Tunable Separation Research Articles

Strong anisotropy and its electric tuning for brownmilleriteSrCoO2.5films with different crystal orientations

Brownmillerite oxides ($A\mathrm{B}{\mathrm{O}}_{2.5}$) with long-range ordering of oxygen vacancies own a distinct superstructure formed by alternately stacked octahedral $\mathrm{B}{\mathrm{O}}_{6}$ and tetrahedral $\mathrm{B}{\mathrm{O}}_{4}$ planes. The one-dimensional oxygen vacancy channels within $\mathrm{B}{\mathrm{O}}_{4}$ layers usually lead to high ionic conductivity of brownmillerite oxides, demonstrating great application potential in solid-oxide fuel cells, the oxygen separation membrane, and catalyzers. Here, high quality brownmillerite-$\mathrm{SrCo}{\mathrm{O}}_{2.5}$ films have been epitaxially grown on differently oriented substrates by pulsed laser deposition. The anisotropic structural and physical properties of (110)- and (111)-oriented $\mathrm{SrCo}{\mathrm{O}}_{2.5}$ films were systematically investigated. We found, unlike the out-of-plane (001)-oriented $\mathrm{SrCo}{\mathrm{O}}_{2.5}$ films, the $\mathrm{Co}{\mathrm{O}}_{6}$ and $\mathrm{Co}{\mathrm{O}}_{4}$ planes would alternately stack along one of the [100] and [010] axes for (110)-oriented films and one of the [100], [010], and [001] axes for (111)-oriented films, forming coexisting crystal domains with different orientations. More importantly, the superstructure of these films could be reversibly tuned by alternately applying an electric field along two orthogonal directions, switching between an ordered and a disordered state. Corresponding to structural anisotropy, strong in-plane electronic anisotropy of the (110)-oriented $\mathrm{SrCo}{\mathrm{O}}_{2.5}$ film was revealed, which was also electrically tunable like the superstructure. This work demonstrates the approaches to modify the ionic conduction channels of brownmillerite oxides, opening avenues towards electrically tunable oxygen separation membrane and catalyzers.

Hydrogel micromotors with catalyst-containing liquid core and shell

Methacrylic anhydride-derived hydrogel microcapsules have unique properties, including reversibly tunable permeation, purification, and separation of dissolved molecular species. Endowing these dynamic encapsulant systems with autonomous motion will significantly enhance their efficiency and applicability. Here, hydrogel micromotors are realized using complex water-in-oil-in-water double emulsion drops and oil-in-water emulsion drops from glass capillary microfluidics and subsequent photopolymerization. Three hydrogel micromotor strategies are explored: microcapsules with thin shells and liquid cores with dispersed catalytic Pt nanoparticles, as well as water-cored microcapsules and homogeneous microparticles selectively coated with Ti/Pt catalytic layers. Autonomous motion of hydrogel particles and capsules is realized in hydrogen peroxide solutions, where generated oxygen microbubbles propel the dynamically responsive micromotors. The micromotors are balanced by weight, buoyancy, lateral capillary forces and show specific autonomous behaviours that significantly extend short range dynamic responses of hydrogels. Drop-based microfluidics represent a paradigm shift in the integration of multifunctional subsystems and high-throughput design of chemical micromachines in reasonable quantities towards their desired biomedical, environmental and flow/diffusion microreactor applications.

Novel Biphasic Solvent with Tunable Phase Separation for CO2 Capture: Role of Water Content in Mechanism, Kinetics, and Energy Penalty

