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In this work, we utilise the disulphide bond structure of insulin and a new benzothiazole Raman probe for the detection of human insulin using surface-enhanced Raman spectroscopy (SERS). The disulphide bond structure of the insulin was reduced to generate free sulfhydryl terminal groups. When reacted with benzothiazole-functionalised gold nanoparticles, the reduced protein desorbs the Raman probe and causes its Raman signal intensity to quench. Using this approach, insulin was quantified in the concentration range of 1 × 10-14 -1 × 10-8 M by SERS quenching. The limit of quantification of insulin by the SERS quenching method was found to be 1 × 10-14 M (0.01 pM or 58 pg/L), which satisfies the requirements for monitoring its blood concentration in patients. Because many proteins and peptides have disulphide bonds in their molecular structures, the new SERS quenching method has a strong potential for the rapid determination of ultralow concentrations of proteins in formulations and biological fluids.

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is a serious threat to human health. Current methods such as reverse transcription polymerase chain reaction (qRT-PCR) are complex, expensive, and time-consuming. Rapid, and simple screening methods for the detection of SARS-CoV-2 are critically required to fight the current pandemic. In this work we present a proof of concept for, a simple optical sensing method for the screening of SARS-CoV-2 through its spike protein subunit S1. The method utilizes a target-specific extractor chip to bind the protein from the biological specimens. The disulfide bonds of the protein are then reduced into a biothiol with sulfhydryl (SH) groups that react with a blue-colored benzothiazole azo dye-Hg complex (BAN-Hg) and causes the spontaneous change of its blue color to pink which is observable by the naked eye. A linear relationship between the intensity of the pink color and the logarithm of reduced S1 protein concentration was found within the working range 130 ng.mL

Despite well documented studies on metal pollutants in aquatic ecosystems, knowledge on the combined effects of catchment characteristics, sediment properties, and emerging pollutants, such as microplastics (MPs) on the presence of metals in urban river sediments is still limited. In this study, the synergistic influence of MPs type and hazard indices, catchment characteristics and sediment properties on the variability of metals present in sediments was investigated based on a typical urban river, Brisbane River, Australia. It was noted that the mean concentrations of metals in Brisbane River decreases in the order of Al (94,142 ± 12,194 μg/g)Fe (62,970 ± 8104 μg/g)Mn (746 ± 258 μg/g)Zn (196 ± 29 μg/g)Cu (50 ± 19 μg/g)Pb (47 ± 25 μg/g)Ni (25 ± 3 μg/g) while the variability of metals decreases in the order of PbCuMnAlNiZnFe along the river. According to enrichment factor (Ef) contamination categories, Mn, Cu and Zn exert a moderate level of contamination (Ef2), while Fe, Ni, and Zn show slight sediment pollution (1Ef2). In the case of Pb, extremely high enrichment (Ef3) was found at sampling locations having a high urbanisation level and traffic related activities. Crustal metal elements (namely, Al, Fe, Mn) were found to be statistically significantly correlated with sediment properties (P0.05). Anthropogenic source metals (namely, Cu, Ni, Pb, Zn) were observed to be highly correlated with catchment characteristics. Additionally, the presence of metals in sediments were positively correlated with MPs concentration, and negatively correlated with MPs hazard indices. The outcomes of this study provide new insights for understanding the relationships among metals and various influential factors in the context of urban river sediment pollution, which will benefit the formulation of risk assessment and regulatory measures for protecting urban waterways.

2D black phosphorus (BP) is one promising electrocatalyst toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalysis. The too strong adsorption of oxygen intermediates during OER, while the too weak adsorption of hydrogen intermediate during HER, however, greatly compromise its practical water splitting applications with overpotentials as high as 450 mV for OER and 420 mV for HER to achieve 10 mA cm-2 under alkaline conditions. Herein, by rationally introducing the nanosized iridium (Ir) modifier together with optimized exposing surface toward electrolytes, an efficient Ir-modified BP electrocatalyst with much favorable adsorption energies toward catalytic intermediates possesses an outstanding pH-universal water splitting performance, surpassing the nearly all reported BP-based catalysts and the commercial noble-metal catalysts. The Ir-modified BP catalyst with the optimized exposed surfaces only requires an overall cell voltage of 1.54 and 1.57 V to achieve 10 mA cm-2 in acidic and alkaline electrolysers, respectively. This design uncovers the potential applications of 2D BP in practical electrocatalysis fields via decreasing reaction intermediate adsorption energy barriers and promoting the interfacial electron coupling for heterostructured catalysts, and offers new insights into the surface-dependent activity enhancement mechanism.

In recent years, conducting polymers are playing a significant role in the field of display devices, transistors, solar cells, sensors, and electrochromic windows due to their outstanding optoelectronic and semiconducting properties due to their conjugated backbone. One potential application that is not as widely explored using these materials is biosensing, where advantage is taken of the porosity that can be generated by the polymerization of a three-dimensional network. There are various approaches for producing conjugated microporous polymers using trifunctional or multifunctional monomers synthesized via chemical or electrochemical methods. In this work, we have used electropolymerization to synthesize conjugated polymer films on a working electrode of flexible indium tin oxide (FITO) using a trifunctional conjugated monomer 1,3,5-tri(furan-2-yl)benzene (TFB). There are several parameters that influence the formation of a porous polymer film, and the most critical ones are substrate conductivity, roughness, method of electropolymerization, and choice of an electrolyte. These porous electropolymerized films were characterized using UV–vis spectroscopy (UV–vis), X-ray photoelectron spectroscopy (XPS), surface profilometry, four-point probe conductivity measurements, and scanning electron microscopy (SEM). The polymer films that were electropolymerized using chronoamperometry rather than repetitive potential cycling demonstrated a more suitable morphology to trap DNA/RNA analytes for biosensing applications.

