MJ m-3 , respectively. To reveal the potentials, PVA contact lens that combine remarkable lubrication, anti-protein adhesion, biocompatibility, and drug-loading functions are demonstrated. This strategy provides a simple and new avenue for developing the mechanically robust, transparent, and hydrated hydrogels, showing the potential in biomedicine and wearable devices.

Facile Photo and Thermal Two-Stage Curing for High-Performance 3D Printing of Poly(Dimethylsiloxane).

Three-dimensional (3D) printing of poly(dimethylsiloxane) (PDMS) is realized with a two-state curing strategy, i.e., photocuring for additively manufacturing high-precision architectures followed by thermal cross-linking for high-performance objects, taking Sylgard-184 as an example. In the mixture of base and curing agent of Sylgard-184, the photocuring ingredient methacrylated PDMS is incorporated to form hybrid inks with not only high-efficiency UV curing ability but also moderate rheological properties for 3D printing. The inks are then used to additively manufacture high-precision architectures by UV-assisted direct ink writing. Various architectures such as lattices and honeycombs, channels that can be used as microfluidics, and pressure-proof pipes with a feature size of ≈100 µm, can be readily printed. Thereafter, thermal cross-linking at elevated temperature is conducted to obtain the 3D PDMS objects with comparable properties to Sylgard-184. The facile, universal two-stage approach to 3D printing of PDMS can facilitate the development of microfluidics, flexible electronics, soft robots, and so on.

3D Printing of Photocuring Elastomers with Excellent Mechanical Strength and Resilience.

Three-dimensional (3D) printing elastomers, as a combination of transformative technology and widely used materials, have received great demand in many fields. However, commercial photocuring elastomer inks for 3D printing usually exhibit poor mechanical strength, inferior resilience, and lower elongation at break. In this study, photocuring inks that can be employed for digital light processing 3D printing are developed with acryloyl-modified polyethylene glycol (Acryl@PEG). The resultant photocuring inks exhibit not only high tensile strength of 14.1 MPa and elongation of 245.0%, but also excellent resilience (recover to 90.85% after 30 min under the 200% strain). With the photocuring elastomer inks, a variety of architectures including hollow vases, eggs, finger rings, and porous lattices are built with excellent precision, which all could experience large shape deformations repeatedly without any damage, indicating the excellent elasticity, outstanding shape-recovery property, and mechanical stability. The present photocuring elastomer inks for 3D printing are therefore believed to be promising for soft robots, wearable devices, flexible electronics, and many other applications.

Versatile Pickering emulsion gel lubricants stabilized by cooperative interfacial graphene oxide-polymer assemblies.

Although a large number of water- and oil-based gel lubricants have found extensive potential applications in industrial and biomedical fields, developing new-type emulsion-based gel lubricants that may effectively integrate their characteristics and preponderances remains a significant challenge. Here a water-in-oil Pickering emulsion gel lubricant that is able to combine the high colloidal stability of traditional Pickering emulsions, the good swelling and corrosion resistance of oil-based gel lubricants, and the high cooling capacity of water-based gel lubricants prepared from a binary mixture of aqueous graphene oxide (GO) dispersion and diamino-functionalized polydimethylsiloxane oil solution in a broad concentration, pH, and water volume fraction range is reported. It can provide favourable lubrication for the Si3N4/steel and Si3N4/silicone tribopairs either in air or under water owing to the formation of a sturdy adsorbed oil film and ball-bearing actions of the GO particles. It can also be printed into various colourful 2D and 3D geometries upon direct extrusion into water, thanks to its water-in-oil nature and inherent shear-thinning and thixotropic properties, which further shows good prospects in underwater operations and artificial biomimetic organs. Our study may provide new insights into the design and preparation of novel semi-solid materials for diverse industrial, engineering, and biomedical applications.

Rational Design and Construction of Monolithic Ordered Mesoporous Co3O4@SiO2 Catalyst by a Novel 3D Printed Technology for Catalytic Oxidation of Toluene.

Here, we report a novel 3D printed layered ordered mesoporous template that can encapsulate active Co-MOFs species in a confined way to achieve the goal of monolithic catalyst. The monolithic OM-Co3O4@SiO2-S catalyst can maintain a macroscopic porous layered structure and a microscopic ordered mesoporous structure. This monolithic OM-Co3O4@SiO2-S catalyst has excellent catalytic performance (T90 = 236 °C), water resistance, and thermal stability in the catalytic combustion of toluene. The catalytic performance of the monolithic OM-Co3O4@SiO2-S catalyst is much better than that of many monolithic catalysts reported in the former. Among them, the introduction of binder aluminum phosphate (AP) can effectively enhance the rheological properties of the printing ink, achieve the purpose of ink writing monolithic layered porous material, enrich the acidic point of the monolithic catalyst, and increase the number of reactive oxygen species. This work reveals a novel monolithic catalyst forming strategy that can combine the advantages of ordered mesoporous materials with active species to form macro-layered porous materials and provide ideas and an experimental basis for the elimination of VOCs in industrial applications.

Effects of Biomimetic Micropatterned Surfaces on the Adhesion and Morphology of Cervical Cancer Cells.

