Three-dimensional (3D) printing has recently been introduced into the field of chemistry as an enabling tool employed to perform reactions, but so far, its use has been limited due to material and structural constraints. We have developed a new approach for fabricating 3D catalysts with high-complexity features for chemical reactions via digital light processing printing (DLP). PtO2-WO3 heterogeneous catalysts with complex shapes were directly fabricated from a clear solution, composed of photo-curable organic monomers, photoinitiators, and metallic salts. The 3D-printed catalysts were tested for the hydrogenation of alkynes and nitrobenzene, and displayed excellent reactivity in these catalytic transformations. Furthermore, to demonstrate the versatility of this approach and prove the concept of multifunctional reactors, a tungsten oxide-based tube consisting of three orderly sections containing platinum, rhodium, and palladium was 3D printed.

Shape memory polymers are attractive smart materials that have many practical applications and academic interest. Three-dimensional (3D) printable shape memory polymers are of great importance for the fabrication of soft robotic devices due to their ability to build complex 3D structures with desired shapes. We present a 3D printable shape memory polymer, with controlled melting and transition temperature, composed of methacrylated polycaprolactone monomers and N-Vinylcaprolactam reactive diluent. Tuning the ratio between the monomers and the diluents resulted in changes in melting and transition temperatures by 20, and 6 °C, respectively. The effect of the diluent addition on the shape memory behavior and mechanical properties was studied, showing above 85% recovery ratio, and above 90% fixity, when the concentration of the diluent was up to 40 wt %. Finally, we demonstrated multi-material printing of a 3D structure that can be activated locally, at two different temperatures, by two different stimuli; direct heating and light irradiation. The remote light activation was enabled by utilizing a coating of Carbon Nano Tubes (CNTs) as an absorbing material, onto sections of the printed objects.

We report a method for the design and fabrication of 3D printed bioanodes for Biophotovotaic (BPV) applications. Electrodes were fabricated in 5 different thicknesses, from 0.2 mm to 1.0 mm with a 0.2 mm increment and the electrodes were coated with multi-wall carbon nanotubes (MWCNTs). Electrochemical characterisation of these electrodes was performed and the performance tested alongside a bare carbon paper electrode in a bespoke designed membrane electrode assembly (MEA)-type BPV device. All of the MWCNTs-coated 3D printed electrodes outperformed the bare carbon paper electrode. The best performing one (1.0 mm) showed a 40 times increment in power density and a 20 times reduction of the internal resistance. The successful development of the 3D printed bioanode can be used as a standardised platform for the comparison of similar materials. The development of the electrodes and MEA-type BPV device will serve as the initial step towards the development of a monolithic 3D printed BPV platform.

The selective removal of radioactive cationic species, specifically 137Cs+ and 90Sr2+, from contaminated water is critical for nuclear waste remediation processes and environmental cleanup after accidents, such as the Fukushima Daiichi Nuclear Power Plant disaster in 2011. Nanoporous silicates, such as zeolites, are most commonly used for this process but in addition to acting as selective ion exchange media must also be deployable in a correct physical form for flow columns. Herein, Digital Light Processing (DLP) three-dimensional (3D) printing was utilized to form monoliths from zeolite ion exchange powders that are known to be good for nuclear wastewater treatment. The monoliths comprise 3D porous structures that will selectively remove radionuclides in an engineered form that can be tailored to various sizes and shapes as required for any column system and can even be made with fine-grained powders unsuitable for normal gravity flow column use. 3D-printed monoliths of zeolites chabazite and 4A were made, characterized, and evaluated for their ion exchange capacities for cesium and strontium under static conditions. The 3D-printed monoliths with 50 wt% zeolite loadings exhibit Cs and Sr uptake with an equivalent ion-capacity as their pristine powders. These monoliths retain their porosity, shape and mechanical integrity in aqueous media, providing a great potential for use to not only remove radionuclides from nuclear wastewater, but more widely in other aqueous separation-based applications and processes.