Metal pollution of stormwater runoff can cause potential toxic impacts on the receiving water environment and human health. Effective pollution mitigation requires accurate stormwater quality modeling. Even though a significant knowledge base exists on the factors influencing metal build-up on urban roads, very limited studies have investigated how metal-particulate interaction influences metal build-up. This study quantitatively assessed the influence of particulate characteristics, together with vehicular traffic and land use, on the build-up of Zn, Cu, Pb, Cr, Ni and Cd on urban roads. The study outcomes revealed that the variability in metal build-up is highly influenced by the variability associated with metal adsorption to particulates. The percentage contribution from particulate properties influencing metal adsorption in the case of150 μm size road dust particles was found to be higher (Zn 44%, Cu 52%, Cr 16%, Ni 27% and Cd 45%) when compared to traffic and land use characteristics (Zn 21%, Cu 13%, Cr and Ni10% and Cd 34%). Similar adsorption behavior was noted for metals associated with150 μm size road dust particles. Among different particulate properties influencing metal adsorption, effective cation exchange capacity showed a strong positive relationship with the build-up of Cd compared to other metals, highlighting the potential role of Cd in stormwater quality as a readily available metal. The build-up of metals such as Cr and Ni are highly influenced by metal oxides of Al, Fe and Mn and clay forming minerals, indicating that Cr and Ni are relatively stable in nature.

The provision of water to meet the needs of an ever increasing urban population is a significant challenge. This is because urban receiving waters are constantly at risk from pollutant inputs via stormwater runoff and wastewater discharge. This research study employed multiple approaches including principal component analysis, Bayesian Networks (BNs) modelling and geospatial analysis to identify patterns in the distributions of nutrients and metals in water and sediments in an urban river and the interactions between the two phases. In both, water and sediments, nutrient concentrations/loads varied in the order of total carbon (TC) total nitrogen (TN) total phosphorus (TP). The river sediments were found to contain the highest crustal metal loads, while in water, the marine-related metals had the highest concentrations. The BNs modelling of pollutant interactions between water and sediment phases indicated that nitrogen is more likely to be transferred from water to sediment than the opposite, while anthropogenic metals are more likely to be transferred from sediments to water. Further, geospatial analysis showed that TN, crustal metals and anthropogenic metal loads in sediments increased from upstream to downstream, while having a decreasing pattern in water. However, marine-related metals in both, water and sediments had increasing concentrations/loads from upstream to downstream. These spatial patterns are attributed to the interactions between water and sediment phases, sediment transport along the river and seawater intrusion in the estuarine area. The study outcomes are expected to contribute to enhancing the knowledge required for developing mitigation strategies to improve urban receiving water quality.

Two-dimensional (2D) bismuth oxide (Bi2O3) heterostructured nanosheets (BOHNs) were first fabricated by a solution-based molecular self-assembly approach. The synthesized BOHNs nanosheets feature mixed α- and β-phases and rich surface/edge-active sites. When utilized as anode materials for rechargeable batteries, dual-phase BOHNs deliver an initial discharge capacity as high as 647.6 mAh g-1 and an increased capacity of over 200 mAh g-1 remained after 260 cycles for lithium-ion batteries (LIBs), and a stable cycling capacity at ∼50 mAh g-1 after 500 cycles for sodium-ion batteries (SIBs). A novel flexible 2D/1D/2D structure is further developed by implanting 2D BOHNs into conductive 1D carbon nanotubes and 2D graphene to form composite (BOHNCG) paper as free-standing anodes for both LIBs and SIBs. The capacity of 2D/1D/2D BOHNCG as a LIB anode reaches 823.5 mAh g-1, corresponding to an enhancement of ∼27%, and remains at >110 mAh g-1 after 80 cycles as a SIB anode with greatly improved cycling stability. This work verifies the promising potential of 2D BOHNs for practical energy-related devices and enriches the current research on emerging 2D nanomaterials.

Product selectivity of alkyne hydroamination over catalytic Au2Co alloy nanoparticles (NPs) can be made switchable by a light-on/light-off process, yielding imine (cross-coupling product of aniline and alkyne) under visible-light irradiation, but 1,4-diphenylbutadiyne in the dark. The low-flux light irradiation concentrates aniline on the catalyst, accelerating the catalytic cross-coupling by several orders of magnitude even at a very low overall aniline concentrations (1.0×10−3 mol L−1). A tentative mechanism is that Au2Co NPs absorb light, generating an intense fringing electromagnetic field and hot electrons. The sharp field-gradient (plasmonic optical force) can selectively enhance adsorption of light-polarizable aniline molecules on the catalyst. The light irradiation thereby alters the aniline/alkyne ratio at the NPs surface, switching product selectivity. This represents a new paradigm to modify a catalysis process by light.

