Concept: Materials science
- Proceedings of the National Academy of Sciences of the United States of America
- Published almost 3 years ago
Poly(ethylene terephthalate) (PET) is one of the most abundantly produced synthetic polymers and is accumulating in the environment at a staggering rate as discarded packaging and textiles. The properties that make PET so useful also endow it with an alarming resistance to biodegradation, likely lasting centuries in the environment. Our collective reliance on PET and other plastics means that this buildup will continue unless solutions are found. Recently, a newly discovered bacterium, Ideonella sakaiensis 201-F6, was shown to exhibit the rare ability to grow on PET as a major carbon and energy source. Central to its PET biodegradation capability is a secreted PETase (PET-digesting enzyme). Here, we present a 0.92 Å resolution X-ray crystal structure of PETase, which reveals features common to both cutinases and lipases. PETase retains the ancestral α/β-hydrolase fold but exhibits a more open active-site cleft than homologous cutinases. By narrowing the binding cleft via mutation of two active-site residues to conserved amino acids in cutinases, we surprisingly observe improved PET degradation, suggesting that PETase is not fully optimized for crystalline PET degradation, despite presumably evolving in a PET-rich environment. Additionally, we show that PETase degrades another semiaromatic polyester, polyethylene-2,5-furandicarboxylate (PEF), which is an emerging, bioderived PET replacement with improved barrier properties. In contrast, PETase does not degrade aliphatic polyesters, suggesting that it is generally an aromatic polyesterase. These findings suggest that additional protein engineering to increase PETase performance is realistic and highlight the need for further developments of structure/activity relationships for biodegradation of synthetic polyesters.
The search for new hard materials is often challenging, but strongly motivated by the vast application potential such materials hold. Ti3Au exhibits high hardness values (about four times those of pure Ti and most steel alloys), reduced coefficient of friction and wear rates, and biocompatibility, all of which are optimal traits for orthopedic, dental, and prosthetic applications. In addition, the ability of this compound to adhere to ceramic parts can reduce both the weight and the cost of medical components. The fourfold increase in the hardness of Ti3Au compared to other Ti-Au alloys and compounds can be attributed to the elevated valence electron density, the reduced bond length, and the pseudogap formation. Understanding the origin of hardness in this intermetallic compound provides an avenue toward designing superior biocompatible, hard materials.
Inducing thermal gradients in fluid systems with initial, well-defined density gradients results in the formation of distinct layered patterns, such as those observed in the ocean due to double-diffusive convection. In contrast, layered composite fluids are sometimes observed in confined systems of rather chaotic initial states, for example, lattes formed by pouring espresso into a glass of warm milk. Here, we report controlled experiments injecting a fluid into a miscible phase and show that, above a critical injection velocity, layering emerges over a time scale of minutes. We identify critical conditions to produce the layering, and relate the results quantitatively to double-diffusive convection. Based on this understanding, we show how to employ this single-step process to produce layered structures in soft materials, where the local elastic properties vary step-wise along the length of the material.
There has been a growing interest in thermal management materials due to the prevailing energy challenges and unfulfilled needs for thermal insulation applications. We demonstrate the exceptional thermal management capabilities of a large-scale, hierarchal alignment of cellulose nanofibrils directly fabricated from wood, hereafter referred to as nanowood. Nanowood exhibits anisotropic thermal properties with an extremely low thermal conductivity of 0.03 W/m·K in the transverse direction (perpendicular to the nanofibrils) and approximately two times higher thermal conductivity of 0.06 W/m·K in the axial direction due to the hierarchically aligned nanofibrils within the highly porous backbone. The anisotropy of the thermal conductivity enables efficient thermal dissipation along the axial direction, thereby preventing local overheating on the illuminated side while yielding improved thermal insulation along the backside that cannot be obtained with isotropic thermal insulators. The nanowood also shows a low emissivity of <5% over the solar spectrum with the ability to effectively reflect solar thermal energy. Moreover, the nanowood is lightweight yet strong, owing to the effective bonding between the aligned cellulose nanofibrils with a high compressive strength of 13 MPa in the axial direction and 20 MPa in the transverse direction at 75% strain, which exceeds other thermal insulation materials, such as silica and polymer aerogels, Styrofoam, and wool. The excellent thermal management, abundance, biodegradability, high mechanical strength, low mass density, and manufacturing scalability of the nanowood make this material highly attractive for practical thermal insulation applications.
The response of amorphous steels to shock wave compression has been explored for the first time. Further, the effect of partial devitrification on the shock response of bulk metallic glasses is examined by conducting experiments on two iron-based in situ metallic glass matrix composites, containing varying amounts of crystalline precipitates, both with initial composition Fe49.7Cr17.7Mn1.9Mo7.4W1.6B15.2C3.8Si2.4. The samples, designated SAM2X5-600 and SAM2X5-630, are X-ray amorphous and partially crystalline, respectively, due to differences in sintering parameters during sample preparation. Shock response is determined by making velocity measurements using interferometry techniques at the rear free surface of the samples, which have been subjected to impact from a high-velocity projectile launched from a powder gun. Experiments have yielded results indicating a Hugoniot Elastic Limit (HEL) to be 8.58 ± 0.53 GPa for SAM2X5-600 and 11.76 ± 1.26 GPa for SAM2X5-630. The latter HEL result is higher than elastic limits for any BMG reported in the literature thus far. SAM2X5-600 catastrophically loses post-yield strength whereas SAM2X5-630, while showing some strain-softening, retains strength beyond the HEL. The presence of crystallinity within the amorphous matrix is thus seen to significantly aid in strengthening the material as well as preserving material strength beyond yielding.