A new approach to fabricate copper, indium, gallium diselenide (CIGSe) solar cells on conductive fluorine-doped tin oxide (FTO) reached an efficiency of over 6% for a champion photovoltaic device. Commercial oxide nanoparticles are formulated into high-quality screen-printable ink based on ethyl cellulose solution in terpineol. The high homogeneity and good adhesion properties of the oxide ink play an important role in obtaining dense and highly crystalline photoabsorber layers. This finding reveals that solution-based screen-printing from readily available oxide precursors provides an interesting cost-effective alternative to current vacuum- and energy-demanding processes of the CIGSe solar cell fabrication.

Millions of people suffer from different types of skin diseases worldwide. In the last decade, the development of nanocarriers has been the focus of the pharmaceutical and cosmetic industries to enhance the performance of their products, and to meet consumers' demands. Several delivery systems have been developed to improve the efficiency and minimize possible side effects. In this study, retinyl palmitate and Dead Sea water loaded nanoemulsions were developed as carriers to treat skin conditions such as photoaging, psoriasis, or atopic dermatitis. Toxicity profiles were carried out by means of viability, cell membrane asymmetry study, evaluation of oxidative stress induction (reactive oxygen species), and inflammation via cytokines production with a human keratinocyte cell line (HaCaT) and a mouse embryo fibroblasts cell line (BALB/3T3). Results showed that loaded nanoemulsions were found to be non-cytotoxic under the conditions of the study. Furthermore, no oxidative stress induction was observed. Likewise, an efficacy test of these loaded nanoemulsions was also tested on human skin organ cultures, before and after ultraviolet B light treatment. Viability and caspase-3 production assessment, in response to the exposure of skin explants to the loaded nanoemulsions, indicated non-toxic effects on human skin in culture, both with and without ultraviolet B irradiation. Further the ability of loaded nanoemulsions to protect the skin against ultraviolet B damage was assessed on skin explants reducing significantly the apoptotic activation after ultraviolet B irradiation. Our promising results indicate that the developed loaded nanoemulsions may represent a topical drug delivery system to be used as an alternative treatment for recurrent skin diseases.

Coordination polymers (CPs) and coordination network solids such as metal-organic frameworks (MOFs) have gained increasing interest during recent years due to their unique properties and potential applications. Preparing 3D printed structures using CP would provide many advantages towards utilization in fields such as catalysis and sensing. So far, functional 3D structures were printed mostly by dispersing pre-synthesized particles of CPs and MOFs within a polymerizable carrier. This resulted in a CP active material dispersed within a 3D polymeric object, which may obstruct or impede the intrinsic properties of the CP. Here, we present a new concept for obtaining 3D free-standing objects solely composed of CP material, starting from coordination metal complexes as the monomeric building blocks, and utilizing the 3D printer itself as a tool to in situ synthesize a coordination polymer during printing, and to shape it into a 3D object, simultaneously. To demonstrate this, a 3D-shaped nickel tetra-acrylamide monomeric complex composed solely of the CP without a binder was successfully prepared using our direct print-and-form approach. We expect that this work will open new directions and unlimited potential in additive manufacturing and utilization of CPs.

By designing an actuator composed of thin layers with different coefficients of thermal expansion (CTE) together with an electrically conductive layer, the CTE mismatch can be utilized to produce soft electrothermal actuators (ETAs). These actuators have been typically implemented using only two layers, commonly relying on Timoshenko's analytic model that correlates the temperature to the actuator's curvature. In this study, we extend the analytic model to include the thermoelectric relation present in ETAs, that is, the conductive layer's properties with respect to the operation temperature. By applying the thermoelectric relation, a minimal voltage optimization can be applied to the analytic model. Using dimensionless analysis, we optimize the ETAs performance for both bi- A nd tri-layer ETAs with and without the thermal modeling. The bi-layer optimization not only predicts the maximal value for the bi-layer performance but also provides the optimal thickness of each layer for any couple of materials. We validate the tri-layer analytic model experimentally by measuring the curvature for different third layer thicknesses. Finally, we optimize the tri-layer design based on the analytic model, which can achieve an improvement in curvature per voltage of >3000% over the optimal bi-layer ETA.

