Colloidal Synthesis of Carbon Dot-ZnSe Nanoplatelet Van der Waals Heterostructures for Boosting Photocatalytic Generation of Methanol-Storable Hydrogen.

Methanol is not only a promising liquid hydrogen carrier but also an important feedstock chemical for chemical synthesis. Catalyst design is vital for enabling the reactions to occur under ambient conditions. This study reports a new class of van der Waals heterojunction photocatalyst, which is synthesized by hot-injection method, whereby carbon dots (CDs) are grown in situ on ZnSe nanoplatelets (NPLs), i.e., metal chalcogenide quantum wells. The resultant organic-inorganic hybrid nanoparticles, CD-NPLs, are able to perform methanol dehydrogenation through CH splitting. The heterostructure has enabled light-induced charge transfer from the CDs into the NPLs occurring on a sub-nanosecond timescale, with charges remaining separated across the CD-NPLs heterostructure for longer than 500 ns. This resulted in significantly heightened H2 production rate of 107 µmole·g-1·h-1 and enhanced photocurrent density up to 34 µA cm-2 at 1 V bias potential. EPR and NMR analyses confirmed the occurrence of α-CH splitting and CC coupling. The novel CD-based organic-inorganic semiconductor heterojunction is poised to enable the discovery of a host of new nano-hybrid photocatalysts with full tunability in the band structure, charge transfer, and divergent surface chemistry for guiding photoredox pathways and accelerating reaction rates.

Spinning Reactors for Process Intensification of Flow Photochemistry.

The design of new and more sustainable synthetic protocols to access new materials or valuable compounds will have a high impact on the broader chemistry community. In this sense, continuous-flow photochemistry has emerged as a powerful technique which has been employed successfully in various areas such as biopharma, organic chemistry, as well as materials science. However, it is important to note that chemical processes must not only advance towards new or improved chemical transformations, but also implement new technologies that enable new process opportunities. For this reason, the design of novel photoreactors is key to advancing photochemical strategies. In this sense, the use of equipment and techniques embracing processes intensification is important in developing more sustainable protocols. Among the most recent applications, spinning continuous flow reactors, such as rotor reactors or vortex reactors, have shown promising performance as new synthetic tools. Nevertheless, there is currently no review in the literature that effectively summarizes and showcases the most recent applications of such type of photoreactors. Herein, we highlight fundamental aspects and applications of two categories of spinning reactors, the Spinning Disc Reactors (SDRs) and Thin Film Vortex reactors, critiquing the scope and limitations of these advanced processing technologies. Further, we take a view on the future of spinning reactors in flow as a synthetic toolbox to explore new photochemical transformations.

Vortex fluidic regulated phospholipid equilibria involving liposomes down to sub-micelle size assemblies.

Conventional channel-based microfluidic platforms have gained prominence in controlling the bottom-up formation of phospholipid based nanostructures including liposomes. However, there are challenges in the production of liposomes from rapidly scalable processes. These have been overcome using a vortex fluidic device (VFD), which is a thin film microfluidic platform rather than channel-based, affording ∼110 nm diameter liposomes. The high yielding and high throughput continuous flow process has a 45° tilted rapidly rotating glass tube with an inner hydrophobic surface. Processing is also possible in the confined mode of operation which is effective for labelling pre-VFD-prepared liposomes with fluorophore tags for subsequent mechanistic studies on the fate of liposomes under shear stress in the VFD. In situ small-angle neutron scattering (SANS) established the co-existence of liposomes ∼110 nm with small rafts, micelles, distorted micelles, or sub-micelle size assemblies of phospholipid, for increasing rotation speeds. The equilibria between these smaller entities and ∼110 nm liposomes for a specific rotational speed of the tube is consistent with the spatial arrangement and dimensionality of topological fluid flow regimes in the VFD. The prevalence for the formation of ∼110 nm diameter liposomes establishes that this is typically the most stable structure from the bottom-up self-assembly of the phospholipid and is in accord with dimensions of exosomes.

High conversion continuous flow exfoliation of 2D MoS2.

We report a low-cost and highly efficient process for exfoliating of MoS2 using an energy efficient vortex fluidic device (VFD). This method is high in green chemistry metrics in avoiding the use of auxiliary substances, and the process is scalable, with a conversion of as received MoS2 into 2D sheets at ∼73%.

Enhanced mechanical strength of vortex fluidic mediated biomass-based biodegradable films composed from agar, alginate and kombucha cellulose hydrolysates.