Recycling rare earth elements (REEs) used in advanced materials such as Nd magnets is important for the efficient use of REE resources when the supply of several REEs is limited. In this work, the feasibility of using salmon milt for REE recovery and separation was examined, along with the identification of the binding site of REEs in salmon milt. Results showed that (i) salmon milt has a sufficiently high affinity to adsorb REEs and (ii) the adsorption capacity of the milt is 1.04 mEq/g, which is comparable with that of commercial cation exchange resin. Heavier REEs have higher affinity for milt. A comparison of stability constants and adsorption patterns of REEs discussed in the literature suggests that the phosphate is responsible for the adsorption of REE in milt. The results were supported by dysprosium (Dy) and lutetium (Lu) LIII-edge extended x-ray absorption fine structure (EXAFS) spectroscopy. The REE-P shell was identified for the second neighboring atom, which shows the importance of the phosphate site as REE binding sites. The comparison of REE adsorption pattern and EXAFS results between the milt system and other adsorbent systems (cellulose phosphate, Ln-resin, bacteria, and DNA-filter hybrid) revealed that the coordination number of phosphate is correlated with the slope of the REE pattern. The separation column loaded with milt was tested to separate REE for the practical use of salmon milt for the recovery and separation of REE. However, water did not flow through the column possibly because of the hydrophobicity of the milt. Thus, sequential adsorption-desorption approach using a batch-type method was applied for the separation of REE. As an example of the practical applications of REE separation, Nd and Fe(III) were successfully separated from a synthetic solution of Nd magnet waste by a batch-type method using salmon milt.
Globally ordered colloidal crystal lattices have broad utility in a wide range of optical and catalytic devices, for example, as photonic bandgap materials. However, the self-assembly of stereospecific structures is often confounded by polymorphism. Small free energy differences often characterize ensembles of different structures, making it difficult to produce a single morphology at will. Current techniques to handle this problem adopt one of two approaches: that of the “top-down,” or “bottom-up” methodology, whereby structures are engineered starting from the largest or smallest relevant length scales, respectively. However, recently a third approach for directing high fidelity assembly of colloidal crystals has been suggested which relies on the introduction of polymer co-solutes into the crystal phase [N. A. Mahynski, A. Z. Panagiotopoulos, D. Meng, S. K. Kumar, Nat. Commun., 2014, 5, 4472]. By tuning the polymer’s morphology to interact uniquely with the void symmetry of a single desired crystal, the entropy loss associated with polymer confinement has been shown to strongly bias the formation of that phase. However, previously this approach has only been demonstrated in the limiting case of close-packed crystals. Here we show how this approach may be generalized and extended to complex open crystals, illustrating the utility of this “structure-directing agent” paradigm in engineering the nanoscale structure of ordered colloidal materials. The high degree of transferability of this paradigm’s basic principles between relatively simple crystals and more complex ones suggests this represents a valuable addition to presently known self-assembly techniques.
Under high-strain-rate compression (strain rate approximately 10(3) s(-1)), nacre (mother-of-pearl) exhibits surprisingly high fracture strength vis-à-vis under quasi-static loading (strain rate 10(-3) s(-1)). Nevertheless, the underlying mechanism responsible for such sharply different behaviors in these two loading modes remains completely unknown. Here we report a new deformation mechanism, adopted by nacre, the best-ever natural armor material, to protect itself against predatory penetrating impacts. It involves the emission of partial dislocations and the onset of deformation twinning that operate in a well-concerted manner to contribute to the increased high-strain-rate fracture strength of nacre. Our findings unveil that Mother Nature delicately uses an ingenious strain-rate-dependent stiffening mechanism with a purpose to fight against foreign attacks. These findings should serve as critical design guidelines for developing engineered body armor materials.
The potential of thermoelectric materials to generate electricity from the waste heat can play a key role in achieving a global sustainable energy future. In order to proceed in this direction, it is essential to have thermoelectric materials that are environmentally friendly and exhibit high figure of merit, ZT. Oxide thermoelectric materials are considered ideal for such applications. High thermoelectric performance has been reported in single crystals of Ca3Co4O9. However, for large scale applications single crystals are not suitable and it is essential to develop high-performance polycrystalline thermoelectric materials. In polycrystalline form, Ca3Co4O9 is known to exhibit much weaker thermoelectric response than in single crystal form. Here, we report the observation of enhanced thermoelectric response in polycrystalline Ca3Co4O9 on doping Tb ions in the material. Polycrystalline Ca3-xTbxCo4O9 (x = 0.0-0.7) samples were prepared by a solid-state reaction technique. Samples were thoroughly characterized using several state of the art techniques including XRD, TEM, SEM and XPS. Temperature dependent Seebeck coefficient, electrical resistivity and thermal conductivity measurements were performed. A record ZT of 0.74 at 800 K was observed for Tb doped Ca3Co4O9 which is the highest value observed till date in any polycrystalline sample of this system.
Electronic carriers in graphene show a high carrier mobility at room temperature. Thus, this system is widely viewed as a potential future charge-based high-speed electronic material to complement-or replace-silicon. At the same time, the spin properties of graphene have suggested improved capability for spin-based electronics or spintronics and spin-based quantum computing. As a result, the detection, characterization and transport of spin have become topics of interest in graphene. Here we report a microwave photo-excited transport study of monolayer and trilayer graphene that reveals an unexpectedly strong microwave-induced electrical response and dual microwave-induced resonances in the dc resistance. The results suggest the resistive detection of spin resonance, and provide a measurement of the g-factor, the spin relaxation time and the sub-lattice degeneracy splitting at zero magnetic field.