Advanced IoT Pressure Monitoring System for Real-Time Landfill Gas Management.

This research presents a novel stand-alone device for the autonomous measurement of gas pressure levels on an active landfill site, which enables the real-time monitoring of gas dynamics and supports the early detection of critical events. The developed device employs advanced sensing technologies and wireless communication capabilities, enabling remote data transmission and access via the Internet. Through extensive field experiments, we demonstrate the high sampling rate of the device and its ability to detect significant events related to gas generation dynamics in landfills, such as flare shutdowns or blockages that could lead to hazardous conditions. The validation of the device's performance against a high-end analytical system provides further evidence of its reliability and accuracy. The developed technology herein offers a cost-effective and scalable solution for environmental landfill gas monitoring and management. We expect that this research will contribute to the advancement of environmental monitoring technologies and facilitate better decision-making processes for sustainable waste management.

Green IoT Event Detection for Carbon-Emission Monitoring in Sensor Networks.

This research addresses the intersection of low-power microcontroller technology and binary classification of events in the context of carbon-emission reduction. The study introduces an innovative approach leveraging microcontrollers for real-time event detection in a homogeneous hardware/firmware manner and faced with limited resources. This showcases their efficiency in processing sensor data and reducing power consumption without the need for extensive training sets. Two case studies focusing on landfill CO2 emissions and home energy usage demonstrate the feasibility and effectiveness of this approach. The findings highlight significant power savings achieved by minimizing data transmission during non-event periods (94.8-99.8%), in addition to presenting a sustainable alternative to traditional resource-intensive AI/ML platforms that comparatively draw and produce 20,000 times the amount of power and carbon emissions, respectively.

Big data and machine learning for materials science.

Herein, we review aspects of leading-edge research and innovation in materials science that exploit big data and machine learning (ML), two computer science concepts that combine to yield computational intelligence. ML can accelerate the solution of intricate chemical problems and even solve problems that otherwise would not be tractable. However, the potential benefits of ML come at the cost of big data production; that is, the algorithms demand large volumes of data of various natures and from different sources, from material properties to sensor data. In the survey, we propose a roadmap for future developments with emphasis on computer-aided discovery of new materials and analysis of chemical sensing compounds, both prominent research fields for ML in the context of materials science. In addition to providing an overview of recent advances, we elaborate upon the conceptual and practical limitations of big data and ML applied to materials science, outlining processes, discussing pitfalls, and reviewing cases of success and failure.

A wearable sensor for the detection of sodium and potassium in human sweat during exercise.

The SwEatch platform, a wearable sensor for sampling and measuring the concentration of electrolytes in human sweat in real time, has been improved in order to allow the sensing of two analytes. The solid contact ion-sensitive electrodes (ISEs) for the detection of Na+ and K+ have been developed in two alternative formulations, containing either poly(3,4-ethylenedioxythiophene) (PEDOT) or poly(3-octylthiophene-2,5-diyl) (POT) as a conductive polymer transducing component. The solution-processable POT formulation simplifies the fabrication process, and sensor to sensor reproducibility has been improved via partial automation using an Opentron® automated pipetting robot. The resulting electrodes showed good sensitivity (52.4 ± 6.3 mV/decade (PEDOT) and 56.4 ± 2.2 mV/decade (POT) for Na+ ISEs, and 45.7 ± 7.4 mV/decade (PEDOT) and 54.3 ± 1.5 mV/decade (POT) for K+) and excellent selectivity towards potential interferents present in human sweat (H+, Na+, K+, Mg2+, Ca2+). The 3D printed SwEatch platform has been redesigned to incorporate a double, mirrored fluidic unit which is capable of drawing sweat from the skin through passive capillary action and bring it in contact with two independent electrodes. The potentiometric signal generated by the electrodes is measured by an integrated electronics board, digitised and transmitted via Bluetooth to a laptop. The results obtained from on-body trials on athletes during cycling show a relatively small increase in sodium (1.89 mM-2.97 mM) and potassium (3.31 mM-7.25 mM) concentrations during the exercise period of up to 90 min.

Direct Laser Writing of Four-Dimensional Structural Color Microactuators Using a Photonic Photoresist.

With the advent of direct laser writing using two-photon polymerization, the generation of high-resolution three-dimensional microstructures has increased dramatically. However, the development of stimuli-responsive photoresists to create four-dimensional (4D) microstructures remains a challenge. Herein, we present a supramolecular cholesteric liquid crystalline photonic photoresist for the fabrication of 4D photonic microactuators, such as pillars, flowers, and butterflies, with submicron resolution. These micron-sized features display structural color and shape changes triggered by a variation of humidity or temperature. These findings serve as a roadmap for the design and creation of high-resolution 4D photonic microactuators.

