Dual carbon sequestration with photosynthetic living materials.

Natural ecosystems offer efficient pathways for carbon sequestration, serving as a resilient approach to remove CO2 from the atmosphere with minimal environmental impact. However, the control of living systems outside of their native environments is often challenging. Here, we engineered a photosynthetic living material for dual CO2 sequestration by immobilizing photosynthetic microorganisms within a printable polymeric network. The carbon concentrating mechanism of the cyanobacteria enabled accumulation of CO2 within the cell, resulting in biomass production. Additionally, the metabolic production of OH- ions in the surrounding medium created an environment for the formation of insoluble carbonates via microbially-induced calcium carbonate precipitation (MICP). Digital design and fabrication of the living material ensured sufficient access to light and nutrient transport of the encapsulated cyanobacteria, which were essential for long-term viability (more than one year) as well as efficient photosynthesis and carbon sequestration. The photosynthetic living materials sequestered approximately 2.5 mg of CO2 per gram of hydrogel material over 30 days via dual carbon sequestration, with 2.2 ± 0.9 mg stored as insoluble carbonates. Over an extended incubation period of 400 days, the living materials sequestered 26 ± 7 mg of CO2 per gram of hydrogel material in the form of stable minerals. These findings highlight the potential of photosynthetic living materials for scalable carbon sequestration, carbon-neutral infrastructure, and green building materials. The simplicity of maintenance, coupled with its scalability nature, suggests broad applications of photosynthetic living materials as a complementary strategy to mitigate CO2 emissions.

Hierarchically roughened microplatelets enhance the strength and ductility of nacre-inspired composites.

Rough interfaces featuring nanoscale asperities are known to play a major role in the mechanics of nacre. Transferring this concept to artificial bioinspired composites requires a detailed understanding about the effect of the surface topography of reinforcing elements on the mechanical performance of such materials. To gain further insights into the effect of asperity size, hierarchy and coverage on the mechanics of nacre-inspired composites, we decorate alumina microplatelets with silica nanoparticles of selected sizes and use the resulting roughened platelets as reinforcing elements (15vol%) in a commercial epoxy matrix. For a single layer of silica nanoparticles on the platelet surface, increased ultimate strain and toughness are obtained with a large roughening particle size of 250nm. On the contrary, strength and stiffness are enhanced by decreasing the size of asperities using 22nm silica particles. By combining particles of two different sizes (100nm and 22nm) in a hierarchical fashion, we are able to improve stiffness and strength of platelet-reinforced polymers while maintaining high ultimate strain and toughness. Our results indicate that carefully designed hierarchically roughened interfaces lead to a more homogeneous stress distribution within the polymer matrix between the stiff reinforcing elements. By enabling the deformation of a larger fraction of the polymer matrix, this design concept improves the mechanical response of bioinspired composites and can possibly also be exploited to enhance the performance of conventional fiber-reinforced polymers.

Ultrahigh magnetically responsive microplatelets with tunable fluorescence emission.

Tuning the optical properties of suspensions by controlling the orientation and spatial distribution of suspended particles with magnetic fields is an interesting approach to creating magnetically controlled displays, microrheology sensors, and materials with tunable light emission. However, the relatively high concentration of magnetic material required to manipulate these particles very often reduces the optical transmittance of the system. In this study, we describe a simple method of generating particles with magnetically tunable optical properties via sol-gel deposition and functionalization of a continuous layer of silica on ultrahigh magnetically responsive (UHMR) alumina microplatelets. UHMR microplatelets with tunable magnetic response in the range of 15-36 G are obtained by the electrostatic adsorption of 2 to 13% of superparamagnetic iron oxide nanoparticles (SPIONs) on the alumina surface. The magnetized platelets are coated with a 20-50 nm layer of SiO2 through the controlled hydrolysis and condensation reactions of tetraethylorthosilicate (TEOS) in an NH3/ethanol mixture. Finally, the silica surface is covalently modified with an organic fluorescent dye by conventional silane chemistry. Because of the anisotropic shape of the particles, control of their orientation and distribution using magnetic fields and field gradients enables easy tuning of the optical properties of the suspension. This strategy allows us to gain both spatial and temporal control over the fluorescence emission from the particle surface, making the multifunctional platelets interesting building blocks for the manipulation of light in colloid-based smart optical devices and sensors.

Unifying model for the electrokinetic and phase behavior of aqueous suspensions containing short and long amphiphiles.

Aqueous suspensions containing oppositely charged colloidal particles and amphiphilic molecules can form fluid dispersions, foams, and percolating gel networks, depending on the initial concentration of amphiphiles. While models have been proposed to explain the electrokinetic and flotation behavior of particles in the presence of long amphiphilic molecules, the effect of amphiphiles with less than six carbons in the hydrocarbon tail on the electrokinetic, rheological, and foaming behavior of aqueous suspensions remains unclear. Unlike conventional long amphiphiles (≥10 carbons), short amphiphiles do not exhibit increased adsorption on the particle surface when the number of carbons in the molecule tail is increased. On the basis of classical electrical double layer theory and the formerly proposed hemimicelle concept, we put forward a new predictive model that reconciles the adsorption and electrokinetic behavior of colloidal particles in the presence of long and short amphiphiles. By introducing in the classical Gouy-Chapman theory an energy term associated with hydrophobic interactions between the amphiphile hydrocarbon tails, we show that amphiphilic electrolytes lead to a stronger compression of the diffuse part of the electrical double layer in comparison to hydrophilic electrolytes. Scaling relationships derived from this model provide a quantitative description of the rich phase behavior of the investigated suspensions, correctly accounting for the effect of the alkyl chain length of short and long amphiphiles on the electrokinetics of such colloidal systems. The proposed model contributes to our understanding of the stabilization mechanisms of particle-stabilized foams and emulsions and might provide new insights into the physicochemical processes involved in mineral flotation.