Biodegradable, biomass derived kombucha cellulose films with increased mechanical strength from 9.98 MPa to 18.18 MPa were prepared by vortex fluidic device (VFD) processing. VFD processing not only reduced the particle size of kombucha cellulose from approximate 2 µm to 1 µm, but also reshaped its structure from irregular to round. The increased mechanical strength of these polysaccharide-derived films is the result of intensive micromixing and high shear stress of a liquid thin film in a VFD. This arises from the incorporation at the micro-structural level of uniform, unidirectional strings of kombucha cellulose hydrolysates, which resulted from the topological fluid flow in the VFD. The biodegradability of the VFD generated polymer films was not compromised relative to traditionally generated films. Both films were biodegraded within 5 days.

Vortex fluidic high shear induced crystallisation of fullerene C70 into nanotubules.

Hollow C70 nanotubules are formed under high shear within the thin film of a vortex fluidic device (VFD) without the need for using auxiliary reagents, high temperatures and pressures, and/or requiring downstream processing. This novel bottom-up crystallisation process involves intense micro mixing of two liquids (toluene solution of C70 and anti-solvent, isopropyl alcohol) within a thin film in the VFD to precisely control the hierarchical assembly of C70 molecules into hollow nanotubules. The mechanism of self-assembly was consistent with them being a mould of the high shear double helical topological flow from Faraday waves coupled with Coriolis forces generated within the thin film.

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.

High Shear Thin Film Synthesis of Partially Oxidized Gallium and Indium Composite 2D Sheets.

Reducing resistance in silicon-based devices is important as they get miniaturized further. 2D materials offer an opportunity to increase conductivity whilst reducing size. A scalable, environmentally benign method is developed for preparing partially oxidized gallium/indium sheets down to 10 nm thick from a eutectic melt of the two metals. Exfoliation of the planar/corrugated oxide skin of the melt is achieved using the vortex fluidic device with a variation in composition across the sheets determined using Auger spectroscopy. From an application perspective, the oxidized gallium indium sheets reduce the contact resistance between metals such as platinum and silicon (Si) as a semiconductor. Current-voltage measurements between a platinum atomic force microscopy tip and a Si-H substrate show that the current switches from being a rectifier to a highly conducting ohmic contact. These characteristics offer new opportunities for controlling Si surface properties at the nanoscale and enable the integration of new materials with Si platforms.

Exploiting angled thin film vortex microfluidics for expeditious syntheses of iminosugars.

Iminosugars are important compounds in the area of carbohydrate-based therapeutics. A simple synthetic methodology utilizing the vortex fluidic thin film microfluidic reactor is effective in the synthesis of such compounds for diverse reaction types, with the optimal tilt angle of the reactor at 45° and the optimal rotational speed dependent on the nature of the liquid.

Continuous flow fabrication of green graphene oxide in aqueous hydrogen peroxide.

Highly processible graphene oxide (GO) has a diversity of applications as a material readily dispersed in aqueous media. However, methods for preparing such free-standing GO use hazardous and toxic reagents and generate significant waste streams. This is an impediment for uptake of GO in any application, for developing sustainable technologies and industries, and overcoming this remains a major challenge. We have developed a robust scalable continuous flow method for fabricating GO directly from graphite in 30% aqueous hydrogen peroxide which dramatically minimises the generation of waste. The process features the continuous flow thin film microfluidic vortex fluidic device (VFD), operating at specific conditions while irradiated sequentially by UV LED than a NIR pulsed laser. The resulting 'green' graphene oxide (gGO) has unique properties, possessing highly oxidized edges with large intact sp2 domains which gives rise to exceptional electrical and optical properties, including purple to deep blue emission of narrow full width at half maximum (<35 nm). Colloidally stable gGO exhibits cytotoxicity owing to the oxidised surface groups while solid-state films of gGO are biocompatible. The continuous flow method of generating gGO also provides unprecedented control of the level of oxidation and its location in the exfoliated graphene sheets by harnessing the high shear topological fluid flows in the liquid, and varying the wavelength, power and pulse frequency of the light source.

Electro-polymerization rates of diazonium salts are dependent on the crystal orientation of the surface.