Cobalt oxide nanostructures have been considered as promising electrode materials for various electrochemical applications, especially for batteries, supercapacitors, and electrocatalysis, owing to their unparalleled advantages of high theoretical capacity, highly-active catalytic properties, and outstanding thermal/chemical stability. If hybridized with property-complementary nanomaterials, such as nanocarbon, CNTs, graphene, metal oxides/sulfides and conductive polymers, their electrochemical properties can be further enhanced in terms of specific reversible capacity/capacitance, rate capability, cycling stability, and catalytic activity. In this review, we first give a comprehensive overview on recent progress in both monolithic cobalt oxide nanostructures and their hybrid nanomaterials for batteries, supercapacitors, and electrocatalysis applications. Then, structure-property relationships of the cobalt oxide-based nanomaterials and current challenges in both nanoarchitectures design and their applications in electrochemical energy devices are proposed, and an outlook on future research of this family of materials in electrochemical energy applications are brought forward. This understanding on the relationships of synthesis-nano/microstructure-property-performance of cobalt oxide-based nanomaterials is expected to lay a good foundation for pushing this promising class of materials to the practical application in energy conversion and storage devices and to provide a good reference for the readers in the fields of materials, chemistry, sustainable energy, and nanotechnology.

In this work, we demonstrate the fabrication of disposable and field deployable nanostructured conductive substrates for dual detection by Surface Enhanced Raman Scattering (SERS) and electrochemistry. Using a one-step potentiostatic process, gold nanostructures were electrodeposited on three substrates: bare indium tin oxide (ITO) electrode, ITO coated with plane gold and carbon fibre (CF) covered with ZnO nanowires (ZnO NWs). Their sensitivities were enhanced by incorporating the plane gold layer and ZnO NWs. The intensity of SERS signals produced on the nanostructured ITO substrates with 0.1 μM quinolinethiol were of the order: nanostructured gold-coated ITO > nanostructured bare ITO. The higher SERS signal on the nanostructured gold-coated ITO was attributed to the coupling between the surface plasmon polariton provided by the gold under layer and the surface plasmon resonance of the Au nanostructures. The ZnO NWs on the carbon fibre provided additional surface area for electrodeposition of gold nanostructures at high density. This led to multiple hotspots formation yielding high SERS signal intensity relative to that on a nanostructured bare carbon fibre. The nanostructured substrates, demonstrated good SERS signal reproducibility with relative standard deviation of 5.19%, 3.28% and 4.53% for Au/ITO, Au/Au-ITO and Au/ZnO-CF respectively. To demonstrate the potential application of these substrates and estimate their sensitivities, they were used to detect melamine by SERS at 1 pM (for Au nanostructures on bare ITO), 1 fM (for Au nanostructured gold-coated ITO), and 0.1 nM (for Au nanostructures on ZnO NWs-coated CF) concentrations with LOD of 0.118 pM, 0.189 fM and 57.4 pM respectively. Taking advantage of the conductive properties of gold nanostructured ITOs, electrochemical detection of 0.1 μM melamine (with an LOD of 0.05 μM) was also demonstrated. Hence, these substrates are potentially useful for SERS and electrochemical-based detection of organic toxicants.

A novel 2D-TiO2-2D van der Waals (vdW) heterostructured (BPNs@TiO2@G) hydrogel is developed as a high-performance anode material for lithium ion batteries by coating black phosphorus nanosheets (BPNs) onto porous graphene/TiO2 composite hydrogel (TiO2@G). This unique 2D-TiO2-2D vdW heterostructure not only prevents close restack between 2D nanosheets, but also provides rapid interlayer transfer paths and enhanced interfacial storage, together with some inherited advantages from 2D BPNs and graphene, such as shortened diffusion pathways, improved conductivity, supressed volume changes and lithium dendrite growth over cycling. As a result, BPNs@TiO2@G anode delivers an attractive initial discharge capacity as high as 1336.1 mAh g−1 (at 0.2 A g−1), a superior rate capability (271.1 mAh g−1 at 5.0 A g−1), and a good cycling life (502 mAh g−1 for 180 cycles) under a potential window close to 3.0 V. This study thus opens a new window for designing novel high-performance electrodes for electrochemical energy storage devices.

In order to investigate the transfer and accumulation pathways of heavy metals in cropland ecosystems, an investigation of the geochemical behaviors of heavy metals in soil and rice plants was carried out in the Yangtze River Delta. Soil is one of the biggest reservoirs of heavy metals and affects food safety at the beginning of the food chain. The results of this study demonstrate that heavy metal levels in soil decreased with increasing soil pH, while rice shoots accumulated heavy metals more readily under low soil pH conditions. The non-carcinogenic hazard quotients (HQ) of heavy metals show that health risks for humans were primarily due to Pb and As. Furthermore, cancer risk (Risk) results suggested that ~76% and ~15.7% of cancer risk was caused by Cd and As levels, respectively. Decreasing soil pH enhanced the non-carcinogenic and carcinogenic health risks for the human body. Through exponential change between transfer factor (TFgrain/soil) and soil metals, HQ, a direct monitoring method for rice plants, was built using regression curves. It is proposed that besides condition of soil with high heavy metal concentration, for rice grown with surface soil metals, the safety of the rice product should be monitored when soil metals are under the following levels after harvest: non-carcinogenic risk, As

The fate of metals in stormwater is primarily influenced by the transformation processes that they undergo during build-up on impervious surfaces. These processes result in changes to the bioavaila...