The biphasic solvent-based absorption process has been regarded as a promising alternative to the monoethanolamine (MEA)-based process because of its high absorption capacity, phase separation behavior, and potential for conserving energy for CO2 capture. A trade-off between the absorption capacity and phase separation ratio is critical for developing an advanced biphasic solvent. Typically, water content in the biphasic solvent can be manipulated to tune the phase separation behavior. To explore the relationship between water content and phase separation behavior, an inert organic solvent, 1-methyl-2-pyrrolidinone, was added as a substitute for water in a biphasic solvent, specifically a triethylenetetramine (TETA) and 2-(diethylamino)ethanol (DEEA) blend. Moreover, the water content-kinetics and thermodynamics relationships were also evaluated. Experimental results revealed that reducing the water content was beneficial for phase separation but adverse for adsorption capacity. Kinetic analysis indicated that the water content did not significantly affect the rate of CO2 absorption at a rich loading. Furthermore, the regeneration heat decreased with the water content. The regeneration heat of TETA-DEEA with a water content of 20 wt % was almost 50% less than that of MEA solution. 13C nuclear magnetic resonance analysis revealed that the water content did not affect the reaction mechanism between CO2 and amines.

Highly tunable sulfur hexafluoride separation by interpenetration control in metal organic frameworks

Abstract The separation of fluid SF6/N2 mixtures using the recently synthesized metal-organic framework SIFSIX-2-Cu and its interpenetrated polymorph SIFSIX-2-Cu-i has been systematically studied by employing Monte Carlo and Molecular Dynamics simulations. These predictions revealed that SIFSIX-2-Cu shows a high thermodynamic adsorption selectivity for SF6 over N2 combined with one of the highest SF6 uptakes reported so far for an adsorbent. On the other hand, the smaller pore dimensions of the interpenetrated network cause a molecular sieving effect, allowing only the adsorption of N2. Furthermore, the self-diffusivity of the adsorbed SF6 molecules in the SIFSIX-2-Cu framework was predicted to be significantly lower than the one corresponding to N2, while the smaller pore channel network of SIFSIX-2-Cu-i decreases the self-diffusivity of N2 by a factor of about 6. This study revealed that controlling the interpenetration in MOFs is an efficient way to tune their separation performances for strategic gas mixtures.

Widely Tunable Dual-Wavelength Fiber Laser in the 2 μm Wavelength Range

In this paper, we demonstrate a widely tunable dual-wavelength fiber laser, which is based on a thulium-doped fiber and volume Bragg gratings triggering the emission wavelengths in the 2-μm band. A continuously tunable wavelength separation range (Δλ), from 1 to 144 nm (0.08–11.47 THz) is demonstrated, with > 4.5 W of output power over the tuning range. The laser emission exhibits a linewidth (FWHM) lower than 0.1 nm independent from wavelengths and Δλ, with more than 45 dB of a signal-to-noise contrast. A maximum output power of 7 W is obtained for shorter Δλ (1–14 nm), corresponding to a slope efficiency of 33% with respect to the incident pump power at 790 nm.

Tunable Mass Separation via Negative Mobility.

A prerequisite for isolating diseased cells requires a mechanism for effective mass-based separation. This objective, however, is generally rather challenging because typically no valid correlation exists between the size of the particles and their mass value. We consider an inertial Brownian particle moving in a symmetric periodic potential and subjected to an externally applied unbiased harmonic driving in combination with a constant applied bias. In doing so, we identify a most efficient separation scheme which is based on the anomalous transport feature of negative mobility, meaning that the immersed particles move in the direction opposite to the acting bias. This work is the first of its kind in demonstrating a tunable separation mechanism in which the particle mass targeted for isolation is effectively controlled over a regime of nearly 2 orders of mass magnitude upon changing solely the frequency of the external harmonic driving. This approach may provide mass selectivity required in present and future separation of a diversity of nano- and microsized particles of either biological or synthetic origin.

Modeling and characterization of a dual-wavelength SOA-based single longitudinal mode random fiber laser with tunable separation

In this work, a novel Single longitudinal mode (SLM) dual-wavelength random fiber laser (DW-RFL) with narrow line-width and tunable separation between the two modes in the range 1.5 – 25 nm (187 GHz – 3.12 THz) is presented. The laser is based on Rayleigh backscattering in a standard single mode fiber of 2 km length acting as distributed mirrors and a semiconductor optical amplifier (SOA) acting as the optical amplifier. Two optical band pass filters are used for the wavelength selection, and two Faraday Rotator mirrors are used to sustain the stability of the two lasing wavelengths against fiber random birefringence. The measured line-width of each mode of the laser varies from 3 to 11.5 kHz with lasing wavelengths and SOA pump currents. The power and the wavelength stabilities at the peak power of each mode were also investigated.