Smartphone based meat freshness detection.

In this work, a freshness colorimetric sensor has been integrated with pork meat packages. The sensor tracks rising CO2 levels in the package associated with meat spoilage, as CO2 levels increase with bacterial population. The color of the sensor changes depending on the quantity of bacteria present, therefore it can be correlated with the freshness of meat, in this case pork loin. Detection is achieved by a simple photograph using a smartphone, and analyzing the grey scale from the RGB space color with a custom made app. Only 2 µL of the cocktail (all components are nontoxic) is needed to prepare the sensor, which have been integrated inside meat packages using a variety of support materials prior to sealing. The Smartphone measurements have been validated using a reference method (Checkpoint Analyzer) and the results suggest it can provide the basis for a quick test of the quality of the packaged pork.

Fully automated, low-cost ion chromatography system for in-situ analysis of nitrite and nitrate in natural waters.

A cost-effective, automated and portable IC has been developed for in-situ analysis of nitrite and nitrate in natural waters. The system employed 3D printed pumps for eluent delivery and a deep-UV LED based optical detector. Isocratic separation and selective detection of nitrite and nitrate was achieved in under 3 min. The total weight of the analyser was ~11 kg, and included electronics along with a sample intake system for automated analysis. Linear calibration ranges were generated using different sample injection loops. Using a 150 µL loop, an analytical range (0.05-30 mg L-1 NO2-, 0.10-75 mg L-1 NO3-) suitable for freshwater analysis was generated, while using a 10 µL loop an analytical range (0.30-100 mg L-1 NO2-, 2.5-500 mg L-1 NO3-) suitable for effluent and domestic wastewater analysis was achieved. Chromatographic repeatability demonstrated by the system is graphically presented and RSD values of <4% were obtained in terms of peak area and retention time over 82 sequential runs. The system was deployed in-situ at multiple sites for varying deployment periods analysing septic tank water, effluent from a waste water treatment plant and stream water. The data generated by the in-situ system were comparable to grab sample data generated by accredited laboratory instrumentation.

3D Printed Sugar-Sensing Hydrogels.

The ability of boronic acids (BAs) to reversibly bind diols, such as sugars, has been widely studied in recent years. In solution, through the incorporation of additional fluorophores, the BA-sugar interaction can be monitored by changes in fluorescence. Ultimately, a practical realization of this technology requires a transition from solution-based methodologies. Herein, the first example of 3D-printed sugar-sensing hydrogels, achieved through the incorporation of a BA-fluorophore pair in a gelatin methacrylamide-based matrix is presented. Through optimization of monomeric cocktails, it is possible to use extrusion printing to generate structured porous hydrogels which show a measurable and reproducible linear fluorescence response to glucose and fructose up to 100 mm.

Integrated 3D printed heaters for microfluidic applications: Ammonium analysis within environmental water.

A multi-material 3D printed microfluidic reactor with integrated heating is presented, which was applied within a manifold for the colorimetric determination of ammonium in natural waters. Graphene doped polymer was used to provide localised heating when connected to a power source, achieving temperatures of up to 120 °C at 12 V, 0.7 A. An electrically insulating layer of acrylonitrile butadiene styrene (ABS) polymer or a new microdiamond-ABS polymer composite was used as a heater coating. The microdiamond polymer composite provided higher thermal conductivity and uniform heating of the serpentine microreactor which resulted in greater temperature control and accuracy in comparison to pure ABS polymer. The developed heater was then applied and demonstrated using a modified Berthelot reaction for ammonium analysis, in which the microreactor was configured at a predetermined optimised temperature. A 5-fold increase in reaction speed was observed compared to previously reported reaction rates. A simple flow injection analysis set up, comprising the microfluidic heater along with an LED-photodiode based optical detector, was assembled for ammonium analysis. Two river water samples and two blind ammonium standards were analysed and estimated concentrations were compared to concentrations determined using benchtop IC. The highest relative error observed following the analysis of the environmental samples was 11% and for the blind standards was 5%.

Fabrication of Rugged and Reliable Fluidic Chips for Autonomous Environmental Analyzers Using Combined Thermal and Pressure Bonding of Polymethyl Methacrylate Layers.