Electro-polymerization of diazonium salts is widely used for modifying surfaces with thin organic films. Initially this method was primarily applied to carbon, then to metals, and more recently to semiconducting Si. Unlike on other surfaces, electrochemical reduction of diazonium salts on Si, which is one of the most industrially dominant material, is not well understood. Here, we report the electrochemical reduction of diazonium salts on a range of silicon electrodes of different crystal orientations (111, 211, 311, 411, and 100). We show that the kinetics of surface reaction and the reduction potential is Si crystal-facet dependent and is more favorable in the hierarchical order (111) > (211) > (311) > (411) > (100), a finding that offers control over the surface chemistry of diazonium salts on Si. The dependence of the surface reaction kinetics on the crystal orientation was found to be directly related to differences in the potential of zero charge (PZC) of each crystal orientation, which in turn controls the adsorption of the diazonium cations prior to reduction. Another consequence of the effect of PZC on the adsorption of diazonium cations, is that molecules terminated by distal diazonium moieties form a compact film in less time and requires less reduction potentials compared to that formed from diazonium molecules terminated by only one diazo moiety. In addition, at higher concentrations of diazonium cations, the mechanism of electrochemical polymerization on the surface becomes PZC-controlled adsorption-dominated inner-sphere electron transfer while at lower concentrations, diffusion-based outer-sphere electron transfer dominates. These findings help understanding the electro-polymerization reaction of diazonium salts on Si en route towards an integrated molecular and Si electronics technology.

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.

Under-5-Minute Immunoblot Assays by Vortex Fluidic Device Acceleration.

Unlocking the potential of personalized medicine in point-of-care settings requires a new generation of biomarker and proteomic assays. Ideally, assays could inexpensively perform hundreds of quantitative protein measurements in parallel at the bedsides of patients. This goal greatly exceeds current capabilities. Furthermore, biomarker assays are often challenging to translate from benchtop to clinic due to difficulties achieving and assessing the necessary selectivity, sensitivity, and reproducibility. To address these challenges, we developed an efficient (<5 min), robust (comparatively lower CVs), and inexpensive (decreasing reagent use and cost by >70 %) immunoassay method. Specifically, the immunoblot membrane is dotted with the sample and then developed in a vortex fluidic device (VFD) reactor. All assay steps-blocking, binding, and washing-leverage the unique thin-film microfluidics of the VFD. The approach can accelerate direct, indirect, and sandwich immunoblot assays. The applications demonstrated include assays relevant to both the laboratory and the clinic.

Developing Novel Fabrication and Optimisation Strategies on Aggregation-Induced Emission Nanoprobe/Polyvinyl Alcohol Hydrogels for Bio-Applications.

The current study describes a new technology, effective for readily preparing a fluorescent (FL) nanoprobe-based on hyperbranched polymer (HB) and aggregation-induced emission (AIE) fluorogen with high brightness to ultimately develop FL hydrogels. We prepared the AIE nanoprobe using a microfluidic platform to mix hyperbranched polymers (HB, generations 2, 3, and 4) with AIE (TPE-2BA) under shear stress and different rotation speeds (0-5 K RPM) and explored the FL properties of the AIE nanoprobe. Our results reveal that the use of HB generation 4 exhibits 30-times higher FL intensity compared to the AIE alone and is significantly brighter and more stable compared to those that are prepared using HB generations 3 and 2. In contrast to traditional methods, which are expensive and time-consuming and involve polymerization and post-functionalization to develop FL hyperbranched molecules, our proposed method offers a one-step method to prepare an AIE-HB nanoprobe with excellent FL characteristics. We employed the nanoprobe to fabricate fluorescent injectable bioadhesive gel and a hydrogel microchip based on polyvinyl alcohol (PVA). The addition of borax (50 mM) to the PVA + AIE nanoprobe results in the development of an injectable bioadhesive fluorescent gel with the ability to control AIEgen release for 300 min. When borax concentration increases two times (100 mM), the adhesion stress is more than two times bigger (7.1 mN/mm2) compared to that of gel alone (3.4 mN/mm2). Excellent dimensional stability and cell viability of the fluorescent microchip, along with its enhanced mechanical properties, proposes its potential applications in mechanobiology and understanding the impact of microstructure in cell studies.

Vortex Fluidic Mediated Oxidative Sulfitolysis of Oxytocin.

In peptide production, oxidative sulfitolysis can be used to protect the cysteine residues during purification, and the introduction of a negative charge aids solubility. Subsequent controlled reduction aids in ensuring correct disulfide bridging. In vivo, these problems are overcome through interaction with chaperones. Here, a versatile peptide production process has been developed using an angled vortex fluidic device (VFD), which expands the viable pH range of oxidative sulfitolysis from pH 10.5 under batch conditions, to full conversion within 20 min at pH 9-10.5 utilising the VFD. VFD processing gave 10-fold greater conversion than using traditional batch processing, which has potential in many applications of the sulfitolysis reaction.

