Nanoarchitectonics of MXene Derived TiO2 /Graphene with Vertical Alignment for Achieving the Enhanced Supercapacitor Performance.

Structural engineering and hybridization of heterogeneous 2D materials can be effective for advanced supercapacitor. Furthermore, architectural design of electrodes particularly with vertical construction of structurally anisotropic graphene nanosheets, can significantly enhance the electrochemical performance. Herein, MXene-derived TiO2 nanocomposites hybridized with vertical graphene is synthesized via CO2 laser irradiation on MXene/graphene oxide nanocomposite film. Instantaneous photon energy by laser irradiation enables the formation of vertical graphene structures on nanocomposite films, presenting the controlled anisotropy in free-standing film. This vertical structure enables improved supercapacitor performance by forming an open structure, increasing the electrolyte-electrode interface, and creating efficient electron transport path. In addition, the effective oxidation of MXene nanosheets by instantaneous photon energy leads to the formation of rutile TiO2 . TiO2 nanoparticles directly generated on graphene enables the effective current path, which compensates for the low conductivity of TiO2 and enables the functioning of an effective supercapacitor by utilizing its pseudocapacitive properties. The resulting film exhibits excellent specific areal capacitance of 662.9 mF cm-2 at a current density of 5 mA cm-2 . The film also shows superb cyclic stability during 40 000 repeating cycles, maintaining high capacitance. Also, the pseudocapacitive redox reaction kinetics is evaluated, showing fast redox kinetics with potential for high-performance supercapacitor applications.

Effects of flow history on extensional rheological properties of wormlike micelle solution.

A wormlike micelle (WLM) solution is a complex fluid that forms when the surfactant concentration is high. It has rheological properties similar to those of polymer solutions. However, unlike polymer molecules, WLM chains possess the dynamic microstructure that can be reversibly broken and reassembled in flows. Therefore, the rheological properties and flow behavior of WLM solutions have attracted much attention owing to their unique dynamic microstructures. However, the effects of the flow history on the extensional rheological properties of WLM solutions remain unclear. In this study, the change in the extensional rheological properties of WLM solutions depending upon on their shear flow histories was investigated by combining the dripping-onto-substrate/capillary break-up extensional rheometry technique with a compressed gas flow (stop-flow) control method. This approach precisely controls the shear flow histories of the WLM solutions. The results revealed that the shear flow history has a substantial impact on elongational rheological properties such as relaxation time. They also showed that the effects of the characteristic shear rate are highly dependent on the surfactant concentration. We expect that the current findings can be applied to understand the extensional rheological properties of complex fluids in industrially relevant processes such as coating and printing.

Equilibrium leaching of selected ultraviolet stabilizers from plastic products.

Despite the importance of (micro)plastics in the release of plastic additives, the leaching mechanism of organic plastic additives from various plastic materials is poorly understood. In this study, the equilibrium leaching of five highly hydrophobic ultraviolet (UV) stabilizers (UV326, UV327, UV328, UV329, and UV531) from three plastics (low-density polyethylene (LDPE), polyethylene terephthalate (PET), and polystyrene (PS)), was investigated employing acetonitrile-water cosolvent systems. Their extrapolated water solubilities were in the 0.15-0.54 µg L-1 range, limiting their transport as "dissolved" in water and (micro)plastics are likely those particulate carriers. The equilibrium leaching of UV stabilizers from plastics was better explained by the Flory-Huggins model incorporating the nonideal behavior caused by the size disparity between UV stabilizers and polymer materials and their compatibility. Specifically, leaching of UV stabilizers from LDPE showed a positive deviation from Raoult's law, whereas slight negative deviations were observed in PET and PS. In addition, the equilibrium concentration of the benzotriazoles in LDPE increased linearly with the volume fraction up to only 0.4%. These observations could be explained by the unfavorable interactions of UV stabilizers with polyethylene, indicating that polymer type should be also important when evaluating the fate of hydrophobic additives. Because equilibrium distribution of additives between (micro)plastics and water is crucial for evaluating the fate and transport of hydrophobic plastic additives, further studies on the leaching equilibrium of various additives from different plastic materials are necessary.

Thermogelling Behaviors of Aqueous Poly(N-Isopropylacrylamide-co-2-Hydroxyethyl Methacrylate) Microgel-Silica Nanoparticle Composite Dispersions.