This work presents the fabrication of 3D-printed composite objects based on copper(II) 1D coordination polymer (CP1) decorated with thymine along its chains with potential utility as an environmental humidity sensor and as a water sensor in organic solvents. This new composite object has a remarkable sensitivity, ranging from 0.3% to 4% of water in organic solvents. The sensing capacity is related to the structural transformation due to the loss of water mols. that CP1 undergoes with temperature or by solvent mols.′ competition, which induces significant change in color simultaneously. The CP1 and 3D printed materials are stable in air over 1 yr and also at biol. pHs (5-7), therefore suggesting potential applications as robust colorimetric sensors. These results open the door to generate a family of new 3D printed materials based on the integration of multifunctional coordination polymers with organic polymers.

3D objects composed of 100% wood components are 3D printed utilizing wood flour microparticles dispersed in a matrix composed of cellulose nanocrystals and xyloglucan. In the printed object, a wood waste product is ``glued'' with extracted wood products, to be a substitute for pristine wood. 3D printing is used to maximize conversion of low value materials into final products that exhibit visual, textural, and physical properties of natural timber. Several 3D printing technologies are applied to achieve a wide range of densities, mechanical properties, colors, and morphologies as well as high thermal insulation. Furthermore, the 3D printing process enables predesigning of fiber layout in the printed wood, which enables control of shrinkage orientation.

The electrophoretic deposition (EPD) of graphene-based materials on transparent substrates is highly potential for many applications. Several factors can determine the yield of the EPD process, such as applied voltage, deposition time and particularly the presence of dispersion additives (stabilisers) in the suspension solution. This study presents an additive-free EPD of graphene quantum dot (GQD) thin films on an indium tin oxide (ITO) glass substrate and studies the deposition mechanism with the variation of the applied voltage (10–50 V) and deposition time (5–25 min). It is found that due to the small size ($\approx$3.9 nm) and high content of deprotonated carboxylic groups, the GQDs form a stable dispersion (zeta-potential of about −35 mV) without using additives. The GQD thin films can be deposited onto ITO with optimal surface morphology at 30 V in 5 min (surface roughness of approximately (3.1$\pm$1.3) nm). In addition, as-fabricated GQD thin films also possess some interesting physico-optical properties, such as a double-peak photoluminescence at about λ=417 and 439 nm, with approximately 98 % visible transmittance. This low-cost and eco-friendly GQD thin film is a promising material for various applications, for example, transparent conductors, supercapacitors and heat conductive films in smart windows.

Semiconductor nanocrystals have been shown to have unique advantages over traditional organic photoinitiators for polymerization in solution However, efficient photoinitiation with such nanoparticles in solvent-free and additive-free formulations so far has not been achieved. Herein, the ability to use semiconductor nanocrystals for efficient bulk polymerization as sole initiators is reported, operating under modern UV-blue-LED light sources found in 3D printers and other photocuring applications. Hybrid semiconductor-metal nanorods exhibit superior photoinitiation capability to their pristine semiconductor counterparts, attributed to the enhanced charge separation and oxygen consumption in such systems. Moreover, photoinitiation by semiconductor nanocrystals overcoated by inorganic ligands is reported, thus increasing the scope of possible applications and shedding light on the photoinitiation mechanism; in light of the results, two possible pathways are discussed - ligand-mediated and cation-coordinated oxidation A demonstration of the unique attributes of the quantum photoinitiators is reported in their use for high-resolution two-photon printing of optically fluorescing microstructures, demonstrating a multi-functionality capability. The bulk polymerization demonstrated here can be advantageous over solvent based methods as it alleviates the need of post-polymerization drying and reduces waste and exposure to toxic solvents, as well as broadens the possible use of quantum photoinitiators for industrial and research uses.

