De Novo Design of Polyhedral Protein Assemblies: Before and After the AI Revolution

Self-assembling polyhedral protein biomaterials have gained attention as engineering targets owing to their naturally evolved sophisticated functions, ranging from protecting macromolecules from the environment to spatially controlling biochemical reactions. Precise computational design of de novo protein polyhedra is possible through two main types of approaches: methods from first principles, using physical and geometrical rules, and more recent data-driven methods based on artificial intelligence (AI), including deep learning (DL). Here, we retrospect first principle- and AI-based approaches for designing finite polyhedral protein assemblies, as well as advances in the structure prediction of such assemblies. We further highlight the possible applications of these materials and explore how the presented approaches can be combined to overcome current challenges and to advance the design of functional protein-based biomaterials.     

Modelling of multicomponent gas separation with asymmetric hollow fibre membranes—methane enrichment from biogas

A mathematical model for the dynamic performance of gas separation with high flux, asymmetric hollow fibre membranes was developed considering the permeate pressure build‐up inside the fibre bore and cross flow pattern with respect to the membrane skin. The solution technique provides reliable examination of pressure and concentration profiles along the permeator length (both residue/permeate streams) with minimal effort. The proposed simulation model and scheme were validated with experimental data of gas separation from literature. The model and solution technique were applied to investigate dynamic performance of several membrane module configurations for methane recovery from biogas (landfill gas or digester gas), considering biogas as a mixture of CO₂, N₂ and CH₄. Recycle ratio plays a crucial role, and optimum recycle ratio vital for the retentate recycle to permeate and permeate recycle to feed operation was found. From the concept of two recycle operations, complexities involved in the design and operation of continuous membrane column were simplified. Membrane permselectivity required for a targeted separation to produce pipeline quality natural gas by methane‐selective or nitrogen‐selective membranes was calculated. © 2012 Canadian Society for Chemical Engineering     

Direct stamping and capillary flow patterning of solution processable piezoelectric polyvinylidene fluoride films

It is well known that the potential applications of polyvinylidene fluoride (PVDF) mainly come from the piezoelectricity and ferroelectricity of its polar β phase. Thus, we have investigated the effect of different preparation conditions namely evaporation temperature, type of solvent and additive to enhance the β crystal structures of PVDF thin film. Subsequently, facile and direct soft lithography technique; direct stamping and capillary flow were employed to demonstrate good pattern transfer of PVDF thin films. The piezoelectricity of the microstructure was characterized using piezoresponse force microscopy (PFM) where fairly good piezoresponse was obtained without further processing procedures i.e., annealing or applied pressure/electric field. As such, our solution processable and direct patterning of PVDF techniques offer facile and promising route to produce arrays of isolated microstructures with improved piezoelectric functionality.     

The effect of partial replacement of carbon black by carbon nanotubes on the properties of natural rubber/butadiene rubber compound

The basic objective of this study is to investigate the mechanical properties of tyre tread compounds by gradual replacement of carbon black by multiwalled carbon nanotubes (MWCNTs) in a natural rubber–butadiene rubber‐based system. A rapid change in the mechanical properties is noticed even at very low concentrations of nanotubes though the total concentration of the filler is kept constant at 25 phr (parts per hundred rubber). The correlation of the bound rubber content with MWCNT loading directly supports the conclusion that MWCNTs increase the occluded rubber fraction. Transmission electron microscopy reveals a good dispersion of the MWCNT up to a certain concentration. In the presence of MWCNT, a prominent negative shift of the glass transition temperature of the compound is found. Thermal degradation behavior, aging, and swelling experiments were also carried out to understand the resulting effect of the incorporation of MWCNT in the rubber matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3153–3160, 2013     

Investigating the role of key ingredients on cathodic delamination resistance of high-build pigmented epoxy coatings

Organic coatings applied on cathodically protected metallic structures must have good resistance to cathodic delamination or disbonding (CD). Both environmental conditions and coating composition influence the CD resistance. In the present study, the effect of types of epoxy resin, curing agents and their mixing ratio on cathodic delamination rate was studied in a high-build pigmented coating. Furthermore, the influence of platey fillers on CD resistance was also studied. In order to bring out correlations, if any, between adhesion and CD resistance, pull-off adhesion strengths (both dry and wet) of these coatings were also measured. Fairly good correlation was found between residual (wet) pull-off adhesion strength and CD resistance. When tested at 60 and 90°C, all the coatings under investigation showed chalking. Among the coatings under investigation, the one based on Bisphenol F epoxy and modified cycloaliphatic amine adduct exhibited excellent CD resistance.     