Gelation behaviors of hydrogels have provided an outlook for the development of stimuli-responsive functional materials. Of these materials, the thermogelling behavior of poly(N-isopropylacrylamide) (p(NiPAm))-based microgels exhibits a unique, reverse sol-gel transition by bulk aggregation of microgels at the lower critical solution temperature (LCST). Despite its unique phase transition behaviors, the application of this material has been largely limited to the biomedical field, and the bulk gelation behavior of microgels in the presence of colloidal additives is still open for scrutinization. Here, we provide an in-depth investigation of the unique thermogelling behaviors of p(NiPAm)-based microgels through poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) microgel (p(NiPAm-co-HEMA))-silica nanoparticle composite to expand the application possibilities of the microgel system. Thermogelling behaviors of p(NiPAm-co-HEMA) microgel with different molar ratios of N-isopropylacrylamide (NiPAm) and 2-hydroxyethyl methacrylate (HEMA), their colloidal stability under various microgel concentrations, and the ionic strength of these aqueous solutions were investigated. In addition, sol-gel transition behaviors of various p(NiPAm-co-HEMA) microgel systems were compared by analyzing their rheological properties. Finally, we incorporated silica nanoparticles to the microgel system and investigated the thermogelling behaviors of the microgel-nanoparticle composite system. The composite system exhibited consistent thermogelling behaviors in moderate conditions, which was confirmed by an optical microscope. The composite demonstrated enhanced mechanical strength at gel state, which was confirmed by analyzing rheological properties.

Viscoelastic particle focusing in human biofluids.

Saliva and blood plasma are non-Newtonian viscoelastic fluids that play essential roles in the transport of particulate matters (e.g., food and blood cells). However, whether the viscoelasticity of such biofluids alters the dynamics of suspended particles is still unknown. In this study, we report that under pressure-driven microflows of both human saliva and blood plasma, spherical particles laterally migrate and form a focused stream along the channel centerline by their viscoelastic properties. We observed that the particle focusing varied among samples on the basis of sampling times/donors, thereby demonstrating that the viscoelasticity of the human biofluids can be affected by their compositions. We showed that the particle focusing, observed in bovine submaxillary mucin solutions, intensified with the increase in mucin concentration. We expect that the findings from this study will contribute to the understanding of the physiological roles of viscoelasticity of human biofluids.

Gear-shaped micromixer for synthesis of silica particles utilizing inertio-elastic flow instability.

Mixing in microscale flows, where turbulence is inherently difficult to generate, has been a challenging issue owing to its laminar flow characteristics. Either the diffusion-based mixing process, or the convective mixing based on the cross-stream secondary flow, has been exploited as a passive mixing scheme that does not require any external force field. However, these techniques suffer from insufficient mixing or complicated channel design step. In this study, we propose an efficient mixing scheme by combining inertio-elastic flow instability in a viscoelastic dilute polymer solution and a modified serpentine channel, termed a gear-shape channel, which has side wells along the serpentine channel. We achieved highly efficient mixing in the gear-shaped channel for a significantly wider range of flow rates than in a conventional serpentine channel. Further, we applied our novel mixing scheme to the continuous synthesis of silica nanoparticles, which demonstrated the synthesis of nanoparticles with more uniform size distribution and regular shape, than those in a Newtonian fluid. In addition, the adsorption of inorganic materials on the channel walls was significantly suppressed by the flow instability of the viscoelastic dilute polymer solution in the gear-shaped channel.

Complete Genome Sequence of the Carotenoid-Producing Strain Gordonia ajoucoccus A2.

Gordonia ajoucoccus strain A2, isolated from crude oil-contaminated soils, synthesizes yellow keto-γ-carotene from various n-alkanes as the sole carbon source. Its complete genome sequence consists of a single circular chromosome (5,090,254 bp, 67.3% G+C content). Seven putative genes were identified supporting the proposed keto-γ-carotene pathway of G. ajoucoccus A2.

Effects of Ionic Strength on Lateral Particle Migration in Shear-Thinning Xanthan Gum Solutions.

Viscoelastic fluids, including particulate systems, are found in various biological and industrial systems including blood flow, food, cosmetics, and electronic materials. Particles suspended in viscoelastic fluids such as polymer solutions migrate laterally, forming spatially segregated streams in pressure-driven flow. Viscoelastic particle migration was recently applied to microfluidic technologies including particle counting and sorting and the micromechanical measurement of living cells. Understanding the effects on equilibrium particle positions of rheological properties of suspending viscoelastic fluid is essential for designing microfluidic applications. It has been considered that the shear-thinning behavior of viscoelastic fluid is a critical factor in determining the equilibrium particle positions. This work presents the lateral particle migration in two different xanthan gum-based viscoelastic fluids with similar shear-thinning viscosities and the linear viscoelastic properties. The flexibility and contour length of the xanthan gum molecules were tuned by varying the ionic strength of the solvent. Particles suspended in flexible and short xanthan gum solution, dissolved at high ionic strength, migrated toward the corners in a square channel, whereas particles in the rigid and long xanthan gum solutions in deionized water migrated toward the centerline. This work suggests that the structural properties of polymer molecules play significant roles in determining the equilibrium positions in shear-thinning fluids, despite similar bulk rheological properties. The current results are expected to be used in a wide range of applications such as cell counting and sorting.