The fabrication of highly reliable and rugged fluidic chips designed for use in autonomous analyses for nutrient monitoring is described. The chips are based on a two-layer configuration with the fluidic channels produced in one layer using precision micromilling. The second capping layer contains through holes for sample/standard and reagent addition and waste removal post-analysis. Two optically clear polymethyl methacrylate (PMMA) windows are integrated into the opaque PMMA chip, orthogonal to a 22.5 mm-long section of the channel downstream from a serpentine reagent and sample/standard mixing region. An LED source is coupled into the channel through one of the windows, and the light intensity is monitored with a photodiode located at the distal end of the channel outside the second optically clear window. Efficient coupling of the source through the channel to the detector is achieved using custom-designed alignment units produced using 3D printing. In contrast to fluidic chips produced using solvent adhesion, the thermal-/pressure-bonded simplified method presented removes the need for surface treatment. Optimization of the thermal/pressure conditions leads to very strong adhesion between the PMMA layers, requiring forces in the region of 2000 N to separate them, which is necessary for the use in long-term deployments. Profilometry imaging shows minimal evidence of channel distortion after bonding. Finally, we show the potential of these techniques for environmental applications. The fluidic chips were integrated into prototype nutrient analyzers that display no evidence of leakage in extensive lab tests involving 2500 phosphate measurements using the yellow (vanadomolybdophosphoric acid) method. Similarly, excellent analytical performance (LOD is 0.09 µM) is reported for a 28-day field trial comprising 188 in situ autonomous phosphate measurements (564 measurements) in total including calibration.

3D Printing of Metallic Microstructured Mould Using Selective Laser Melting for Injection Moulding of Plastic Microfluidic Devices.

A new method, a 3D printing technique, in particular, selective laser melting (SLM), has been used to fabricate moulds for the injection moulding of thermoplastic microfluidic chips that are suitable for prototyping and early stage scale-up. The micro metallic patterns are printed on to a pre-finished substrate to form a microstructured mould. The dimensional accuracy, surface morphology, bonding strength between the printed patterns and substrate, as well as the microstructure of micro features were all characterized. A microfluidic mould was successfully printed and used directly for injection moulding of cyclic olefin copolymer (COC) microfluidic chips, which were used subsequently to successfully monitor nitrite concentrations in environmental water. The characterization indicated that this new process can be used for fast fabrication of mould tools for injection moulding/hot embossing microfluidic devices. It is faster, more flexible and less expensive than conventional micro-machining processes, although the accuracy and finish are still needed to improve though process optimization and hybrid SLM and machining processes.

Dual Droplet Functionality: Phototaxis and Photopolymerization.

The use of phototaxis to move droplets in liquids offers the opportunity to emulate natural processes such as the controlled transport of materials in fluidic environments and to undertake chemistry at specific locations. We have developed a photoactive organic droplet, whose movement in aqueous solution is driven by a photoinitiator, as a result of a light-induced reaction within the droplet generating a Marangoni flow. The photoinitiator not only drives the droplet motion but can also be used to initiate polymerization following transfer of the droplet to a specific location and its merging with a monomer-containing droplet. The same light is used to control the transport of the droplet and the polymerization. The efficacy of this droplet transport and reactor system has been demonstrated by the site-specific underwater polymerization of N-isopropylacrylamide to repair a leaking vessel and the adhesion of two materials together.

Low cost 235 nm ultra-violet light-emitting diode-based absorbance detector for application in a portable ion chromatography system for nitrite and nitrate monitoring.

A low cost, UV absorbance detector incorporating a 235 nm light emitting diode (LED) for portable ion chromatography has been designed and fabricated to achieve rapid, selective detection of nitrite and nitrate in natural waters. The optical cell was fabricated through micromilling and solvent vapour bonding of two layers of poly (methyl methacrylate) (PMMA). The cell was fitted within a 3D printed housing and the LED and photodiode were aligned using 3D printed holders. Isocratic separation and selective detection of nitrite and nitrate was achieved in under 2.5 min using the 235 nm LED based detector and custom electronics. The design of the new detector assembly allowed for effective and sustained operation of the deep UV LED source at a low current (<10 mA), maintaining consistent and low LED temperatures during operation, eliminating the need for a heat sink. The detector cell was produced at a fraction of the cost of commercial optical cells and demonstrated very low stray light (0.01%). For retention time and peak area repeatability, RSD values ranged from 0.75 to 1.10 % and 3.06-4.19 %, respectively. Broad dynamic linear ranges were obtained for nitrite and nitrate, with limits of detection at ppb levels. The analytical performance of the IC set up with optical cell was compared to that of an ISO-accredited IC through the analysis of five various water samples. Relative errors not exceeding 6.86% were obtained for all samples. The detector was also coupled to a low pressure, low cost syringe pump to assess the potential for use within a portable analytical system. RSD values for retention time and peak area using this simple configuration were <1.15% and <3.57% respectively, highlighting repeatability values comparable to those in which a commercial HPLC pump was used.