Growing covalent organic frameworks on porous substrates for molecule-sieving membranes with pores tunable from ultra- to nanofiltration

Crystalline imine-based covalent organic frameworks (COFs) have attracted great interest as next-generation water treatment materials owning to their numerous merits. The construction of COF layers with tunable pore sizes ranging from meso- to micropores, which can significantly broaden the membrane selectivity from ultra- (UF) to nanofiltration (NF), has remained unexplored. Herein, we demonstrate the controllable solvothermal synthesis of COF layers with adjustable pore sizes on anodic aluminum oxide (AAO) substrates. With rising synthesis duration the modulation on pore sizes of AAO supports can be achieved till the formation of continuous COF layers, leading to a gradually enhanced selectivity. Importantly, the synthesized microporous COFs shrink the pore sizes of AAO substrates and provide additional nanochannels for water transporting, eventuating in a ~2–9 times higher permeance than other reported UF membranes with comparable rejections. Once forming continuous COF layers, more rigid selectivities based on COF inherent nanochannels (~1.83 nm) can be realized with capacities of removing dyes from water or organic solvent. This work provides a facile methodology to construct COF-based membranes with broadly tunable separation performance, recommending the membranes for removing targeted molecules including proteins, nanoparticles, and dyes.

Bosons condensed in two modes with flavor-changing interaction

A quantum model is considered for $N$ bosons populating two orthogonal single-particle modes with tunable energy separation in the presence of flavour-changing contact interaction. The quantum ground state is well approximated as a coherent superposition (for zero temperature) or a mixture (at low temperature) of two quasi-classical states. In a mean field description, the systems realizes one of these states via spontaneous symmetry breaking. Both mean field states, in a certain parameter range, possess finite angular momentum and exhibit broken time-reversal symmetry in contrast to the quantum ground state. The phase diagram is explored at the mean-field level and by direct diagonalisation. The nature of the quantum ground state at zero and finite temperature is analyzed by means of the Penrose Onsager criterion. One of three possible phases shows fragmentation on the single-particle level together with a finite pair order parameter. Thermal and quantum fluctuations are characterized with respect to regions of universal scaling behavior. The non-equilibrium dynamics shows a sharp transition between a self-trapping and a pair-tunneling regime. A recently realized experimental implementation is discussed with bosonic atoms condensed in the two inequivalent energy minima $X_{\pm}$ of the second band of a bipartite two-dimensional optical lattice.

Biodegradable zwitterionic nanoparticles with tunable UCST-type phase separation under physiological conditions.

Thermo-responsive polymeric nanoparticles (NPs) are emerging as a powerful tool in nanomedicine for the fabrication of advanced drug delivery systems. In addition to their size and biodegradation rate, phase separation of NPs upon application of a thermal stimulus provides an additional switch to control the rate of release of active components. Among the materials currently developed for biomedical applications, NPs stabilized by zwitterionic polymers are gaining increasing interest due to their high stability and ability to escape the body immune response. Yet, biodegradable zwitterionic NPs with temperature response under physiological conditions are currently not available. Here, we develop a new class of biodegradable zwitterionic NPs that exhibit UCST phase transition in the biological temperature range (T = 30-45 °C) and in physiological solution (i.e. 0.9% w/w NaCl). We design a strategy that relies on the self-assembly of block copolymers produced via reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization. These copolymers comprise a zwitterionic portion exhibiting an upper critical solution temperature (UCST) and a biodegradable hydrophobic block consisting of oligoesters functionalized with a vinyl group. This modular macromolecular architecture allows us to independently control a variety of NP properties by modifying the individual components of the copolymer. In particular, the zwitterionic block of the copolymers controls the UCST-type phase separation behavior, while the number of the oligoester repeating units governs the size of the NPs and the length of the oligoester dictates the degradation rate. After demonstrating the synthesis of highly controlled degradable NPs, we show the potential of this new class of materials in the context of drug delivery by controlling the release of a drug-mimic molecule upon temperature variations in a broad time range from few minutes to 20 hours.