Normal stress difference-driven particle focusing in nanoparticle colloidal dispersion.

Colloidal dispersion has elastic properties due to Brownian relaxation process. However, experimental evidence for the elastic properties, characterized with normal stress differences, is elusive in shearing colloidal dispersion, particularly at low Péclet numbers (Pe < 1). Here, we report that single micrometer-sized polystyrene (PS) beads, suspended in silica nanoparticle dispersion (8 nm radius; 22%, v/v), laterally migrate and form a tightly focused stream by the normal stress differences, generated in pressure-driven microtube flow at low Pe. The nanoparticle dispersion was expected to behave as a Newtonian fluid because of its ultrashort relaxation time (2 µs), but large shear strain experienced by the PS beads causes the notable non-Newtonian behavior. We demonstrate that the unique rheological properties of the nanoparticle dispersion generate the secondary flow in perpendicular to mainstream in a noncircular conduit, and the elastic properties of blood plasma-constituting protein solutions are elucidated by the colloidal dynamics of protein molecules.

Desorption modeling of hydrophobic organic chemicals from plastic sheets using experimentally determined diffusion coefficients in plastics.

To evaluate rate of migration from plastic debris, desorption of model hydrophobic organic chemicals (HOCs) from polyethylene (PE)/polypropylene (PP) films to water was measured using PE/PP films homogeneously loaded with the HOCs. The HOCs fractions remaining in the PE/PP films were compared with those predicted using a model characterized by the mass transfer Biot number. The experimental data agreed with the model simulation, indicating that HOCs desorption from plastic particles can generally be described by the model. For hexachlorocyclohexanes with lower plastic-water partition coefficients, desorption was dominated by diffusion in the plastic film, whereas desorption of chlorinated benzenes with higher partition coefficients was determined by diffusion in the aqueous boundary layer. Evaluation of the fraction of HOCs remaining in plastic films with respect to film thickness and desorption time showed that the partition coefficient between plastic and water is the most important parameter influencing the desorption half-life.

Shape Measurement of Ellipsoidal Particles in a Cross-Slot Microchannel Utilizing Viscoelastic Particle Focusing.

Shape measurement of nonspherical microparticles by conventional methods such as optical microscopy is challenging owing to particle aggregation or uncertainty regarding the out-of-plane arrangement of particles. In this work, we propose a facile microfluidic method to align particles in-plane utilizing the extensional flow field generated in a cross-slot microchannel. Viscoelastic particle focusing is also harnessed to move particles toward the stagnation point of the cross-slot microchannel. We demonstrate that the shapes of ellipsoidal particles with various aspect ratios can be successfully measured using our novel microfluidic method. This method is expected to be useful in a wide range of applications such as shape measurement of nonspherical cells.

Inertio-elastic flow instabilities in a 90° bent microchannel.

Biological samples having viscoelastic properties are frequently tested using microfluidic devices. In addition, viscoelastic fluids such as polymer solutions have been used as a suspending medium to spatially focus particles in microchannels. The occurrence of flow instability even at low Reynolds number is a unique property of viscoelastic fluids. In this study, we report the instability in viscoelastic flow for a channel having a 90° bent geometry, which is a characteristic of many microfluidic devices. Interestingly, we observed that the flow instability in aqueous poly(ethylene oxide) (PEO) solution occurs when the concentration of PEO is as low as 50 ppm. We systematically investigated the effects of the polymer concentration, flow rate, and elasticity number on the flow instability. The results show that the flow is stabilized in shear-thinning fluids, whereas the flow instability is amplified when both elastic and inertial effects are pronounced. We believe that this study is useful to design microfluidic devices such as cell-deformability measurement devices based on viscoelastic particle focusing.

Elasto-inertial particle focusing under the viscoelastic flow of DNA solution in a square channel.