Paper based electronic tongue - a low-cost solution for the distinction of sugar type and apple juice brand.

This work reports on a low cost microfluidic electronic tongue (e-tongue) made with carbon interdigitated electrodes, printed on paper, and coated with boronic acid-containing hydrogels. Using capacitance measurements, the e-tongue was capable of distinguishing between different types of sugars (e.g. glucose, fructose and sucrose), in addition to distinguishing between commercial brands of apple juice using a small volume of sample (6 µL). The channels of the microfluidic e-tongue were made using a wax printer, and were modified with hydrogels containing acrylamide copolymerized with 5 or 20 mol% 3-(acrylamido) phenyl boronic acid (Am-PBA), or a crosslinked homopolymeric hydrogel based on N-(2-boronobenzyl)-2-hydroxy-N,N-dimethylethan-1-aminium-3-sulfopropyl acrylate (DMA-PBA). Such hydrogels, containing a phenyl boronic acid (PBA) moiety, can bind saccharides. Combining various hydrogels of this nature in an e-tongue device enabled discrimination between apple juices, which are known to contain higher amounts of fructose compared to glucose or sucrose. Changes in capacitance were captured with impedance spectroscopy in the frequency range from 0.1 to 10 MHz for solutions with varying concentrations of glucose, fructose and sucrose (from 0 to 0.056 g mL-1). The capacitance data were treated with Principal Component Analysis (PCA) and Interactive Document Map (IDMAP), which then correlated overall sugar content from different brands of apple juice. This low-cost, easy-to-use, disposable e-tongue offers great potential in the routine analysis of food and beverages, while offering comparative performance to alternatives in the literature.

Fluorescent Probes for Sugar Detection.

Herein, a new class of polymerizable boronic acid (BA) monomers are presented, which are used to generate soft hydrogels capable of accurate determination of saccharide concentration. By exploiting the interaction of these cationic BAs with an anionic fluorophore, 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (pyranine), a two-component sugar-sensing system was realized. In the presence of such cationic BAs ( o-BA, m-BA, and p-BA), the fluorescence of pyranine becomes quenched because of the formation of a nonfluorescent BA-fluorophore complex. Upon addition of saccharides, formation of a cyclic boronate ester results in dissociation of the nonfluorescent complex and recovery of the pyranine fluorescence. The response of this system was examined in solution with common monosaccharides, such as glucose, fructose, and galactose. Subsequent polymerization of the BA monomers yielded cross-linked hydrogels which showed similar reversible recovery of fluorescence in the presence of glucose.

A wearable patch for continuous monitoring of sweat electrolytes during exertion.

Implementation of wearable sweat sensors for continuous measurement of fluid based biomarkers (including electrolytes, metabolites and proteins) is an attractive alternative to common, yet intrusive and invasive, practices such as urine or blood analysis. Recent years have witnessed several key demonstrations of sweat based electrochemical sensing in wearable formats, however, there are still significant challenges and opportunities in this space for clinical acceptance, and thus mass implementation of these devices. For instance, there are inherent challenges in establishing direct correlations between sweat-based and gold-standard plasma-based biomarker concentrations for clinical decision-making. In addition, the wearable sweat monitoring devices themselves may exacerbate these challenges, as they can significantly alter sweat physiology (example, sweat rate and composition). Reported here is the demonstration of a fully integrated, wireless, wearable and flexible sweat sensing device for non-obtrusive and continuous monitoring of electrolytes during moderate to intense exertion as a metric for hydration status. The focus of this work is twofold: 1- design of a conformable fluidics systems to suit conditions of operation for sweat collection (to minimize sensor lag) with rapid removal of sweat from the sensing site (to minimize effects on sweat physiology). 2- integration of Na+ and K+ ion-selective electrodes (ISEs) with flexible microfluidics and low noise small footprint electronics components to enable wireless, wearable sweat monitoring. While this device is specific to electrolyte analysis during intense perspiration, the lessons in microfluidics and overall system design are likely applicable across a broad range of analytes.

