A Novel Approach for Measuring Gas Solubility in Liquids Using a Tube-in-Tube Membrane Contactor

A novel approach using a semipermeable Teflon AF‐2400 tube‐in‐tube membrane contactor was developed for the measurement of gas solubility in organic solvents. This membrane ensures gas saturation of liquids in continuous flow at a specific pressure and temperature. After liquid decompression, the amount of gas outgassed was measured with a bubble meter and used for solubility calculation. The proposed method was applied to the measurement of oxygen solubility in toluene and benzyl alcohol. Validation experiments were initially performed by comparing the obtained oxygen solubility in toluene with literature data. With higher temperature, the solubility of oxygen in benzyl alcohol was found to increase, indicating that the oxygen‐dissolving process is endothermic. Finally, an empirical correlation of Henry's law constant as a function of temperature was determined

Development of a Flat Membrane Microchannel Packed- Bed Reactor for Scalable Aerobic Oxidation of Benzyl Alcohol in Flow

A Teflon AF-2400 flat membrane microchannel reactor was designed and demonstrated for safe and scalable oxidation of solvent-free benzyl alcohol with molecular oxygen on Au- Pd/TiO2 catalyst. The microchannel reactor employed a mesh-supported Teflon AF-2400 flat membrane, with gas and liquid channels on each side. Catalyst particles were packed in the liquid flow channel. Operation with 20 bara pressure difference between the gas and the liquid phases was possible at 120 ºC. Pervaporation of organics through the membrane was experimentally measured to assure that the organic vapour concentration remains below the lower explosive limit during the reaction. The effect of oxygen pressure was studied, and the oxygen was shown to have a positive effect on the oxidation of benzyl alcohol. A conversion of benzyl alcohol of 70% with 71% selectivity to benzaldehyde was obtained at 1150 gcat·s/galcohol, 8.4 bara oxygen pressure and 10 bara liquid pressure. Doubling the membrane thickness led to a 20% drop of oxygen consumption rate, indicating the main oxygen transfer resistance not existing in the membrane. When changing the catalyst particle size and the liquid flow rate, no significant effect was observed on the oxidation reaction rate. An effectiveness factor approach is proposed to predict the effect of oxygen permeation and transverse mass transfer on the catalyst packed in the membrane reactor, which suggests that the oxidation of benzyl alcohol on the highly active Au-Pd/TiO2 catalyst is controlled by the oxygen transverse mass transfer in the bulk liquid within the catalyst bed. Scale-up of the flat membrane microchannel reactor was demonstrated through widening the liquid channel width by ~10 times, which increased the reactor productivity by a factor of 8

A Hydrodynamic Study of Benzyl Alcohol Oxidation in a Micro-Packed Bed Reactor

The various flow regimes prevalent during gold-palladium catalyzed benzyl alcohol oxidation in a micro-packed bed reactor and their influence on reaction performance are identified. The reaction is studied in a 300μm deep x 600μm wide silicon-glass micro-structured reactor packed with 65μm catalyst particles at a temperature of 120°C, pressure of 1 bar (g), using pure oxygen and neat benzyl alcohol as the feed. Significant improvement in the conversion and selectivity to the main product, benzaldehyde, is observed with increasing gas flowrate and decreasing liquid flowrate, which coincides with a change in the flow pattern from “liquid-dominated slug” (segregated regions of liquid and gas slugs) to “gas-continuous trickle” (thin film coated catalyst particles with gas flowing through the voids). The latter flow regime results in enhanced external mass transfer due to an increase in the available interfacial area and shorter diffusional distances. Results show selectivity up to 81% at a catalyst space time of 76 gcatgalc -1.s, outperforming a conventional batch laboratory reactor

Ultra high molecular weight polyethylene with incorporated crystal violet and gold nanoclusters is antimicrobial in low intensity light and in the dark

Antibiotics lose their effectiveness over time due to antimicrobial resistance. The increasing risk of hospital-acquired infections from contaminated surfaces and medical interventions requires the development of new antimicrobial materials. We report the first example of a modified ultra high molecular weight polyethylene that showed good antibacterial properties on light activation. Its efficacy was due to the production of reactive oxygen species under low-intensity white light sources (ca. 375 lux). Crystal violet and cysteine capped gold nanoclusters were successfully incorporated into the polymer using a readily available solvent as a dispersing agent followed by the process of compression moulding at 200 °C, 4.5 MPa for 1 min. This modified ultra-high molecular weight polyethylene demonstrates excellent robustness with regards to dye and metal leaching as well as photostability. Despite incorporating antimicrobial agents, the modified ultra-high molecular weight polyethylene retained its mechanical properties and showed >99% reduction in bacterial numbers against Escherichia coli and. To our knowledge, this paper reports the first use of compression moulding to create a light-activated antimicrobial surface which has distinct processing advantages over the widely used “swell-encapsulation-shrink” method and is potentially scalable

