Capturing the Transient Microstructure of a Physically Assembled Gel Subjected to Temperature and Large Deformation

The microstructure of physically assembled gels depends on mechanical loading and environmental stimuli such as temperature. Here, we report the real-time change in the structure of physically assembled triblock copolymer gels that consist of 10 wt% and 20 wt% of poly(styrene)-poly(isoprene)-poly(styrene) [PS-PI-PS] triblock copolymer in mineral oil (i) during the gelation process with decreasing temperature, (ii) subjected to large oscillatory deformation, and (iii) during the stress-relaxation process after the application of a step-strain. The presence of loosely bounded PS-aggregates at temperatures higher than the rheologically determined gelation temperature (Tgel) captures the progressive gelation process spanning over a broad temperature range. However, the microstructure fully develops at temperatures sufficiently lower than Tgel. The microstructure orients in the stretching direction with the applied strain. In an oscillation strain cycle, such oriented structure has been observed at low-strain. But, at large-strain, because of strain-localization the oriented structure splits, and only a fraction of midblock participates in load-bearing. Both microstructure recovery and time-dependent moduli during the stress-relaxation process after the application of a step-strain have been captured using a stretched-exponential model. However, the microstructure recovery time has been found to be two orders of magnitude slower than the stress-relaxation time at room temperature, indicating a complex nature of stress-relaxation and microstructure recovery processes involving midblock relaxation, endblock pullout and reassociation. Due to their viscoelastic nature, these gels' mechanical responses are sensitive to strain, temperature, and rate of deformation. Therefore, insights into the microstructural information as a function of these parameters will assist these gels' real-life applications and design new gels with improved properties.

Capturing the Transient Microstructure of a Physically Assembled Gel Subjected to Temperature and Large Deformation

The microstructure of physically assembled gels depends on mechanical loading and environmental stimuli such as temperature. Here, we report the real-time change in the structure of physically assembled triblock copolymer gels that consist of 10 wt% and 20 wt% of poly(styrene)-poly(isoprene)-poly(styrene) [PS-PI-PS] triblock copolymer in mineral oil (i) during the gelation process with decreasing temperature, (ii) subjected to large oscillatory deformation, and (iii) during the stress-relaxation process after the application of a step-strain. The presence of loosely bounded PS-aggregates at temperatures higher than the rheometrically determined gelation temperature (Tgel) captures the progressive gelation process spanning over a broad temperature range. However, the microstructure fully develops at temperatures suciently lower than Tgel, and the storage modulus (G0 ) also reaches a plateau at those temperatures. The microstructure orients in the stretching direction with the applied strain. In an oscillation strain cycle, such oriented structure has been observed at low-strain. But, at large-strain, the oriented structure splits, and only a fraction of midblock participates in load-bearing. This has been attributed to the endblock pullout from the aggregates, likely caused by the strain localization in the samples. Both microstructure recovery and time-dependent moduli during the stress-relaxation process after the application of a step-strain can be captured using a stretched-exponential model. However, the microstructure recovery time has been found to be two orders of magnitude slower than the stress-relaxation time at room temperature, indicating a complex nature of relaxation process involving midblock relaxation, endblock pullout and reassociation process. Due to their viscoelastic nature, these gels' mechanical responses are sensitive to strain, temperature, and rate of deformation. Therefore, insights into the microstructural information as a function of these parameters will assist these gels' real-life applications and design new gels with improved properties<br>

Capturing the Transient Microstructure of a Physically Assembled Gel Subjected to Temperature and Large Deformation

The microstructure of physically assembled gels depends on mechanical loading and environmental stimuli such as temperature. Here, we report the real-time change in the structure of physically assembled triblock copolymer gels that consist of 10 wt% and 20 wt% of poly(styrene)-poly(isoprene)-poly(styrene) [PS-PI-PS] triblock copolymer in mineral oil (i) during the gelation process with decreasing temperature, (ii) subjected to large oscillatory deformation, and (iii) during the stress-relaxation process after the application of a step-strain. The presence of loosely bounded PS-aggregates at temperatures higher than the rheometrically determined gelation temperature (Tgel) captures the progressive gelation process spanning over a broad temperature range. However, the microstructure fully develops at temperatures suciently lower than Tgel, and the storage modulus (G0 ) also reaches a plateau at those temperatures. The microstructure orients in the stretching direction with the applied strain. In an oscillation strain cycle, such oriented structure has been observed at low-strain. But, at large-strain, the oriented structure splits, and only a fraction of midblock participates in load-bearing. This has been attributed to the endblock pullout from the aggregates, likely caused by the strain localization in the samples. Both microstructure recovery and time-dependent moduli during the stress-relaxation process after the application of a step-strain can be captured using a stretched-exponential model. However, the microstructure recovery time has been found to be two orders of magnitude slower than the stress-relaxation time at room temperature, indicating a complex nature of relaxation process involving midblock relaxation, endblock pullout and reassociation process. Due to their viscoelastic nature, these gels' mechanical responses are sensitive to strain, temperature, and rate of deformation. Therefore, insights into the microstructural information as a function of these parameters will assist these gels' real-life applications and design new gels with improved properties<br>

Surface energy and separation mechanics of droplet interface phospholipid bilayers