Due to its high analytical sensitivity and field deplorability, surface enhanced Raman spectroscopy (SERS) has emerged as an analytical tool for detecting environmental toxicants in different matrices. Progress has been made towards development of methods for depositing nanostructures onto solid platforms to design SERS substrates. The properties of the solid platforms used for SERS substrates fabrications such as electrical and heat conductivity, malleability and foldability, have significant influence on then design of the nanostructures and are critical for SERS technique. This review takes a look at recent advances in commonly employed conductive solid materials such as indium tin oxide, carbon fiber, silicon wafers, polyaniline fiber and carbon nanotubes as the supporting platforms for fabricating SERS substrates. It also examines their influence on the fabrication method, the morphology of the nanostructures formed as well as the hot spot density on the resultant novel SERS substrates. Real world applications of these substrates for the detection of environmental toxicants over the past decade have been shown. The review indicates that while significant advances have been made on the use of the conductive properties of these support platforms for SERS substrate fabrication, their subsequent application to detect environmental toxicants have not been fully explored.

A functional palygorskite-supported Fe/Ni (Pal-Fe/Ni) nanocomposite material is synthesised to remove 2,4-dichlorophenol (2,4-DCP) in an aqueous solution. The hypothesis is that Pal-Fe/Ni has superior efficacy than other Fe materials, such as Pal-Fe and Fe/Ni with regard to 2,4-DCP removal even though it requires less loading amount of metallic influencing the reaction. The surface morphology and surface chemical environments of Pal-Fe/Ni are studied using SEM, TEM, XRD and XPS characterisation methods. As revealed from batch experiments, initial pH, sample amount and reaction time are the key parameters influencing the 2,4-DCP removal efficiency. A further experiment reveals that iron leaching plays a main role for 2,4-DCP removal. Kinetic study reveals that removal of 2,4-DCP can be described by pseudo first-order model. A synergistic adsorption and catalytic reduction mechanism for the removal of 2,4-DCP by Pal-Fe/Ni is studied using UV–Vis, total organic carbon and HPLC-MS analyses. The results reveal complete dechlorination and 2,4-DCP degradation together with high total organic carbon removal. This study on immobilising Fe/Ni bimetallic nanoparticles onto palygorskite creates a new prospect for the practical application of Pal-Fe/Ni nanocomposite in remediation of contaminated aqueous solutions.

Influence of land use and population characteristics on solid-liquid partitioning of heavy metals in aquatic ecosystems is little understood. This study hypothesised that the partitioning of heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) between water and sediments is influenced by different land use classes, their configuration patterns including patch density, Shannon's diversity index, largest patch index, and splitting index and population density. Relationships between variables were investigated from different distances to the stream network (sub-catchment and riparian scales) and considering land use patterns within individual land use classes and individual sub-catchments as a whole (class and landscape levels, respectively). The study outcomes confirmed that the influence of land use and configuration on metals partitioning is scale independent. However, population density increases metal bioavailability at the riparian scale compared to the sub-catchment scale. Agricultural lands discharge the highest fractions of dissolved metals at both spatial scales (eigenvectors = 0.409 – sub-catchment, and −0.533 – riparian, whilst metals have opposite loadings). Positive relationships between splitting index and metal partitioning confirmed that the division of anthropogenic land uses into smaller patches reduces water pollution. However, high fragmentation of forested areas increases the fraction of soluble metals. Further, high patch density and patch diversity are beneficial for controlling the solubility of some metals. Configuration metrics at the landscape level fundamentally reproduce the patterns of the largest land use type and are not effective for assessing metal partitioning. Therefore, analyses at the class level are preferred. This research investigation contributes essential knowledge to improve land use management strategies and, thereby, help safeguard urban waterways.

Cardiac troponin I (cTnI) is a sensitive biomarker for cardiovascular disease (CVD). Rapid determination of cTnI concentration in blood can greatly reduce the potential of significant heart damage and heart failure. Herein, we demonstrate a new electrochemical immunosensor for selective affinity binding and rapid detection of cTnI in blood plasma by an electrochemical method. A conductive film of “poly 2,5-bis(2-thienyl)3,4-diamine-terthiophene (PDATT)” was deposited onto an Indium Tin Oxide (ITO) electrode using chronoamperometry. Anti-cardiac troponin I antibody was then attached to the two amine (NH2) groups substituted on the central thiophene of terthiophene repeating unit of the polymer chain via amide bond formation. The gaps on the surface of the antibody coated immunosensor were backfilled with bovine serum albumin (BSA) to prevent nonspecific binding of interfering molecules. Differential pulse voltammetry (DPV) was used to determine cTnI upon the formation of cTnI immunocomplex on the sensing surface, appearing a peak at 0.27 V. The response range was 0.01–100 ng mL−1 with limit of quantification down to 0.01 ng mL−1. The developed immunosensor was used to determine cTnI in spiked blood plasma without interference from cardiac troponin T (cTnT). Therefore, this new sensor can be utilised for the detection of cTnI biomarker in pathological laboratories and points of care in less than 15 min.

Limited knowledge of the combined effects of water and sediment properties and metal ionic characteristics on the solid-liquid partitioning of heavy metals constrains the effective management of urban waterways. This study investigated the synergistic influence of key water, sediment and ionic properties on the adsorption-desorption behavior of weakly-bound heavy metals. Field study results indicated that clay minerals are unlikely to adsorb heavy metals in the weakly-bound fraction of sediments (e.g., r = −0.37, kaolinite vs. Cd), whilst dissociation of metal-phosphates can increase metal solubility (e.g., r = 0.61, dissolved phosphorus vs. Zn). High salinity favors solubility of weakly-bound metals due to cation exchange (e.g., r = 0.60, conductivity vs. Cr). Dissolved organic matter does not favor metal solubility (e.g., r = −0.002, DOC vs. Pb) due to salt-induced flocculation. Laboratory study revealed that water pH and salinity dictate metal partitioning due to ionic properties of Ca2+ and H+. Selectivity for particulate phase increased in the order Cu>Pb>Ni>Zn, generally following the softness (2.89, 3.58, 2.82, 2.34, respectively) of the metal ions. Desorption followed the order Ni>Zn>Pb>Cu, which was attributed to decreased hydrolysis constant (pK1 = 9.4, 9.6, 7.8, 7.5, respectively). The study outcomes provide fundamental knowledge for understanding the mobility and potential ecotoxicological impacts of heavy metals in aquatic ecosystems.