A study of the interaction of cationic dyes with gold nanostructures

The interaction of methylene blue and crystal violet dyes with a range of gold nanoparticles (AuNPs), gold nanoclusters and gold/silver nanoclusters is reported

A Modular Millifluidic Platform for the Synthesis of Iron Oxide Nanoparticles with Control over Dissolved Gas and Flow Configuration

Gas–liquid reactions are poorly explored in the context of nanomaterials synthesis, despite evidence of significant effects of dissolved gas on nanoparticle properties. This applies to the aqueous synthesis of iron oxide nanoparticles, where gaseous reactants can influence reaction rate, particle size and crystal structure. Conventional batch reactors offer poor control of gas–liquid mass transfer due to lack of control on the gas–liquid interface and are often unsafe when used at high pressure. This work describes the design of a modular flow platform for the water-based synthesis of iron oxide nanoparticles through the oxidative hydrolysis of Fe2+ salts, targeting magnetic hyperthermia applications. Four different reactor systems were designed through the assembly of two modular units, allowing control over the type of gas dissolved in the solution, as well as the flow pattern within the reactor (single-phase and liquid–liquid two-phase flow). The two modular units consisted of a coiled millireactor and a tube-in-tube gas–liquid contactor. The straightforward pressurization of the system allows control over the concentration of gas dissolved in the reactive solution and the ability to operate the reactor at a temperature above the solvent boiling point. The variables controlled in the flow system (temperature, flow pattern and dissolved gaseous reactants) allowed full conversion of the iron precursor to magnetite/maghemite nanocrystals in just 3 min, as compared to several hours normally employed in batch. The single-phase configuration of the flow platform allowed the synthesis of particles with sizes between 26.5 nm (in the presence of carbon monoxide) and 34 nm. On the other hand, the liquid–liquid two-phase flow reactor showed possible evidence of interfacial absorption, leading to particles with different morphology compared to their batch counterpart. When exposed to an alternating magnetic field, the particles produced by the four flow systems showed ILP (intrinsic loss parameter) values between 1.2 and 2.7 nHm2/kg. Scale up by a factor of 5 of one of the configurations was also demonstrated. The scaled-up system led to the synthesis of nanoparticles of equivalent quality to those produced with the small-scale reactor system. The equivalence between the two systems is supported by a simple analysis of the transport phenomena in the small and large-scale setup

Microfluidic synthesis of protein-loaded nanogels in a coaxial flow reactor using a design of experiments approach

Ionic gelation is commonly used to generate nanogels but often results in poor control over size and polydispersity. In this work we present a novel approach to the continuous manufacture of protein-loaded chitosan nanogels using microfluidics whereby we demonstrate high control and uniformity of the product characteristics. Specifically, a coaxial flow reactor (CFR) was employed to control the synthesis of the nanogels, comprising an inner microcapillary of internal diameter (ID) 0.595 mm and a larger outer glass tube of ID 1.6 mm. The CFR successfully facilitated the ionic gelation process via chitosan and lysozyme flowing through the inner microcapillary, while cross-linkers sodium tripolyphosphate (TPP) and 1-ethyl-2-(3-dimethylaminopropyl)-carbodiimide (EDC) flowed through the larger outer tube. In conjunction with the CFR, a four-factor three-level face-centered central composite design (CCD) was used to ascertain the relationship between various factors involved in nanogel production and their responses. Specifically, four factors including chitosan concentration, TPP concentration, flow ratio and lysozyme concentration were investigated for their effects on three responses (size, polydispersity index (PDI) and encapsulation efficiency (% EE)). A desirability function was applied to identify the optimum parameters to formulate nanogels in the CFR with ideal characteristics. Nanogels prepared using the optimal parameters were successfully produced in the nanoparticle range at 84 ± 4 nm, showing a high encapsulation efficiency of 94.6 ± 2.9% and a high monodispersity of 0.26 ± 0.01. The lysis activity of the protein lysozyme was significantly enhanced in the nanogels at 157.6% in comparison to lysozyme alone. Overall, the study has demonstrated that the CFR is a viable method for the synthesis of functional nanogels containing bioactive molecules

Kinetics-based design of a flow platform for highly reproducible on demand synthesis of gold nanoparticles with controlled size between 50 and 150 nm and their application in SERS and PIERS sensing