Impermeable Graphene Oxide Protects Silicon from Oxidation.

The presence of a natural silicon oxide (SiOx) layer over the surface of silicon (Si) has been a roadblock for hybrid semiconductor and organic electronics technology. The presence of an insulating oxide layer is a limiting operational factor, which blocks charge transfer and therefore electrical signals for a range of applications. Etching the SiOx layer by fluoride solutions leaves a reactive Si-H surface that is only stable for few hours before it starts reoxidizing under ambient conditions. Controlled passivation of silicon is also of key importance for improving Si photovoltaic efficiency. Here, we show that a thin layer of graphene oxide (GOx) prevents Si surfaces from oxidation under ambient conditions for more than 30 days. In addition, we show that the protective GOx layer can be modified with molecules enabling a functional surface that allows for further chemical conjugation or connections with upper electrodes, while preserving the underneath Si in a nonoxidized form. The GOx layer can be switched electrochemically to reduced graphene oxide, allowing the development of a dynamic material for molecular electronics technologies. These findings demonstrate that 2D materials are alternatives to organic self-assembled monolayers that are typically used to protect and tune the properties of Si and open a realm of possibilities that combine Si and 2D materials technologies.

In Situ Monitored Vortex Fluidic-Mediated Protein Refolding/Unfolding Using an Aggregation-Induced Emission Bioprobe.

Protein folding is important for protein homeostasis/proteostasis in the human body. We have established the ability to manipulate protein unfolding/refolding for ß-lactoglobulin using the induced mechanical energy in the thin film microfluidic vortex fluidic device (VFD) with monitoring as such using an aggregation-induced emission luminogen (AIEgen), TPE-MI. When denaturant (guanidine hydrochloride) is present with ß-lactoglobulin, the VFD accelerates the denaturation reaction in a controlled way. Conversely, rapid renaturation of the unfolded protein occurs in the VFD in the absence of the denaturant. The novel TPE-MI reacts with exposed cysteine thiol when the protein unfolds, as established with an increase in fluorescence intensity. TPE-MI provides an easy and accurate way to monitor the protein folding, with comparable results established using conventional circular dichroism. The controlled VFD-mediated protein folding coupled with in situ bioprobe AIEgen monitoring is a viable methodology for studying the denaturing of proteins.

Four component Passerini polymerization of bulky monomers under high shear flow.

We introduce a four component Passerini polymerization utilizing sterically bulky isocyanide monomers. Under typical Passerini conditions, bulky isocyanides do not react within standard Passerini reaction timescales (hours). We overcome this challenge via the unique physiochemical conditions present in a vortex fluidic device, reducing the reaction time to 2 h on average. Under these high-shear thin-film conditions, bulky isocyanides are readily incorporated into the multicomponent polymerization without the need of high-pressure or temperature. Finally, we demonstrate that the four component approach using functional cyclic anhydrides allows for post-polymerization modification.

Carbonisation of a polymer made from sulfur and canola oil.

A polymer made from equal masses of sulfur and canola oil was carbonised at 600 °C for 30 minutes. The resulting material exhibited improved uptake of mercury from water compared to the polymer. The carbonisation could also be done after using the polymer to clean up oil spills, which suprisingly improved mercury uptake to levels rivaling commercial carbons.

Noncovalent Protein-Pseudorotaxane Assembly Incorporating an Extended Arm Calix[8]arene with α-Helical Recognition Properties.

Water-soluble, anionic calix[n]arenes are useful receptors for protein recognition and assembly. For example, sulfonato-calix[8]arene (sclx 8 ) can encapsulate proteins and direct their assembly into porous frameworks. In this work, we turned our attention to an "extended arm" calixarene with 16 phenyl rings. We hypothesized that this larger receptor would have increased capacity for protein masking/encapsulation. A cocrystal structure of p-benzyl-sulfonato-calix[8]arene (b-sclx 8 ) and cytochrome c (cyt c) revealed a surprising assembly. A pseudorotaxane comprising a stack of three b-sclx 8 molecules threaded by polyethylene glycol (PEG) was bound to the protein. The trimeric b-sclx 8 stack, a tubelike structure with a highly charged surface, mediated assembly via a new mode of protein recognition. The calixarene stack presents four hydrophobic grooves, each of which binds to one cyt c by accommodating the N-terminal α-helix. This unprecedented binding mode suggests new possibilities for supramolecular protein chemistry.