Dynamic tensile strength of polyurea-bonded steel/E-glass composite joints

The dynamic tensile strengths of E-glass composite/polyurea and polyurea/steel interfaces within the E-glass composite/polyurea/AL-6XN stainless steel joint were measured using a laser spallation technique. Values of 370?±?20?MPa were obtained for the polyurea/composite interface while a much higher value of 486?±?20?MPa was obtained for the steel/polyurea interface. Because of the transient nature of the stress pulse, the strain rate changes continuously as the interface stress builds up. A peak strain rate of 5?×?10⁵?s^?1 was estimated. The effect of moisture on the tensile strength of the E-glass/polyurea interface was also examined. The effect was found to be minimal, with the tensile strength stabilizing at 320?±?25?MPa after 30?days of exposure to a 90%RH, 50?°C environment. When comparing the strengths of corresponding interfaces in an epoxy-bonded joint from a previous study, it was concluded that polyurea results in a much stronger and durable joint.     

Impact of electrically formed interfacial layer and improved memory characteristics of IrOx/high-κx/W structures containing AlOx,GdOx, HfOx,and TaOx switching materials

Improved switching characteristics were obtained from high-κ oxides AlO_x, GdO_x, HfO_x, and TaO_x in IrO_x/high-κ_x/W structures because of a layer that formed at the IrO_x/high-κ_x interface under external positive bias. The surface roughness and morphology of the bottom electrode in these devices were observed by atomic force microscopy. Device size was investigated using high-resolution transmission electron microscopy. More than 100 repeatable consecutive switching cycles were observed for positive-formatted memory devices compared with that of the negative-formatted devices (only five unstable cycles) because it contained an electrically formed interfacial layer that controlled ‘SET/RESET’ current overshoot. This phenomenon was independent of the switching material in the device. The electrically formed oxygen-rich interfacial layer at the IrO_x/high-κ_x interface improved switching in both via-hole and cross-point structures. The switching mechanism was attributed to filamentary conduction and oxygen ion migration. Using the positive-formatted design approach, cross-point memory in an IrO_x/AlO_x/W structure was fabricated. This cross-point memory exhibited forming-free, uniform switching for >1,000 consecutive dc cycles with a small voltage/current operation of ±2 V/200 μA and high yield of >95% switchable with a large resistance ratio of >100. These properties make this cross-point memory particularly promising for high-density applications. Furthermore, this memory device also showed multilevel capability with a switching current as low as 10 μA and a RESET current of 137 μA, good pulse read endurance of each level (>10⁵ cycles), and data retention of >10⁴ s at a low current compliance of 50 μA at 85°C. Our improvement of the switching characteristics of this resistive memory device will aid in the design of memory stacks for practical applications.     

Resistive switching memory characteristics of Ge/GeOx nanowires and evidence of oxygen ion migration

The resistive switching memory of Ge nanowires (NWs) in an IrO_x/Al₂O₃/Ge NWs/SiO₂/p-Si structure is investigated. Ge NWs with an average diameter of approximately 100 nm are grown by the vapor–liquid-solid technique. The core-shell structure of the Ge/GeO_x NWs is confirmed by both scanning electron microscopy and high-resolution transmission electron microscopy. Defects in the Ge/GeO_x NWs are observed by X-ray photoelectron spectroscopy. Broad photoluminescence spectra from 10 to 300 K are observed because of defects in the Ge/GeO_x NWs, which are also useful for nanoscale resistive switching memory. The resistive switching mechanism in an IrO_x/GeO_x/W structure involves migration of oxygen ions under external bias, which is also confirmed by real-time observation of the surface of the device. The porous IrO_x top electrode readily allows the evolved O₂ gas to escape from the device. The annealed device has a low operating voltage (<4 V), low RESET current (approximately 22 μA), large resistance ratio (>10³), long pulse read endurance of >10⁵ cycles, and good data retention of >10⁴ s. Its performance is better than that of the as-deposited device because the GeO_x film in the annealed device contains more oxygen vacancies. Under SET operation, Ge/GeO_x nanofilaments (or NWs) form in the GeO_x film. The diameter of the conducting nanofilament is approximately 40 nm, which is calculated using a new method.     

Solubilities of Carbon Dioxide in Polyethylene Glycol Ethers

New extensive data are reported for the solubility of carbon dioxide in fourteen physical solvents, and compared to two other solvents widely used in industry (selexol® and sulfolane). The solubility data are expressed by Henry's law constants and have been measured at 25 °C, 40 °C and 60 °C, using an Autoclave cell. The study concludes that polyethylene glycol dimethyl ethers, and mixtures of these solvents are the best solvents for CO₂ removal.