Seeded-growth synthetic protocols enable precise control of particle size and shape, crucial for many sensing applications. However, scaling-up these syntheses in a reproducible way is challenging, as minimal variation in process parameters such as seed size, concentration or reaction temperature can significantly alter the final product. Flow reactors enable tight control in the process parameters and high reproducibility of the synthesis, representing a potential technology to perform seeded-growth syntheses in large scale. This work reports the design of a flow platform for the controlled synthesis of spherical gold nanoparticles with size up to 150nm through a seeded-growth approach, and their use in Surface Enhanced Raman Scattering (SERS) and Photoinduced Enhanced Raman Spectroscopy (PIERS). The particle growth kinetics were studied via in situ time-resolved UV–Vis spectroscopy. The spectroscopic data were fitted with a kinetic model, which was subsequently used for the design of the reactor. The kinetics-based design approach enabled fast translation of the growth synthesis in flow, eventually allowing the on demand flow synthesis of particles with controllable size, ranging from 50 to 150nm, with high reproducibility and full precursor conversion. The particles were tested for SERS and PIERS for different substrates, including warfare agents and biomolecules, with enhancement factors between 103 and 108 depending on the analyte, demonstrating their potential for detection of various analytes

Highly reproducible, high-yield flow synthesis of gold nanoparticles based on a rational reactor design exploiting the reduction of passivated Au(III)

Reproducibility in the synthesis of nanomaterials is a crucial aspect for their real-life applications. It is particularly pertinent in the context of gold nanoparticles, where a plethora of seeded-growth methods are being developed to control particle morphology and size. The translation of such methods to manufacturing can be hindered by poor reproducibility of the seed production step. This study focuses on the development of a highly reproducible platform for the synthesis of gold nanoparticles, as potential substrates for glucose sensing. A flow reactor was designed, starting from a detailed study of the synthesis in batch. The well-established Turkevich synthesis was investigated via in situ time-resolved UV-vis spectroscopy. In order to enhance the reproducibility of the synthesis the effect of passivating the gold precursor stock before its use in the synthesis was investigated. It is shown that starting from a pre-passivated precursor provided improved control over the initial reaction stage, at the expense of a small increase in the reaction time. At the optimal reaction conditions, the proposed modified Turkevich method allowed for the synthesis in batch of ∼12 nm monodisperse (RSD ∼10%) particles, with a variability from batch to batch of only ∼5%. The information gathered from the batch study, in particular the reaction time, was used to translate the synthesis from batch to flow. The system utilized for the flow synthesis consisted of a segmented flow reactor, where an organic stream was employed to segment the reactive aqueous stream to avoid reactor fouling and improve monodispersity. The use of segmented flow enables treating each droplet as a “travelling batch”, hence allowing the direct use of the kinetic data obtained in batch to design the flow reactor, leading to the rapid identification of the minimum residence time to allow for reaction completion. The flow reactor enabled the synthesis of ∼11 nm monodisperse (RSD ∼10%) particles, with full precursor conversion and reproducibility between reactor runs higher than that obtained in batch (variability of ∼2%). The flow-produced gold nanoparticles were tested for glucose sensing, exploiting their glucose oxidase-mimicking behaviour and demonstrated satisfactory glucose detection in the range of 1–10 mM

Synthesis of PEG-PPG-PEG templated polydopamine nanoparticles under intensified conditions: Kinetics investigation, continuous process design and demonstration for photothermal application

Polydopamine is a nature inspired functional material with promising applications in a plethora of fields due to its structural, chemical, and optical properties. While there is significant interest in the preparation of polydopamine based nanomaterials that take advantage of its properties, less attention has been given to the optimisation of the synthetic process, which typically involves the oxidative self-polymerisation of dopamine under basic pH and requires 24–72 h for reaction completion. The present work investigated the kinetics of polydopamine formation in the presence of Pluronic P-123 (PEG-PPG-PEG) micelles acting as a soft template, in low monomer concentrations (that promote particle growth instead of nucleation) as a function of temperature and pressure. Simultaneous increase of pressure and temperature (up to 50 °C and 5 bar O2) was found to significantly reduce the reaction time to 20–40 min without compromising the particle quality. Based on the results of the kinetic investigation, the polydopamine synthesis was translated into a continuous process utilising a millifluidic co-axial membrane reactor with a focus on ease of use, process conditions’ reproducibility and safety of operation. The reactor produced nanoparticles similar to the batch synthesis and resisted fouling (which is generally expected in a compact flow reactor) due to the action of the P-123 surfactant. Due to the nontoxic process that utilises only biocompatible materials and oxygen as the oxidising agent, and the melanin-like structure of polydopamine, photothermal heating of the synthesised nanoparticles under concentrated IR irradiation at 808 nm light was studied, as this can potentially be used for photo-induced hyperthermia. The hyperthermia threshold of 10 °C temperature increase at relatively low laser power settings (fluence 1.77 W/cm2) was achieved, making it a promising candidate for this application