Semiconductor nanocrystals have been shown to have unique advantages over traditional organic photoinitiators for polymerization in solution. However, efficient photoinitiation with such nanoparticles in solvent-free and additive-free formulations so far has not been achieved. Herein, the ability to use semiconductor nanocrystals for efficient bulk polymerization as sole initiators is reported, operating under modern UV-blue-LED light sources found in 3D printers and other photocuring applications. Hybrid semiconductor-metal nanorods exhibit superior photoinitiation capability to their pristine semiconductor counterparts, attributed to the enhanced charge separation and oxygen consumption in such systems. Moreover, photoinitiation by semiconductor nanocrystals overcoated by inorganic ligands is reported, thus increasing the scope of possible applications and shedding light on the photoinitiation mechanism; in light of the results, two possible pathways are discussed - ligand-mediated and cation-coordinated oxidation. A demonstration of the unique attributes of the quantum photoinitiators is reported in their use for high-resolution two-photon printing of optically fluorescing microstructures, demonstrating a multi-functionality capability. The bulk polymerization demonstrated here can be advantageous over solvent based methods as it alleviates the need of post-polymerization drying and reduces waste and exposure to toxic solvents, as well as broadens the possible use of quantum photoinitiators for industrial and research uses.

This review describes recent developments in the field of conductive nanomaterials and their application in 2D and 3D printed flexible electronics, with particular emphasis on inks based on metal nanoparticles and nanowires, carbon nanotubes, and graphene sheets. We present the basic properties of these nanomaterials, their stabilization in dispersions, formulation of conductive inks and formation of conductive patterns on flexible substrates (polymers, paper, textile) by using various printing technologies and post-printing processes. Applications of conductive nanomaterials for fabrication of various 2D and 3D electronic devices are also briefly discussed.

This review describes recent developments in the field of conductive nanomaterials and their application in 2D and 3D printed flexible electronics, with particular emphasis on inks based on metal nanoparticles and nanowires, carbon nanotubes, and graphene sheets. We present the basic properties of these nanomaterials, their stabilization in dispersions, formulation of conductive inks and formation of conductive patterns on flexible substrates (polymers, paper, textile) by using various printing technologies and post-printing processes. Applications of conductive nanomaterials for fabrication of various 2D and 3D electronic devices are also briefly discussed.

Local mechanical cues can affect crucial fate decisions of living cells. Transepithelial stress has been discussed in the context of epithelial monolayers, but the lack of appropriate experimental systems leads current studies to approximate it simply as an in-plane stress. To evaluate possible contribution of force vectors acting in other directions, double epithelium in a 3D-printed "GeminiChip" containing a sessile and a pendant channel is reconstituted. Intriguingly, the sessile epithelia is prone to apoptotic cell extrusion upon crowding, whereas the pendant counterpart favors live cell delamination. Transcriptome analyses show upregulation of RhoA, BMP2, and hypoxia-signaling genes in the pendant epithelium, consistent with the onset of an epithelial-mesenchymal transition program. HepG2 microtumor spheroids also display differential spreading patterns in the sessile and pendant configuration. Using this multilayered GeminiChip, these results uncover a progressive yet critical role of perpendicular force vectors in collective cell behaviors and point at fundamental importance of these forces in the biology of cancer.

Aerogel objects inspired by plant cell wall components and structures were fabricated using extrusion-based 3D printing at cryogenic temperatures. The printing process combines 3D printing with the alignment of rod-shaped nanoparticles through the freeze-casting of aqueous inks. We have named this method direct cryo writing (DCW) as it encompasses in a single processing step traditional directional freeze casting and the spatial fidelity of 3D printing. DCW is demonstrated with inks that are composed of an aqueous mixture of cellulose nanocrystals (CNCs) and xyloglucan (XG), which are the major building blocks of plant cell walls. Rapid fixation of the inks is achieved through tailored rheological properties and controlled directional freezing. Morphological evaluation revealed the role of ice crystal growth in the alignment of CNCs and XG. The structure of the aerogels changed from organized and tubular to disordered and flakey pores with an increase in XG content. The internal structure of the printed objects mimics the structure of various wood species and can therefore be used to create wood-like structures via additive manufacturing technologies using only renewable wood-based materials.