It has been demonstrated that micropatterned surfaces have an important influence on modulating cellular behavior. In recent years, with the rapid development of microfabrication techniques and in-depth study of nature, an increasing number of patterned structures imitating natural organisms have been successfully fabricated and widely evaluated. However, there are only a few reports about biomimetic patterned microstructures in biologically related fields. In our work, micropatterned polydimethylsiloxane (PDMS) was fabricated by mimicking the surface microstructures of natural Trifolium and Parthenocissus tricuspidata leaves using the template duplication method. The interactions between the two types of biomimetic micro-PDMS surfaces and two kinds of human cervical cancer cells (HeLa and SiHa) were investigated. HeLa and SiHa cells cultured on the two micropatterned PDMS samples exhibited more stretchable morphology, higher diffusion, and a much lower nuclear/cytoplasmic ratio than those cultured on flat PDMS surfaces, indicating a higher adhesion area of the cells. Both of the micro-PDMS substrates were found to induce significantly different morphological changes between HeLa and SiHa cells. This suggests that the micropatterned structure affects cell adhesion and morphology correlated with their surface geometric structure and roughness. The results reveal that biomimetic micropatterned surfaces from natural leaves significantly regulate the morphology and adhesion behavior of cervical cancer cells and are believed to be the new platforms for investigating the interaction between cells and substrates.

Direct Ink Writing of Phenylethynyl End-Capped Oligoimide/SiO2 to Additively Manufacture High-Performance Thermosetting Polyimide Composites.

The three-dimensional (3D) printing of a SiO2-filled thermosetting polyimide (SiO2@TSPI) composite with outstanding performance is realized via the direct ink writing (DIW) of polyamide acid (PAA) composite ink and thermal treatment conducted thereafter. The composite ink consists of phenylethynyl-terminated PAA and silica nanoparticles, where the SiO2 nanoparticles serve as the rheology modifier that is necessary for the DIW technique to obtain self-supporting feedstock during 3D printing and the reinforcement filler that is used to enhance the performance of the final composite. As a result, printed parts with complex geometry and robust thermal stability are obtained. Due to the extrusion-based DIW technique, the printed structures exhibit anisotropic mechanical strength that highly depends on printing roads. This simple and convenient means of realizing 3D structures of thermosetting polyimides is a promising strategy in aerospace and other fields.

Bioinspired Design of a Cartilage-like Lubricated Composite with Mechanical Robustness.

Natural articular cartilages show extraordinary tribological performance based on their penetrated surface lubricated biomacromolecules and good mechanical tolerance. Hydrogels are considered to be potential alternatives to cartilages due to their low surface friction and good biocompatibility, although the poor mechanical properties limited their applications. Inspired by the excellent mechanical properties and the remarkable surface lubrication mechanism of natural articular cartilages, one kind of cartilage-like composite material with a lubrication phase (Composite-LP) was developed by chemically grafting a thick hydrophilic polyelectrolyte brush layer onto the subsurface of a three-dimensional manufactured elastomer scaffold-hydrogel composite architecture. The Composite-LP exhibited good load-bearing capacities because of the nondissipation strategy and the stress dispersion mechanism resulting from the elastomer scaffold enhancement. In the presence of the top lubrication layer, the Composite-LP showed superior friction reduction functionality and wear resistance under a dynamic shearing process. This design concept of coupling the non-dissipative mechanism and interface lubrication provides a new avenue for developing cartilage-like hydrogels and soft robots.

Knockout of OsNRAMP5 enhances rice tolerance to cadmium toxicity in response to varying external cadmium concentrations via distinct mechanisms.

OsNRAMP5 is a transporter responsible for cadmium (Cd) and manganese (Mn) uptake and root-to-shoot translocation of Mn in rice plants. Knockout of OsNRAMP5 is regarded as an effective approach to minimize Cd uptake and accumulation in rice. It is vital to evaluate the effects of knocking out OsNRAMP5 on Cd and Mn accumulation, as well as Cd tolerance of rice plants in response to varying environmental Cd concentrations, and to uncover the underlying mechanism, which until now, has remained largely unexplored. This study showed that knockout of OsNRAMP5 decreased Cd uptake, but simultaneously facilitated Cd translocation from roots to shoots. The effect of OsNRAMP5 knockout on reducing root Cd uptake weakened, however its effect on improving root-to-shoot Cd translocation was constant with increasing environmental Cd concentrations. As a result, its mutation dramatically reduced Cd accumulation in shoots under low and moderate Cd stress, but inversely increased that under high Cd conditions. Interestingly, Cd tolerance of its knockout mutants was persistently enhanced, irrespective of lower or higher Cd concentrations in shoots, compared with that of wild-type plants. Knockout of OsNRAMP5 mitigated Cd toxicity by dramatically diminishing Cd uptake at low or moderate external Cd concentrations. Remarkably, its knockout effectively complemented deficient mineral nutrients in shoots, thereby indirectly enhancing rice tolerance to severe Cd stress. Additionally, its mutation conferred preferential delivery of Mn to young leaves and grains. These results have important implications for the application of the OsNRAMP5 mutation in mitigating Cd toxicity and lowering the risk of excessive Cd accumulation in rice grains.

