Printable Hydrogel Arrays for Portable and High-Throughput Shear-Mediated Assays.

Hydrogels have been widely used to entrap biomolecules for various biocatalytic reactions. However, solute diffusion in these matrices to initiate such reactions can be a very slow process. Conventional mixing remains a challenge as it can cause irreversible distortion or fragmentation of the hydrogel itself. To overcome the diffusion-limit, a shear-stress-mediated platform named the portable vortex-fluidic device (P-VFD) is developed. P-VFD is a portable platform which consists of two main components, (i) a plasma oxazoline-coated polyvinyl chloride (POx-PVC) film with polyacrylamide and alginate (PAAm/Alg-Ca2+) tough hydrogel covalently bound to its surface and (ii) a reactor tube (L × D: 90 mm × 20 mm) where the aforementioned POx-PVC film could be readily inserted for reactions. Through a spotting machine, the PAAm/Alg-Ca2+ hydrogel can be readily printed on a POx-PVC film in an array pattern and up to 25.4 J/m2 adhesion energy can be achieved. The hydrogel arrays on the film not only offer a strong matrix for entrapping biomolecules such as streptavidin-horseradish peroxidase but are also shear stress-tolerant in the reactor tube, enabling a >6-fold increase in its reaction rate after adding tetramethylbenzidine, relative to incubation. Through using the tough hydrogel and its stably bonded substrate, this portable platform effectively overcomes the diffusion-limit and achieves fast assay detection without causing appreciable hydrogel array deformation or dislocation on the substrate film.

Vortex fluidic induced mass transfer across immiscible phases.

Mixing immiscible liquids typically requires the use of auxiliary substances including phase transfer catalysts, microgels, surfactants, complex polymers and nano-particles and/or micromixers. Centrifugally separated immiscible liquids of different densities in a 45° tilted rotating tube offer scope for avoiding their use. Micron to submicron size topological flow regimes in the thin films induce high inter-phase mass transfer depending on the nature of the two liquids. A hemispherical base tube creates a Coriolis force as a 'spinning top' (ST) topological fluid flow in the less dense liquid which penetrates the denser layer of liquid, delivering liquid from the upper layer through the lower layer to the surface of the tube with the thickness of the layers determined using neutron imaging. Similarly, double helical (DH) topological flow in the less dense liquid, arising from Faraday wave eddy currents twisted by Coriolis forces, impact through the less dense liquid onto the surface of the tube. The lateral dimensions of these topological flows have been determined using 'molecular drilling' impacting on a thin layer of polysulfone on the surface of the tube and self-assembly of nanoparticles at the interface of the two liquids. At high rotation speeds, DH flow also occurs in the denser layer, with a critical rotational speed reached resulting in rapid phase demixing of preformed emulsions of two immiscible liquids. ST flow is perturbed relative to double helical flow by changing the shape of the base of the tube while maintaining high mass transfer between phases as demonstrated by circumventing the need for phase transfer catalysts. The findings presented here have implications for overcoming mass transfer limitations at interfaces of liquids, and provide new methods for extractions and separation science, and avoiding the formation of emulsions.

Sub-micron moulding topological mass transport regimes in angled vortex fluidic flow.

Shear stress in dynamic thin films, as in vortex fluidics, can be harnessed for generating non-equilibrium conditions, but the nature of the fluid flow is not understood. A rapidly rotating inclined tube in the vortex fluidic device (VFD) imparts shear stress (mechanical energy) into a thin film of liquid, depending on the physical characteristics of the liquid and rotational speed, ω, tilt angle, θ, and diameter of the tube. Through understanding that the fluid exhibits resonance behaviours from the confining boundaries of the glass surface and the meniscus that determines the liquid film thickness, we have established specific topological mass transport regimes. These topologies have been established through materials processing, as spinning top flow normal to the surface of the tube, double-helical flow across the thin film, and spicular flow, a transitional region where both effects contribute. The manifestation of mass transport patterns within the film have been observed by monitoring the mixing time, temperature profile, and film thickness against increasing rotational speed, ω. In addition, these flow patterns have unique signatures that enable the morphology of nanomaterials processed in the VFD to be predicted, for example in reversible scrolling and crumbling graphene oxide sheets. Shear-stress induced recrystallisation, crystallisation and polymerisation, at different rotational speeds, provide moulds of high-shear topologies, as 'positive' and 'negative' spicular flow behaviour. 'Molecular drilling' of holes in a thin film of polysulfone demonstrate spatial arrangement of double-helices. The grand sum of the different behavioural regimes is a general fluid flow model that accounts for all processing in the VFD at an optimal tilt angle of 45°, and provides a new concept in the fabrication of novel nanomaterials and controlling the organisation of matter.

Vortex Fluidic-Mediated Fabrication of Fast Gelated Silica Hydrogels with Embedded Laccase Nanoflowers for Real-Time Biosensing under Flow.

The fabrication of hybrid protein-Cu3(PO4)2 nanoflowers (NFs) via an intermediate toroidal structure is dramatically accelerated under shear using a vortex fluidic device (VFD), which possesses a rapidly rotating angled tube. As-prepared laccase NFs (LNFs) exhibit ≈1.8-fold increase in catalytic activity compared to free laccase under diffusion control, which is further enhanced by ≈ 2.9-fold for the catalysis under shear in the VFD. A new LNF immobilization platform, LNF@silica incorporated in a VFD tube, was subsequently developed by mixing the LNFs for 15 min with silica hydrogel resulting in gelation along the VFD tube surface. The resulting LNFs@silica coating is highly stable and reusable, which allows a dramatic 16-fold enhancement in catalytic rates relative to LNF@silica inside glass vials. Ultraviolet-visible spectroscopy-based real-time monitoring within the LNFs@silica-coated tube reveals good stability of the coating in continuous flow processing. The results demonstrate the utility of the VFD microfluidic platform, further highlighting its ability to control chemical and enzymatic processes.

Vortex fluidic mediated synthesis of polysulfone.

Polysulfone (PSF) was prepared under high shear in a vortex fluidic device (VFD) operating in confined mode, and its properties compared with that prepared using batch processing. This involved reacting the pre-prepared disodium salt of bisphenol A (BPA) with a 4,4'-dihalodiphenylsulfone under anhydrous conditions. Scanning electron microscopy (SEM) established that in the thin film microfluidic platform, the PSF particles are sheet-like, for short reaction times, and fibrous for long reaction times, in contrast to spherical like particles for the polymer prepared using the conventional batch synthesis. The operating parameters of the VFD (rotational speed of the glass tube, its tilt angle and temperature) were systematically varied for establishing their effect on the molecular weight (M w), glass transition temperature (T g) and decomposition temperature, featuring gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) respectively. The optimal VFD prepared PSF was obtained at 6000 rpm rotational speed, 45° tilt angle and 160 °C, for 1 h of processing with M w ∼10 000 g mol-1, T g ∼158 °C and decomposition temperature ∼530 °C, which is comparable to the conventionally prepared PSF.