Particle focusing is an essential step in a wide range of applications such as cell counting and sorting. Recently, viscoelastic particle focusing, which exploits the spatially non-uniform viscoelastic properties of a polymer solution under Poiseuille flow, has attracted much attention because the particles are focused along the channel centerline without any external force. Lateral particle migration in polymer solutions in square channels has been studied due to its practical importance in lab-on-a-chip applications. However, there are still many questions about how the rheological properties of the medium alter the equilibrium particle positions and about the flow rate ranges for particle focusing. In this study, we investigated lateral particle migration in a viscoelastic flow of DNA solution in a square microchannel. The elastic property is relevant due to the long relaxation time of a DNA molecule, even when the DNA concentration is extremely low. Further, the shear viscosity of the solution is essentially constant irrespective of shear rate. Our current results demonstrate that the particles migrate toward the channel centerline and the four corners of a square channel in the dilute DNA solution when the inertia is negligible (elasticity-dominant flow). As the flow rate increases, the multiple equilibrium particle positions are reduced to a single file along the channel centerline, due to the elasto-inertial particle focusing mechanism. The current results support that elasto-inertial particle focusing mechanism is a universal phenomenon in a viscoelastic fluid with constant shear viscosity (Boger fluid). Also, the effective flow rate ranges for three-dimensional particle focusing in the DNA solution were significantly higher and wider than those for the previous synthetic polymer solution case, which facilitates high throughput analysis of particulate systems. In addition, we demonstrated that the DNA solution can be applied to focus a wide range of particle sizes in a single channel and also align red blood cells without any significant deformation.

Microfluidic assessment of mechanical cell damage by extensional stress.

Mammalian cells have been widely used in bioreactors to produce biological products such as pharmaceutical materials. The productivity of such bioreactors is vastly affected by flow-induced cell damage in complicated flow environments, such as agitation-driven turbulence and oxygen bubble bursting at the interface between the culturing medium and air. However, there is no systematic approach to diagnose the cell damage caused by the hydrodynamic stress. In this work, we propose a novel microfluidic method to accurately assess the mechanical cell damage under a controlled extensional stress field, generated in a microfluidic cross-slot geometry. The cell damage in the extensional field is related to the oxygen bubble bursting process. We employed viscoelasticity-induced particle focusing to align the cells along the shear-free channel centerline, so that all the cells experience a similar extensional stress field, which also precludes the cell damage due to wall shear stress. We applied our novel microfluidic sensor to find the critical extensional stress to damage Chinese hamster ovary (CHO) cells; the critical stress is found to be ∼250 Pa. Our current results are relevant in the design of practical bioreactors, as our results clearly demonstrate that the control of the bubble bursting process is critical in minimizing cell damage in bioreactor applications. Further, our results will provide useful information on the biophysical cell properties under fluid flow environments.

PDMS-based turbulent microfluidic mixer.

Over the past decade, homogeneous mixing in microfluidic devices has been a critical challenge, because of the inherently low flow rates in microfluidic channels. Although several mixer designs have been suggested to achieve efficient mixing, most of them involve intricate structures requiring a series of laborious fabrication processes. Operation at high flow rates can greatly enhance mixing by induction of turbulence, but devices that can resist such a high pressure drop to induce turbulence in microfluidic channels are difficult to fabricate, especially for commonly used poly(dimethylsiloxane) (PDMS)-based microfluidic devices. We have developed a Y-shaped, turbulent microfluidic mixer made of PDMS and a glass substrate by strong bonding of the substrates to a nanoadhesive layer deposited via initiated chemical vapor deposition. The high bonding strength of the nanoadhesive layer enables safe operation of the PDMS/glass turbulent microfluidic mixer at a total water flow rate of 40 mL min(-1), corresponding to a Reynolds number, Re, of ~4423, one of the highest values achieved in a microfluidic channel. The turbulence generated as a result of the high Re allows rapid mixing of the input fluids on contact. Image analysis showed that mixing started as soon as the fluids were introduced into the mixer. The experimental results matched the numerical predictions well, demonstrating that convective mixing was dominant as a result of turbulence induced in the microfluidic channel. Using the turbulent microfluidic mixer, we have demonstrated high throughput formation of emulsions with narrower size distribution. It was shown that as the flow rate increases inside the microfluidic channel, the size distribution of resulting emulsions decreases owing to the increase in the turbulent energy dissipation. The turbulent microfluidic mixer developed in this work not only enables rapid mixing of streams, but also increases throughputs of microfluidic reactors.

Topographic pattern of cortical thinning with consideration of motor laterality in Parkinson disease.