Miniaturized capillary ion chromatograph with UV light-emitting diode based indirect absorbance detection for anion analysis in potable and environmental waters.

A miniaturized, flexible, and low-cost capillary ion chromatography system has been developed for anion analysis in water. The ion chromatography has an open platform, modular design, and allows for ease of modification. The assembled platform weighs ca. 0.6 kg and is 25 × 25 cm in size. Isocratic separation of common anions (F- , Cl- , NO2- , Br- , and NO3- ) could be achieved in under 15 min using sodium benzoate eluent at a flow rate of 3 µL/min, a packed capillary column (0.150 × 150 mm) containing Waters IC-Pak 10 µm anion exchange resin, and light-emitting diode based indirect UV detection. Several low UV light-emitting diodes were assessed in terms of sensitivity, including a new 235 nm light-emitting diode, however, the highest sensitivity was demonstrated using a 255 nm light-emitting diode. Linear calibration ranges applicable to typical natural water analysis were obtained. For retention time and peak area repeatability, relative standard deviation values ranged from 0.60-0.95 and 1.95-3.53%, respectively. Several water samples were analysed and accuracy (recovery) was demonstrated through analysis of a prepared mixed anion standard. Relative errors of -0.36, -1.25, -0.80, and -0.76% were obtained for fluoride, chloride, nitrite, and nitrate, respectively.

Moving Droplets in 3D Using Light.

The emulation of the complex cellular and bacterial vesicles used to transport materials through fluids has the potential to add revolutionary capabilities to fluidic platforms. Although a number of artificial motile vesicles or microdroplets have been demonstrated previously, control over their movement in liquid in 3D has not been achieved. Here it is shown that by adding a chemical "fuel," a photoactive material, to the droplet, it can be moved in any direction (3D) in water using simple light sources without the need for additives in the water. The droplets can be made up of a range of solvents and move with speeds as high as 10.4 mm s-1 toward or away from the irradiation source as a result of a light-induced isothermal change in interfacial tension (Marangoni flow). It is further demonstrated that more complex functions can be accomplished by merging a photoactive droplet with a droplet carrying a "cargo" and moving the new larger droplet to a "reactor" droplet where the cargo undergoes a chemical reaction. The control and versatility of this light-activated, motile droplet system will open up new possibilities for fluidic chemical transport and applications.

Micro-Capillary Coatings Based on Spiropyran Polymeric Brushes for Metal Ion Binding, Detection, and Release in Continuous Flow.

Micro-capillaries, capable of light-regulated binding and qualitative detection of divalent metal ions in continuous flow, have been realised through functionalisation with spiropyran photochromic brush-type coatings. Upon irradiation with UV light, the coating switches from the passive non-binding spiropyran form to the active merocyanine form, which binds different divalent metal ions (Zn2+, Co2+, Cu2+, Ni2+, Cd2+), as they pass through the micro-capillary. Furthermore, the merocyanine visible absorbance spectrum changes upon metal ion binding, enabling the ion uptake to be detected optically. Irradiation with white light causes reversion of the merocyanine to the passive spiropyran form, with simultaneous release of the bound metal ion from the micro-capillary coating.

Photoswitchable Layer-by-Layer Coatings Based on Photochromic Polynorbornenes Bearing Spiropyran Side Groups.

Herein, we present the synthesis of linear photochromic norbornene polymers bearing spiropyran side groups (poly(SP-R)) and their assembly into layer-by-layer (LbL) films on glass substrates when converted to poly(MC-R) under UV irradiation. The LbL films were composed of bilayers of poly(allylamine hydrochloride) (PAH) and poly(MC-R), forming (PAH/poly(MC-R)) n coatings. The merocyanine (MC) form presents a significant absorption band in the visible spectral region, which allowed tracking of the LbL deposition process by UV-vis spectroscopy, which showed a linear increase of the characteristic MC absorbance band with increasing number of bilayers. The thickness and morphology of the (PAH/poly(MC-R)) n films were characterized by ellipsometry and scanning electron microscopy, respectively, with a height of ∼27.5 nm for the first bilayer and an overall height of ∼165 nm for the (PAH/poly(MC-R))5 multilayer film. Prolonged white light irradiation (22 h) resulted in a gradual decrease of the MC band by 90.4 ± 2.9% relative to the baseline, indicating the potential application of these films as coatings for photocontrolled delivery systems.