Rivers are viewed as major pathways of microplastic transport from terrestrial areas to marine ecosystems. However, there is paucity of knowledge on the dispersal pattern and transport of microplastics in river sediments. In this study, a three dimensional hydrodynamic and particle transport modelling framework was created to investigate the dispersal and transport processes of microplastic particles commonly present in the environment, namely, polyethylene (PE), polypropylene (PP), polyamide (PA), and polyethylene terephthalate (PET) in river sediments. The study outcomes confirmed that sedimental microplastics with lower density would have higher mobility. PE and PP are likely to be transported for a relatively longer distance, while PA and PET would likely accumulate close to source points. High water flow would transport more microplastics from source points, and high flow velocity in bottom water layer are suggested to facilitate the transport of sedimental microplastics. Considering the limited dispersal and transport, the study outcomes indicated that river sediments would act as a sink for microplastic pollutants instead of being a transport pathway. The patchiness associated with the hotspots of different plastic types is expected to provide valuable information for microplastic source tracking.

Bioavailability is a critical facet of metal toxicity. Although past studies have investigated the individual role of sediment physico-chemical properties in relation to the bioavailability of heavy metals, their collective effects are little-known. Further, limited knowledge exists on the contribution of nutrients to metal bioavailability. In this study, the influence of physico-chemical properties of sediments, including total organic carbon (TOC), total phosphorus (TP), total nitrogen (TN), cation exchange capacity (CEC), specific surface area (SSA), and mineralogical composition to metal bioavailability is reported. The weak-acid extraction method was used to measure Cd, Cr, Cu, Ni, Pb and Zn as the potentially bioavailable fraction in sediments in an urban creek. The results confirmed that Cu has strong selectivity for organic matter (r = 0.814, p

Recombinant human erythropoietin (rHuEPO) is an important hormone drug that is used to treat several medical conditions. It is also frequently abused by athletes as a performance enhancing agent at sporting events. The time window of the rHuEPO in blood is short. Therefore, the rapid detection of rHuEPO use/abuse at points of care and in sports requires a selective analytical method and a sensitive sensor. Herein, we present a highly selective method for the rapid detection of rHuEPO in human blood plasma by a sensitive optical sensor. rHuEPO is selectively extracted from human blood plasma by a target-specific extractor chip and converted into a biothiol by reducing its disulfide bond structure. The formed biothiol reacts with a water soluble (E)-1-((6-methoxybenzo[d]thiazole-2-yl)diazenyl)naphthalene-2,6-diolHg(ii) (BAN-Hg) optical sensor and causes its rapid decomposition. This leads to a rapid change in the sensor color from blue to pink that can be observed by the naked eye. The optical sensor was used to quantify rHuEPO in the concentration range 1 × 10-8 M to 1 × 10-12 M by UV-Vis spectroscopy. For the screening of blood plasma, an EPO-specific extractor chip was synthesized and used to selectively extract the protein from the biological matrix prior to its conversion into biothiol and quantification by the optical sensor. Since many proteins have a disulfide bond structure, the new method has strong potential for their rapid sensitive and selective detection by the BAN-Hg sensor and UV-Vis spectroscopy.

Diketopyrrolopyrrole (DPP) is one of the most fascinating organic dyes, and has gained significant attention in the organic electronic community in recent times. Due to their outstanding semiconducting properties, DPP-based small molecules and polymers can be used as active semiconductor thin films for various high performance electronic devices. However, although several flanking groups attached to the DPP backbone have been reported in the literature for DPP molecules, there is little study about the effect of fused rings flanked on both sides of the DPP core. Recently our group reported for the first time a naphthalene-flanked DPP as a new DPP family member. In this work, we have performed electropolymerization studies on a newly synthesized naphthalene flanked DPP core with two alkyl chains, hexyl (H-DPPN) and octyl (O-DPPN), as conjugated monomers. Electrochemical studies have been carried out on glassy carbon (GC) and indium tin oxide (ITO) electrodes by using repetitive cyclic voltammetry (CV) as the deposition technique for up to 50 cycles. The concentration of H-DPPN and O-DPPN solution in dichloromethane was found to be a key parameter when optimizing conditions for obtaining an electropolymerised thin film, although other parameters such as the electrolyte, potential range, number of cycles, and the nature of the electrode all play a role in successful thin film formation. The electropolymerized thin films were characterised using UV-Vis spectroscopy, atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photon spectroscopy (XPS) and surface profilometry. We found that each monomer produced different film morphologies on glassy carbon and ITO electrodes. We believe that electropolymerized poly(H-DPPN) and poly(O-DPPN) thin film electrodes could be used for various applications such as studying redox reactions and bio-sensing.