Self-assembled membrane composed of amyloid-like proteins for efficient size-selective molecular separation and dialysis

The design and scalable construction of robust ultrathin protein membranes with tunable separation properties remain a key challenge in chemistry and materials science. Here, we report a macroscopic ultrathin protein membrane with the potential for scaled-up fabrication and excellent separation efficiency. This membrane, which is formed by fast amyloid-like lysozyme aggregation at air/water interface, has a controllable thickness that can be tuned to 30–250 nm and pores with a mean size that can be tailored from 1.8 to 3.2 nm by the protein concentration. This membrane can retain > 3 nm molecules and particles while permitting the transport of small molecules at a rate that is 1~4 orders of magnitude faster than the rate of existing materials. This membrane further exhibits excellent hemodialysis performance, especially for the removal of middle-molecular-weight uremic toxins, which is 5~6 times higher in the clearance per unit area than the typical literature values reported to date.

High‐Temperature Large‐Scale Self‐Assembly of Highly Faceted Monocrystalline Au Metasurfaces

AbstractLocalized surface plasmon resonance (LSPR) devices based on resonant metallic metasurfaces have shown disruptive potential for many applications including biosensing and photocatalysis. Despite significant progress, highly performing Au plasmonic nanotextures often suffer of suboptimal electric field enhancement, due to damping effects in multicrystalline domains. Fabricating well‐defined Au nanocrystals over large surfaces is very challenging, and usually requires time‐intensive multi‐step processes. Here, presented are first insights on the large‐scale self‐assembly of monocrystalline Au nano‐islands with tunable size and separation, and their application as efficient LSPR surfaces. Highly homogeneous centimeter‐sized Au metasurfaces are fabricated by one‐step deposition and in situ coalescence of hot nanoparticle aerosols into a discontinuous monolayer of highly faceted monocrystals. First insights on the mechanisms driving the high‐temperature synthesis of these highly faceted Au nanotextures are obtained by molecular dynamic and detailed experimental investigation of their growth kinetics. Notably, these metasurfaces demonstrat high‐quality and tunable LSPR, enabling the fabrication of highly performing optical gas molecule sensors detecting down to 3 × 10−6 variations in refractive index at room temperature. It is believed that these findings provide a rapid, low‐cost nanofabrication tool for the engineering of highly homogenous Au metasurfaces for large‐scale LSPR devices with application ranging from ultrasensitive optical gas sensors to photocatalytic macroreactors.

Giant magnetoelectric field separation via anapole-type states in high-index dielectric structures

Quality of spatial separation between electric and magnetic fields in an electromagnetic wave is fundamentally constrained by nonlocal nature of Maxwell equations. While electric and magnetic energy densities in a wave, propagating in vacuum, are equal at each point in space, carefully designed photonic structures can enable surpassing this limit. Here, a set of high index dielectric tubes was for the first time proposed and theoretically and experimentally demonstrated to deliver a record high spatial separation, overcoming the free space scenario by more than three orders of magnitude with simultaneous enhancement of the magnetic field. Separation effect in the proposed structure is enabled by the near-field interference on anapole-like states, designed by tuning geometrical parameters of coupled dielectric tubes. The void layout of the structure enables the direct observation of the effect with near-field probes and could be further employed for relevant applications. Novel devices, providing tunable high quality separation between electric and magnetic fields, are extremely important for metrology, spectroscopy, spintronics, and opto-electronic applications.