Droplet interface bilayers are a convenient model system to study the physio-chemical properties of phospholipid bilayers, the major component of the cell membrane. The mechanical response of these bilayers to various external mechanical stimuli is an active area of research because of its implications for cellular viability and the development of artificial cells. In this article, we characterize the separation mechanics of droplet interface bilayers under step strain using a combination of experiments and numerical modelling. Initially, we show that the bilayer surface energy can be obtained using principles of energy conservation. Subsequently, we subject the system to a step strain by separating the drops in a step-wise manner, and track the evolution of the bilayer contact angle and radius. The relaxation time of the bilayer contact angle and radius along with the decay magnitude of the bilayer radius were observed to increase with each separation step. By analysing the forces acting on the bilayer and the rate of separation, we show that the bilayer separates primarily through the peeling process with the dominant resistance to separation coming from viscous dissipation associated with corner flows. Finally, we explain the intrinsic features of the observed bilayer separation by means of a mathematical model comprising the Young–Laplace equation and an evolution equation. We believe that the reported experimental and numerical results extend the scientific understanding of lipid bilayer mechanics, and that the developed experimental and numerical tools offer a convenient platform to study the mechanics of other types of bilayers.

Efficient Optimization of Gluconobacter oxydans Based on Protein Scaffold-Trimeric CutA to Enhance the Chemical Structure Stability of Enzymes for the Direct Production of 2-Keto-L-gulonic Acid

2-Keto-L-gulonic acid (2-KLG), the direct precursor of vitamin C, is produced by a two-step fermentation route from D-sorbitol in industry. However, this route is a complicated mix-culture system which involves three bacteria. Thus, replacement of the conventional two-step fermentation process with a one-step process could be revolutionary in vitamin C industry. The one-step fermentation of 2-keto-L-gulonic acid (2-KLG) has been achieved in our previous study; 32.4 g/L of 2-KLG production was obtained by the one-step strain G. oxydans/pGUC-tufB-sdh-GGGGS-sndh after 168 h. In this study, L-sorbose dehydrogenase (SDH) and L-sorbosone dehydrogenase (SNDH) were expressed in G. oxydans after the codon optimization. Furthermore, the trimeric protein CutA was used to improve the chemical structure stability of SDH and SNDH. The recombinant strain G. oxydans/pGUC-tufB-SH3-sdh-GGGGS-sndh-tufB-SH3lig-(GGGGS)2-cutA produced 40.3 g/L of 2-KLG after 168 h. In addition, the expression levels of the cofactor PQQ were enhanced to further improve 2-KLG production. With the stepwise metabolic engineering of G. oxydans, the final 2-KLG production was improved to 42.6 g/L. The efficient one-step production of 2-KLG was achieved, and the final one-step industrial-scale production of 2-KLG is drawing near.

Strain-Level Determination Procedure for Small-Specimen Cyclic Fatigue Testing in the Asphalt Mixture Performance Tester

With an increase in small-specimen cyclic fatigue testing using the Asphalt Mixture Performance Tester (AMPT), researchers have observed that the strain-selection guidelines in AASHTO TP 107-14 that are intended for large AMPT cyclic fatigue tests are inadequate for testing small specimens. The machine compliance factor is significantly different for testing small specimens compared with large specimens because of different required load levels, resulting in a significant offset in the relationship between the input strain and the number of cycles to failure. To this end, this paper presents the development and verification of a phenomenological model that relates strain levels to dynamic modulus and number of cycles to failure for small-specimen AMPT cyclic fatigue tests, as well as the development of a corresponding stepped strain-level determination procedure that takes into account cases when the initially selected strain-level results in an unexpected number of cycles to failure. The final procedure includes a table with input strain levels and step strain increments for a wide range of dynamic modulus values as well as a flow chart to guide the use of the step strain adjustment procedure.

Macromolecular relaxation, strain, and extensibility determine elastocapillary thinning and extensional viscosity of polymer solutions

Delayed capillary break-up of viscoelastic filaments presents scientific and technical challenges relevant for drop formation, dispensing, and adhesion in industrial and biological applications. The flow kinematics are primarily dictated by the viscoelastic stresses contributed by the polymers that are stretched and oriented in a strong extensional flow field resulting from the streamwise gradients created by the capillarity-driven squeeze flow. After an initial inertiocapillary (IC) or viscocapillary (VC) regime, where elastic effects seem to play no role, the interplay of capillarity and viscoelasticity can lead to an elastocapillary (EC) response characterized by exponentially-slow thinning of neck radius (extensional relaxation time is determined from the delay constant). Less frequently, a terminal visco-elastocapillary (TVEC) response with linear decay in radius can be observed and used for measuring terminal, steady extensional viscosity. However, both IC/VC–EC and EC–TVEC transitions are inaccessible in devices that create stretched necks by applying a step strain to a liquid bridge (e.g., capillary breakup extensional rheometer). In this study, we use dripping-onto-substrate rheometry to obtain radius evolution data for unentangled polymer solutions. We deduce that the plots of transient extensional viscosity vs. Hencky strain (scaled by the respective values at the EC–TVEC transition) emulate the functional form of the birefringence–macromolecular strain relationship based on Peterlin’s theory. We quantify the duration and strain between the IC/VC–EC and the EC–TVEC transitions using measures we term elastocapillary span and elastocapillary strain increment and find both measures show values directly correlated with the corresponding variation in extensional relaxation time.