Overexpression of OsLCT2, a Low-Affinity Cation Transporter Gene, Reduces Cadmium Accumulation in Shoots and Grains of Rice.

Cadmium (Cd)-contaminated rice is a serious issue affecting food safety. Understanding the molecular regulatory mechanisms of Cd accumulation in rice grains is crucial to minimizing Cd concentrations in grains. We identified a member of the low-affinity cation transporter family, OsLCT2 in rice. It was a membrane protein. OsLCT2 was expressed in all tissues of the elongation and maturation zones in roots, with the strongest expression in pericycle and stele cells adjacent to the xylem. When grown in Cd-contaminated paddy soils, rice plants overexpressing OsLCT2 significantly reduced Cd concentrations in the straw and grains. Hydroponic experiment demonstrated its overexpression decreased the rate of Cd translocation from roots to shoots, and reduced Cd concentrations in xylem sap and in shoots of rice. Moreover, its overexpression increased Zn concentrations in roots by up-regulating the expression of OsZIP9, a gene responsible for Zn uptake. Overexpression of OsLCT2 reduces Cd accumulation in rice shoots and grains by limiting the amounts of Cd loaded into the xylem and restricting Cd translocation from roots to shoots of rice. Thus, OsLCT2 is a promising genetic resource to be engineered to reduce Cd accumulation in rice grains.

[Stability analysis of on-board calibration system of spatially modulated imaging Fourier transform spectrometer].

Spatially modulated imaging Fourier transform spectrometer (SMIFTS) was an instrument that depended on interference, and after calibration, the reconstruction spectrum can quantificationally reflect the diffuse reflection of target under sunshine. On-board calibration of SMIFTS confirmed the change of SMIFTS according to relative spectrum calibration, inspected long-time attenuation of SMIFTS optical system, and corrected export data of SMIFTS. According to the requirement of remote sensor application, it must stay in vacuum environment for a long time. As a radiant standard, the stability of lamp-house in long time is the most important characteristic of on-board calibration system. By calculation and experimentation, analyses of on-board calibration of SMIFTS, and testing spaceflight environment characteristic of on-board calibration, the difficulty in the key parts of on-board calibration of SMIFTS such as lamp-house, spectrum filter and integrating sphere was solved. According to the radiation-time stability testing for lamp-house and optics, particle-radiation testing, environmental-mechanics testing and hot vacuum examination, good result was obtained. By whole-aperture and part-field comparative wavelength calibration, the spectrum curve and before-launch interferogram were obtained. After comparison with reconstruction spectrum under different condition, the stability and credibility of SMIFTS on-board calibration system was proved.

3D Printing of an Oil/Water Mixture Separator with In Situ Demulsification and Separation.

Currently, many meshes, membranes, and fabrics with extreme wettability of superhydrophobicity/superoleophilicity, or superhydrophilicity and underwater superoleophobicity are promising candidates for oil/water mixture separation. Nevertheless, a facile yet effective way to design and fabricate porous mesh still remains challenging. In this work, fused deposition modeling (FDM) 3D printing of Fe/polylactic acid (PLA) composites was employed to fabricate superhydrophilic and underwater superoleophobic mesh (S-USM) with hydrogel coatings via the surface polymerization of Fe(II)-mediated redox reaction. In addition, salt of aluminum chloride was incorporated within the hydrogel coating, which was attributed to strengthening the demulsification of oil-in-water emulsions, resulting in efficient separation of oil-in-water mixtures. The S-USM was efficient for a wide range of oil-in-water mixtures, such as dodecane, diesel, vegetable oil, and even crude oil, with a separation efficiency of up to 85%. In this study, the flexible design and fabrication of 3D printing were used for the facile creation of spherical oil skimmers with hydrogel coatings that were capable of removing the floating oil. Most importantly, this work is expected to promote post-treatment processes using 3D printing as a new manufacturing technology and, in this way, a series of devices of specific shape and function will be expanded to satisfy desired requirements and bring great convenience to personal life.

Drawing High-Definition and Reversible Hydrogel Paintings with Grayscale Exposure.

High-definition and arbitrary grayscale hydrogel paintings that can appear reversibly with hydration/dehydration are realized through spatially grayscale exposure. Spatio-temporally grayscale images are used to guide the exposure of a hydrogel processor to dictate the gradient cross-linking density spatially, which thereafter results in the heterogeneity of hydrogels in swelling ratio, mechanical properties, and especially visible light transmittance, leading to swelling-induced patterns by gradient and local visible light scattering difference based on tunable mesh size and microphase separation. The resultant grayscale hydrogel patterns, with visible light transmittance adjustable, are reversible during hydration (in 1-2 s) and dehydration and possess the feature size of 70 µm and more pattern information compared with previous hydrogel patterning. Uniquely, the patterns can be realized not only on the outmost surface of hydrogels as usual but inside. Combining the unique grayscale exposure with three-dimensional printing technology, arbitrary hydrogel patterns that have plenty of details and even vary at different layers are fabricated readily, indicating its broad potential in smart anti-counterfeiting of security field, mechanics, engineering, and many others.