THz generation from DFG in a noncollinear phase-matched GaP crystal pumped with a compact diode-pumped two-frequency LiYF4:Nd laser

Pumping with a nanosecond two-frequency compact diode-pumped LiYF4:Nd laser emitting at 1047 and 1053 nm, a THz wave has been produced in a GaP crystal, attributed to the difference frequency generation process $$\frac{1}{{{\lambda _3}}} - \frac{1}{{{\lambda _2}}}=\frac{1}{{{\lambda _{{\text{TH}}z}}}}$$ . In a first set-up, the two pumping beams had a tunable angular separation provided by a sapphire prism. The phase matching angle of the noncollinear interaction has been determined to be 0.202° external angle and the refractive index 3.377 at 1.6 THz. The angular acceptance was rather broad, due to the fact that the thickness of the nonlinear crystal was only 3 mm. With a second set-up using a beam displacer constituted by YVO4 plates of different thicknesses, smaller angular separations were explored under other directions of polarizations of the pump beams. Because at the three wavelengths involved in this study the velocity of the nonlinear polarization wave inside GaP is higher than the THz wave phase velocity, a Cerenkov phase matching is possible. The plane-wave calculations show that the THz radiation under this process exits from the output face of the crystal, as it is experimentally observed.

Bio-inspired fabrication of asymmetric wettability Janus porous membrane for secure F-oil infused F-free-membrane filtration

Porous membranes, which consist of air-filled or liquid-filled pores, provide a gating strategy for tunable multiphase selectivity separation, and exhibit tremendous application potential in fields involving intelligent liquid management. Herein, we report the fabrication of a novel asymmetric wettability Janus porous membrane (JPM) based on bio-inspired models that integrate the air-gate floating mechanism and adhesive proteins secreted by mussels to attach to material-independent surfaces. The JPM fabricated through this novel and straightforward methodology has distinct hydrophobic-hydrophilic properties and interfacial compatibility. These features were engineered for F-oil (lubricant oil, Dupont Krytox 105) infused F-free JPM membrane filtration. The hydrophilic layer infused with high-surface-energy water acts as a perfect barrier (liquid gating) preventing invasion of the low-surface-energy F-oil which was infused in the hydrophobic surface, protecting the F-oil in the JPM. This is the first report regarding F-oil infused membrane filtration using the F-free-membrane, which can overcome the limitations of F-substrates for F-oil infused filtration.

Self-referenced axial chromatic dispersion measurement in multiphoton microscopy through 2-color third-harmonic generation imaging.

With tunable excitation light, multiphoton microscopy is widely used for imaging biological structures at subcellular resolution. Axial chromatic dispersion, present in virtually every transmissive optical system including the multiphoton microscope, leads to focal (and the resultant image) plane separation. Here, we experimentally demonstrate a technique to measure the axial chromatic dispersion in a multiphoton microscope, using simultaneous 2-color third-harmonic generation imaging excited by a 2-color soliton source with tunable wavelength separation. Our technique is self-referenced, eliminating potential measurement error when 1-color tunable excitation light is used which necessitates reciprocating motion of the mechanical translation stage. Using this technique, we demonstrate measured axial chromatic dispersion with 2 different objective lenses in a multiphoton microscope. Further measurement in a biological sample also indicates that this axial chromatic dispersion, in combination with 2-color imaging, may open up opportunity for simultaneous imaging of 2 different axial planes.

PDMS-Parylene Hybrid, Flexible Microfluidics for Real-Time Modulation of 3D Helical Inertial Microfluidics.