Directed-assembly by standing surface acoustic waves (SSAWs) only requires an acoustic contrast between particles and their surrounding medium. It is therefore highly attractive as this requirement is fulfilled by almost all dispersed systems. Previous studies utilizing SSAWs demonstrated mainly reversible microstructure arrangements from nanoparticles. The surface chemistry of colloids dramatically influences their tendency to aggregate and sinter; therefore, it should be possible to form permanent microstructures with intimate contact between nanoparticles by controlling this property. Dispersed silver nanoparticles in a microfluidic channel were exposed to SSAWs and reversibly accumulated at the pressure nodes. We show that addition of chloride ions that remove the polyacrylic capping of the nanoparticles trigger their sintering and the formation of stable conducting silver microstructures. Moreover, if the destabilizing ions are added prior to nanoparticle assembly while continuously streaming the dispersion through the acoustic aperture, the induced aggregation leads to formation of significantly thinner microstructures, which are (for the first time) unlimited in length by the acoustic apparatus. This new approach overcomes the discrepancy between the need for organic dispersants to prevent unwanted aggregation in the dispersion, and the end product's requirement for intimate contact between the colloidal particles.

Renewable energy technol. and effective energy management are the most crucial factors to consider in the progress toward worldwide energy sustainability. Smart window technol. has a huge potential in energy management as it assists in reducing energy consumption of indoor lighting and air-conditioning in buildings. Electrochromic (EC) materials, which can elec. modulate the transmittance of solar radiation, are one of the most studied smart window materials. In this work, highly transparent SnO2 inverse opal (IO) is used as the framework to electrochem. deposit amorphous WO3 layer to fabricate hybrid SnO2-WO3 core-shell IO structure. The hybrid structure is capable of effective near IR (NIR) modulation while maintaining high visible light transparency in the colored and bleached states. By varying the initial diameter of the polystyrene (PS) opal template and the WO3 electrodeposition time, optimal results can be obtained with the smallest PS diameter of 392 nm and 180 s WO3 electrodeposition. In its colored state, the 392-SnO2-WO3-180 core-shell IO structure shows ≈70% visible light transparency, 62% NIR blockage at 1200 nm, and ≈15% drop in NIR blocking stability after 300 cycles. The SnO2-WO3 core-shell IO structure in this study is a promising EC material for advanced smart window technol.

Two kinds of carbon-based nanozymes were constructed from the same precursor of zeolitic imidazolate framework-8 (ZIF-8) for O2•- determination Hollow carbon cubic nanomaterial (labeled as HCC) was obtained by chem. etching ZIF-8 with tannic acid and a subsequent calcination. A porous carbon cubic nanomaterial (labeled as PCC) was prepared by directly pyrolysis. Then HCC and PCC were immobilized on the surface of screen printed carbon electrodes (SPCE), fabricating HCC and PCC modified electrodes (denoted as HCC/SPCE and PCC/SPCE). HCC/SPCE, best operated at -0.5 V (vs. Ag/AgCl), has a sensitivity of 6.55 × 102 nA μM-1 cm-2 with a detection limit of 207 nM (at S/N = 3) for O2•- sensing. And PCC/SPCE, best operated at -0.4 V (vs. Ag/AgCl), exhibited a superior performance for O2•- detection with a sensitivity of 1.14 × 103 nA μM-1 cm-2 and a low detection limit of 140 nM (at S/N = 3). The two sensors possess excellent reproducibility and stability. They were used to sense O2•- released from HeLa cells. [Figure not available: see fulltext.]