Heteroatom-doping engineering has been verified as an effective strategy to tailor the electronic and chemical properties of materials. The high amount doping of nonmetal atoms to achieve desired performance, however, is always a grand challenge. Herein, a new strategy to achieve ultrahigh-level doping of phosphorus in a 3D graphene skeleton is proposed by sacrificing heterostructured two-dimensional black phosphorus on graphene. Via this approach, the phosphorus-loading in graphene hydrogel reached a record of 4.84 at. %, together with the formation of tunable pores of size 1.7–17.5 nm in graphene. During reaction kinetic analysis, the highly phosphorus-doped 3D graphene hydrogel anode exhibited more favorable capacitive-controlled ion storage behaviors, leading to a specific capacity as high as 1000 mA h g–1 after 1700 cycles, which is superior to the pristine graphene hydrogel electrode. This simple but effective phosphorization offers an effective doping strategy for producing ultrahigh-level phosphorous doping but avoids the usual use of toxic phosphorous precursors. Furthermore, the modulation on the activation process over cycling investigated in this work gives us a new insight into designing stable anodes for carbonaceous electrode materials.

Rivers are regarded as sinks and pathways of plastic pollutants from terrestrial environments to various other aquatic systems such as lakes and oceans. Although extensive research has been conducted in recent years on microplastic pollution in river sediments, knowledge on the relationships between potential influential factors such as catchment characteristics and sediment properties, and microplastics occurrence in river sediments, is still considered an under-researched area. This study evaluated the influence of land use, population, and sediment particle size on the presence of microplastics abundance and types. Based on a Bayesian Network modelling approach to characterise the correlations between influencing factors and microplastics occurrence, it was evident that microplastics type had a positive correlation with different land use types and population. Catchment characteristics were found to play a more important role in influencing microplastics type than microplastics concentration. A statistically significant positive relationship was observed between microplastics concentration and clay particles which suggested that the occurrence of microplastics in sediments can be impacted by the presence of clay particles.

Road dust is a key repository for PAHs and transformed PAH products (TPPs) generated from natural and anthropogenic sources in the urban environment. Eventhough PAHs and TPPs are prone to post-emission photochemical processes, very limited studies exist on the subject for road dust. This knowledge gap is of particular concern since some of the resultant TPPs are notably more carcinogenic than their precursor PAHs. This study evaluated the role of 254 nm ultraviolet (UV) photons on the photochemistry of PAHs and TPPs in road dust. The findings show that UV irradiation had varying effects on the fate of analytes, particularly naphthalene (NAP), phenanthrene (PHE), 7, 12-dimethylbenz(a)anthracene (DMBA), 1-hydroxypyrene (HPY), 1-nitropyrene (1NPY), pyrene (PYR) and 5-nitroacenaphthene (5NAC). Photochemical relationship was identified between PYR, 1NPY and HPY, and DMBA and benzo(a)anthracene. Unlike carbonyl-PAHs, parent PAHs, nitro-PAHs and hydroxy-PAHs can originate from photolysis. Photon irradiation durations of 3, 6 and 7.5 h had the most intense influence on the photolytic process with 7.5 h as optimum. The photochemical rate at optimum irradiation duration shows an increasing trend of NAP PHE1NPY DMBA5NAC HPY with respective estimates of 0.08, 0.11, 0.21, 0.22, 0.43, and 0.59 mg kg

Heteroatom doped-graphene is a potential candidate as an anode material in sodium-ion batteries (SIBs). However, one of the major issues holding back its development is that a complete understanding of the doping effects accounting for the Na-ion storage of heteroatom-doped graphene has remained elusive. In this work, first principles calculations have been conducted to systematically investigate the electronic and geometric effects in various heteroatom-doped graphene. Graphene doping with pyridinic-N, pyrrolic-N, F and B improves the electrochemical Na storage due to the electronic effect which originates from electron deficient sites (i.e. defects or electron deficient atoms). On the other hand, P doping improves the Na storage ability of graphene due to the geometric effect caused by bond length mismatch. In contrast, the introduction of graphitic-N and S into graphene is inefficient for Na storage because of their inability to accept electrons from Na. Interestingly, the diffusion energy barriers obtained for Na on doped graphene are lower than that for the pristine graphene. Furthermore, co-doping strategy is predicted to achieve even better Na storage capacity due to the synergistic effect.

Particle build-up is a key stormwater pollutant process that is typically replicated using a power function with increasing antecedent dry days. Though the use of a power function is recommended by a range of researchers, its applicability is demonstrated primarily for residential roads. Particle build-up process is also subjected to significant variability due to catchment heterogeneity and variability associated with source characteristics such as traffic and land use. Variability in the build-up process and use of stereotypical coefficients can lead to significant model uncertainty. This study evaluates particle build-up characteristics on urban road surfaces using an extensive field investigation program, giving specific priority to industrial and commercial roads. Based on the outcomes, particle build-up process characteristics and respective uncertainties were evaluated and compared for road surfaces in residential, industrial and commercial areas. The study primarily found that both, industrial and commercial land uses generally manifested greater particle build-up loads compared to residential land uses. The study provides estimates for build-up coefficients for a range of land uses, including industrial and commercial with their potential uncertainties in build-up predictions. This provides new knowledge to improve stormwater quality modelling. Aside from land use, the proximity of sites to major road networks was also identified as a critical factor influencing the variability and uncertainty in particle build-up. Variability of the fraction of particles in the

Graphene hydrogel (GH) has attracted increasing attention in energy storage and conversion, pollutant adsorption, catalysis, sensors and tissue engineering applications. However, a good understanding of the structure-property relationship is essential to precisely tune their properties. In this work, a pH assisted hydrothermal process was used to synthesize reduced graphene oxide (rGO) hydrogels with different three-dimensional (3D) porous structures. We systematically investigated the structure-property relationships in the GH, with a focus on the effects of geometrical dimensions of the pore structure. We found that the best mechanical properties were achieved in a compact microstructure consisting of small pores but thick walls. Despite having a lower C/O ratio, the compact structure gave rise to the highest electrical conductivity, attributed to the highly interconnected 3D porous structure providing conductive pathways. On the other hand, the hydrogels prepared under basic conditions exhibited higher C/O ratio but lower mechanical and electrical properties due to the disordered pore structure with large pores and thin walls.