Inertial microfluidics has drawn much attention for its applications for circulating tumor cell separations from blood. The fluid flows and the inertial particle focusing in inertial microfluidic systems are highly dependent on the channel geometry and structure. Flexible microfluidic systems can have adjustable 3D channel geometries by curving planar 2D channels into 3D structures, which will enable tunable inertial separation. We present a poly(dimethylsiloxane) (PDMS)-parylene hybrid thin-film microfluidic system that can provide high flexibility for 3D channel shaping while maintaining the channel cross-sectional shape. The PDMS-parylene hybrid microfluidic channels were fabricated by a molding and bonding technique using initiated chemical vapor deposition (iCVD) bonding. We constructed 3D helical inertial microfluidic channels by coiling a straight 2D channel and studied the inertial focusing while varying radius of curvature and Reynolds number. This thin film structure allows for high channel curvature and high Dean numbers which leads to faster inertial particle focusing and shorter channel lengths than 2D spiral channels. Most importantly, the focusing positions of particles and cells in the microchannel can be tuned in real time by simply modulating the channel curvature. The simple mechanical modulation of these 3D structure microfluidic systems is expected to provide unique advantages of convenient tuning of cell separation thresholds with a single device.

Fabrication of mixed‐matrix membranes with MOF‐derived porous carbon for CO2 separation

Mixed‐matrix membranes (MMMs) have shown great advantages but still face some challenges, such as the trade‐off between permeability and selectivity, stability, and the lack of efficient ways to enhance them simultaneously. Here, the fabrication of MMMs with metal‐organic frameworks derived porous carbons (MOF‐PCs) as fillers which exhibit selective‐facilitating CO2 transport passage originating from interactions between fillers and CO2 is showed. With the aid of the developed multicalcination method, MOF‐PCs with variable N‐contents were prepared and incorporated into PPO‐PEG matrix for the first time to prepare MMMs, which show excellent separation performance for CO2/CH4 mixture with a tunable separation performance by combining different N‐contents and surface areas of MOF‐PCs. Moreover, the developed MMMs have hydrothermal and chemical stability. This work not only presents a series of MMMs with both good separation properties and stability, it also provides useful information for guiding the fabrication of high performance MMMs for practical application. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3400–3409, 2018

Solvent‐Responsive and Switchable Nanofiltration Membranes based on Hypercrosslinked Polymers with Permanent Porosity

AbstractPorous organic framework materials such as hypercrosslinked polymers (HCP) show a high chemical stability and dynamic behavior in a variety of solvents while their pore properties exhibit great potential for mixed matrix membrane (MMM) applications. However, their influence as porous filler in MMMs, especially for applications in liquid‐phase filtration is still unexploited. Herein, we demonstrate an HCP‐based MMM for molecular separation in the liquid phase by nanofiltration (NF). Depending on the solvent, the membrane changes its fractional free volume by shrinking or swelling. In connection to that, the pore size is also influenced, hence, providing a tunable permeance and molecular cut‐off. The reduction of the pore volume and size directly correlates to the improvement of the NF performance, while the volume increase completely diminishes it. The extraordinary flexibility and high degree of crosslinking assure permanent porosity and render the dynamic behavior fully reversible. Thereby, a solvent‐responsive “on” and “off” switching of the NF properties is enabled and was experimentally proven. Overall, this provides alternative strategies regarding the fouling and regeneration of membranes as well as the inhibition of pore blocking in membrane‐derived processes by a tunable separation performance.

Tunable particle separation in a hybrid dielectrophoresis (DEP)- inertial microfluidic device

Particle separation is indispensable in many microfluidic systems and holds a broad range of biomedical applications. Inertial microfluidic devices that work solely on intrinsic hydrodynamic forces and inertial effects can offer label-free, high throughput and high efficiency separation performance. However, the working range of the current inertial microfluidic systems is obtained by tailoring the inertial lift forces and secondary flow drag through flow speed. Each channel design is normally effective for specific target particles, which inevitably lacks the flexibility for various particle mixtures. Redesigning the structure and dimension of microchannels for new sets of particle mixtures is often time-consuming and expensive. In this work, by introducing an external dielectrophoretic force field and coupling it with inertial forces, we proposed here an innovative hybrid DEP-inertial microfluidic platform for particle tunable separation. The working principle of the device was explained and its functionality was validated by experiments. In addition, the dimension of target particle mixture can be varied by adjusting the electrical voltage without redesigning the channel structure or dimensions. It is expected that the proposed DEP-inertial concept can work as a flexible platform for a wide range of biomedical applications.