Bioinspired design and assembly of platelet reinforced polymer films.

Although strong and stiff human-made composites have long been developed, the microstructure of today's most advanced composites has yet to achieve the order and sophisticated hierarchy of hybrid materials built up by living organisms in nature. Clay-based nanocomposites with layered structure can reach notable stiffness and strength, but these properties are usually not accompanied by the ductility and flaw tolerance found in the structures generated by natural hybrid materials. By using principles found in natural composites, we showed that layered hybrid films combining high tensile strength and ductile behavior can be obtained through the bottom-up colloidal assembly of strong submicrometer-thick ceramic platelets within a ductile polymer matrix.

Colloidal stabilization of nanoparticles in concentrated suspensions.

The stabilization of nanoparticles in concentrated aqueous suspensions is required in many manufacturing technologies and industrial products. Nanoparticles are commonly stabilized through the adsorption of a dispersant layer around the particle surface. The formation of a dispersant layer (adlayer) of appropriate thickness is crucial for the stabilization of suspensions containing high nanoparticle concentrations. Thick adlayers result in an excessive excluded volume around the particles, whereas thin adlayers lead to particle agglomeration. Both effects reduce the maximum concentration of nanoparticles in the suspension. However, conventional dispersants do not allow for a systematic control of the adlayer thickness on the particle surface. In this study, we synthesized dispersants with a molecular architecture that enables better control over the particle adlayer thickness. By tailoring the chemistry and length of these novel dispersants, we were able to prepare fluid suspensions (viscosity < 1 Pa.s at 100 s-1) with more than 40 vol % of 65-nm alumina particles in water, as opposed to the 30 vol % achieved with a state-of-the-art dispersing agent. This remarkably high concentration facilitates the fabrication of a wide range of products and intermediates in materials technology, cosmetics, pharmacy, and in all other areas where concentrated nanoparticle suspensions are required. On the basis of the proposed molecular architecture, one can also envisage other similar molecules that could be successfully applied for the functionalization of surfaces for biosensing, chromatography, medical imaging, drug delivery, and aqueous lubrication, among others.

Mechanical and fracture behavior of veneer-framework composites for all-ceramic dental bridges.

OBJECTIVES: High-strength ceramics are required in dental posterior restorations in order to withstand the excessive tensile stresses that occur during mastication. The aim of this study was to investigate the fracture behavior and the fast-fracture mechanical strength of three veneer-framework composites (Empress 2/IPS Eris, TZP/Cercon S and Inceram-Zirconia/Vita VM7) for all-ceramic dental bridges. METHODS: The load bearing capacity of the veneer-framework composites were evaluated using a bending mechanical apparatus. The stress distribution through the rectangular-shaped layered samples was assessed using simple beam calculations and used to estimate the fracture strength of the veneer layer. Optical microscopy of fractured specimens was employed to determine the origin of cracks and the fracture mode. RESULTS: Under fast fracture conditions, cracks were observed to initiate on, or close to, the veneer outer surface and propagate towards the inner framework material. Crack deflection occurred at the veneer-framework interface of composites containing a tough framework material (TZP/Cercon S and Inceram-Zirconia/Vita VM7), as opposed to the straight propagation observed in the case of weaker frameworks (Empress 2/IPS Eris). SIGNIFICANCE: The mechanical strength of dental composites containing a weak framework (K(IC)<3 MPam(1/2)) is ultimately determined by the low fracture strength of the veneer layer, since no crack arresting occurs at the veneer-framework interface. Therefore, high-toughness ceramics (K(IC)>5 MPam(1/2)) should be used as framework materials of posterior all-ceramic bridges, so that cracks propagating from the veneer layer do not lead to a premature failure of the prosthesis.

Cyclic fatigue in water of veneer-framework composites for all-ceramic dental bridges.

OBJECTIVES: Ceramic materials applied in dentistry may exhibit significant subcritical crack growth due to the severe cyclic loading in the aqueous environment encountered in the mouth during mastication. The authors report on the subcritical crack growth behavior of three dental restoration systems (Empress 2/IPS Eris, TZP/Cercon S and Inceram-Zirconia/Vita VM7) under cyclic loading in water, in order to establish guidelines for the use and design of long-lifetime all-ceramic posterior bridges. METHODS: Inert strength and lifetime tests under cyclic loading in an aqueous environment were performed in a mechanical bending apparatus and evaluated with Weibull statistics. RESULTS: Subcritical crack growth occurred predominantly in the outer veneer layer of the veneer-framework composites. The apatite-based veneer (IPS Eris) was more susceptible to subcritical crack propagation compared to the feldspathic glass veneers (Cercon S and Vita VM7). SIGNIFICANCE: Dental restoration systems containing apatite-based veneers and weak frameworks (Empress 2/IPS Eris) are not recommended for the fabrication of all-ceramic bridges in the molar region. Conversely, veneer-framework systems consisting of feldspathic glass veneers and tough zirconia-based frameworks (TZP/Cercon S and Inceram-Zirconia/Vita VM7) may exhibit lifetimes longer than 20 years if the bridge connector is properly designed.