Metals deposited on urban road surfaces and incorporated in stormwater runoff are discharged into receiving waters, influencing their quality and can pose human health risks. Effective design of stormwater treatment measures is closely dependent on the in-depth understanding of stormwater pollutant sources and the associated health risks. The study discussed in this paper has linked the sources of metals in stormwater runoff and the accompanying human health risk to rainfall characteristics. The study outcomes confirmed that the metal contributions to stormwater runoff from the primary sources were in the order of sea salt > soil > traffic. Although traffic contributes a relatively lower percentage to wash-off, the human health risks posed by traffic sourced metals were relatively much higher. This implies that traffic sources should receive particular attention in treating stormwater. These outcomes have the potential to contribute to enhancing effective source control measures in order to safeguard natural waterways from polluted road wash-off.

The adsorption behaviour of metals deposited on road surfaces undergo changes during dry weather periods, with the bioavailability varying compared to the original species, prior to incorporation in stormwater runoff. This study investigated the role of antecedent dry days on the transformation characteristics of Zn, Cu, Pb and Cd attached to different geochemical forms of road dust, in order to predict potential stormwater quality impacts. The study outcomes showed that the exchangeable fraction generally decreased with the increase in antecedent dry days, but the reducible, oxidisable and residual fractions increased. This implies that there is a time-dependent transformation of weakly bound metals in road dust to more persistent chemical forms. The transformation rate of metals was found to be in the order of Pb > Cu > Zn > Cd. Significant changes in metal distribution among the geochemical fractions were observed up to seven dry days, suggesting that during the initial antecedent dry days, the transformations can be relatively more significant. Among the analysed metals, Cd present on road surfaces has a higher potential for being bioavailable during the antecedent dry days.

In this work, we propose a new sensitive, selective and portable surface enhanced Raman spectroscopy (SERS) methodology for the rapid on site detection of Pb(II) pollution in water. The new method utilises aminobenzo-18-crown-6 (AB18C6) as a selective recognition molecule to form a spontaneous complex with Pb(II) ions. The formed AB18C6-Pb(II) complex was rapidly immobilised onto a nanostructured gold substrate via Au-N bond formation and reproducibly screened by SERS using a handheld Raman device. For the SERS measurements, a substrate was fabricated by electrochemical deposition of gold nanostructures onto a flat gold disc, creating multiple hotspots for ultrasensitive SERS measurements. The limit of quantification (LOQ) for Pb(II) ions by the SERS method was 2.20 pM. The limit of detection (LOD) was 0.69 pM which is five orders of magnitude lower than the maximum Pb(II) level of 72 nM allowed by the US Environmental Protection Agency. The high sensitivity of the SERS substrate is attributed to the coupling between the Surface Plasmon Polariton (SPP) of its gold surface, the localised Surface Plasmon Resonance (SPR) of the gold nanostructures and the Raman radiation from the immobilised AB18C6-Pb(II) complex. The new SERS detection method was successfully applied for the selective and rapid screening of Pb(II) ion contamination in water proving its practical application for environmental analysis.

As one of the most popular beverages around world, factors influencing transfer of heavy metals from soil to tea leaves is crucial to investigate and assess health risk through tea drinking. Parent material (PM), soil and tea samples from Anhui province, typical tea producing area in China were collected in this study. To find out distribution characteristics of heavy metals in tea and soil, and influencing factors for transfer process, variables of plantation factors, soil properties and geological background were taken into account. The results showed that weathering pedogenic process could be the main release source of heavy metals in soil under the acid environment for tea growth. More than 75% of soil Cd, Hg, Pb and Zn exceeded background. However heavy metals in tea samples were below the limits of China, WHO and EU standards. Soil organic matter and redox process influenced the distribution and transfer of As, Pb, Cd and Hg in soil and tea. While geochemical behaviours of Cr, Cu, Ni and Zn were mainly related to soil pH and iron oxides in tea garden. The method of classification and regression trees (CART) showed clones of tea type, bedrock type, soil texture, soil organic and fertilizer application were identified as the main factors influencing transfer factors of heavy metals from soil to tea. The specific types of tea grown in the soil with sandy clay and bedrock of granite/granodiorite and shale should be given more monitoring. The non-carcinogenic hazard quotients (HQ) and cancer risk (Risk) through tea drinking were primarily caused by Pb and Cd respectively. To reduce the potential health risk from tea, application of organic and/or compound fertilizer were thought to be the effective management strategy for tea plantation.