BACKGROUND: The asymmetry of Parkinson's disease (PD) may contribute to the unilateral appearance of parkinsonism, as well as its cerebral morphological changes. However, previous studies have not considered that cerebral involvement would probably be asymmetric. Our study aimed to identify whether one-sided symptom dominance has an influence on cortical thinning patterns in early-stage, non-demented PD patients from cortical thickness analyses and cortical thinning patterns are associated with motor functions. METHODS: We used cortical thickness analysis in 64 non-demented right-handed subjects: 21 PD patients with left-sided disease onset (LPD), 21 PD patients with right-sided disease onset (RPD) and 22 control subjects. We modeled local cortical thickness as a linear association with each motor symptom. RESULTS: We identified three clusters exhibiting significant cortical thinning (p < 0.01 RFT corrected) in the LPD group compared with the control group: a cluster including the right primary sensory, motor cortex and paracentral lobule, as well as another two clusters in bilateral parahippocampal gyri. In the RPD group, there was only one cluster that exhibited significant cortical thinning compared with the control group, located in the left lingual gyrus. There were no significant correlations between cortical thinning clusters and motor severity, any of the motor subscales including tremor, rigidity, bradykinesia and axial impairment. CONCLUSIONS: Our right-handed PD population revealed that significant thinning of motor-related cortical areas in contralateral hemisphere to symptomatic side in LPD, but not in RPD group. Our results support that neuroprotective effect of enhanced physical activity by handedness on contralateral motor cortex.

High-throughput DNA separation in nanofilter arrays.

We numerically investigated the dynamics of short double-stranded DNA molecules moving through a deep-shallow alternating nanofilter, by utilizing Brownian dynamics simulation. We propose a novel mechanism for high-throughput DNA separation with a high electric field, which was originally predicted by Laachi et al. [Phys. Rev. Lett. 2007, 98, 098106]. In this work, we show that DNA molecules deterministically move along different electrophoretic streamlines according to their length, owing to geometric constraint at the exit of the shallow region. Consequently, it is more probable that long DNA molecules pass over a deep well region without significant lateral migration toward the bottom of the deep well, which is in contrast to the long dwelling time for short DNA molecules. We investigated the dynamics of DNA passage through a nanofilter facilitating electrophoretic field kinematics. The statistical distribution of the DNA molecules according to their size clearly corroborates our assumption. On the other hand, it was also found that the tapering angle between the shallow and deep regions significantly affects the DNA separation performance. The current results show that the nonuniform field effect combined with geometric constraint plays a key role in nanofilter-based DNA separation. We expect that our results will be helpful in designing and operating nanofluidics-based DNA separation devices and in understanding the polymer dynamics in confined geometries.

DNA-based highly tunable particle focuser.

DNA is distinguished by both long length and structural rigidity. Classical polymer theories predict that DNA enhances the non-Newtonian elastic properties of its dilute solution more significantly than common synthetic flexible polymers because of its larger size and longer relaxation time. Here we exploit this property to report that under Poiseuille microflow, rigid spherical particles laterally migrate and form a tightly focused stream in an extremely dilute DNA solution (0.0005 (w/v)%). By the use of the DNA solution, we achieve highly efficient focusing (>99.5%) over an unprecedented wide range of flow rates (ratio of maximum to minimum flow rates ~400). This highly tunable particle-focusing technique can be used in the design of cost-effective portable flow cytometers, high-throughput cell analysis and also for cell sorting by size. We demonstrate that DNA is an efficient elasticity enhancer, which originates from its unique structural properties.

Cell stretching measurement utilizing viscoelastic particle focusing.

We present an efficient method for measuring cell stretching based on three-dimensional viscoelastic particle focusing. We suspended cells in a biocompatible viscoelastic medium [poly(vinylpyrrolidone) solution in phosphate-buffered saline]. The medium viscoelasticity significantly homogenized the trajectories of cells along the centerline of a simple straight channel, which could not be achieved in conventional Newtonian media. More than 95% of red blood cells (RBCs) were successfully delivered to the stagnation point of a cross-slot microchannel and stretched by extensional flow. By computational simulations, we proved that this method prevents inaccuracies due to random lateral distributions of cells and, further, guarantees rotational-free cell stretching along the shear-free channel centerline. As a demonstration, we characterized the differences in RBC deformabilities among various heat treatments. Furthermore, we monitored the decrease of deformability due to nutrient starvation in human mesenchymal stem cells. We envisage that our novel method can be extended to versatile applications such as the detection of pathophysiological evolution in impaired RBCs due to malaria or diabetes and the monitoring of cell quality in stem cell therapeutics.