The adsorption-desorption behaviour of heavy metals in aquatic environments is complex and the processes are regulated by the continuous interactions between water and sediments. This study provides a quantitative understanding of the effects of nutrients and key water and sediment properties on the adsorption-desorption behaviour of heavy metals in riverine and estuarine environments. The influence levels of the environmental factors were determined as conditional regression coefficients. The research outcomes indicate that the mineralogical composition of sediments, which influence other sediment properties, such as specific surface area and cation exchange capacity, play the most important role in the adsorption and desorption of heavy metals. It was found that particulate organic matter is the most influential nutrient in heavy metals adsorption in the riverine environment, while particulate phosphorus is more important under estuarine conditions. Dissolved nutrients do not exert a significant positive effect on the release of heavy metals in the riverine area, whilst dissolved phosphorus increases the transfer of specific metals from sediments to the overlying water under estuarine conditions. Furthermore, the positive interdependencies between marine-related ions and the release of most heavy metals in the riverine and estuarine environments indicate an increase in the mobility of heavy metals as a result of cation exchange reactions.

Earth‐abundant and environmentally friendly aluminosilicate minerals can be one of the promising alternatives to develop cost‐effective energy conversion and storage devices. Herein, in situ growth of transition metal nanoparticles is proposed to modify two commonly available feldspar minerals, albite and microcline, for promoting electrocatalytic oxygen evolution reaction activity via a one‐step thermal reduction strategy. Three types of transition metal nanoparticles, namely, Ni, Co, and Fe, are selected to modify the albite or microcline surfaces. As expected, these modified products deliver enhanced catalytic activities compared to the pristine minerals. Particularly, Co‐modified microcline (C‐KASO) demonstrates the best performance that even outperforms the commercial RuO2 catalyst. This design by coupling low‐cost aluminosilicate minerals with active transition metal nanoparticles offers a new insight into directly utilizing the natural abundant resources to address the current energy crisis.

Adsorption of iodate (IO3−) from concentrated solutions by LDH materials has been investigated in laboratory scale batch experiments. Very high iodate (IO3−) uptake (close to 100%) was observed in almost all experiments. Adsorption data was compared to the Langmuir and Freundlich adsorption isotherm models as well as the pseudo first and second order kinetic models. The data from the 3:1 Mg/Al LDH thermally activated to 500 °C was best described by the Freundlich isotherm and the pseudo second order model, suggesting that adsorption was a heterogeneous or multilayer process. HPLC data was used in an attempt to identify any conversion of iodate (IO3−) to iodide (I−) during the adsorption process, however, the residual concentration of iodide (I−) was close to or below the limit of detection of the particular analytical technique. This suggests that little or no conversion happened under experimental conditions.

Detailed knowledge of the processes that metals undergo during dry weather periods whilst deposited on urban surfaces and their environmental significance is essential to predict the potential influence of metals on stormwater quality in order to develop appropriate stormwater pollution mitigation measures. However, very limited research has been undertaken in this area. Accordingly, this study investigated the geochemical phase and particle size relationships of seven metals which are commonly associated with urban road dust, using sequential extraction in order to assess their mobility characteristics. Metals in the sequentially extracted fractions of exchangeable, reducible, oxidisable and residual were found to follow a similar trend for different land uses even though they had variable accumulation loads. The high affinity of Cd and Zn for exchangeable reactions in both, bulk and size-fractionated solid samples confirmed their high mobility, while the significant enrichment of Ni and Cr in the stable residual fraction indicated a low risk of mobility. The study results also confirmed the availability of Cu, Pb and Mn in both, stable and mobile fractions. The fine fraction of solids (

In this article, the authors report the adsorption of iodide by Mg/Al LDHs and thermally activated LDH materials in laboratory scale batch experiments. The optimal Mg/Al cation ratio was 3:1while the percentage iodide uptake increased with increasing adsorbent dose up to 1 g/20 mL of solution. The effect of initial iodide concentration was investigated using the Langmuir and Freundlich adsorption isotherm models, while the pseudo second order kinetic model appeared to provide the best fit for the experimental data. High iodide uptake of over 80% could be achieved without completely eliminating dissolved or atmospheric carbonate and leaching of 131I from LDHs did not appear to be a significant problem over the period of 28 days investigated. These results demonstrate that LDHs, which are already commercially available in large quantities, are a technology that shows considerable promise for the removal of radioiodine from aqueous solution.

Highlights - Sofosbuvir metabolite was studied for the first time by Raman spectroscopy. - Cheap and disposable paper substrate was utilized for the determination of PSI-6206 by HPLC-SERS. - The use of disposable substrate eliminated the memory effect problem in the HPLC-SERS. - The SERS LOQ of PSI-6206 was 13 ng L-1 (R2 = 0.959, RSD = 5.23%), 4 orders of magnitude less than HPLC-DAD. - The HPLC-SERS method provided unique structural identification of PSI-6206 similar to HPLC-MS Abstract Sofosbuvir metabolite, 2′-deoxy-2′-fluoro-2′-C-methyluridine (PSI-6206) was studied for the first time by surface enhanced Raman spectroscopy (SERS) using the paper-based SERS substrate. The quantification limit of PSI-6206 by SERS was found to be 13 ng L−1 (R2 value = 0.959, RSD = 5.23%). For the structural and quantitative analysis of PSI-6206 in blood plasma, an interference-free HPLC-SERS method was developed and compared to HPLC-DAD and HPLC–MS methods. The SERS quantification of the drug by the paper substrate was 4 orders of magnitude more sensitive than that by the diode array detector. In addition, the SERS detection provided unique structural identification of the drug in blood plasma, similar to Mass spectroscopy detector. Due to the disposable nature of the SERS substrate, the new method does not suffer from the known “memory effect” which is known to lead to false positive identification in traditional HPLC-SERS methods. Therefore, the presented HPLC-paper SERS platform holds great potential for the sensitive and cost effective determination of drugs and their metabolites in biological fluids.