Structure and Dynamics of Aqueous 2-Aminothiazole/NaCl Electrolytes at Electrified Interfaces.

A computational study was performed to investigate the dynamics of aqueous electrolytes containing organic corrosion inhibitors near electrified interfaces by using the constant-charge model in classical molecular dynamics simulations. The results showed that when inhibitors form films at the interface, the surface charge of the electrode causes displacement of the molecules, referred to as electroporation. The hydrophobicity of the inhibitor molecules affects both the stability of the films and their recovery time. This study highlights the value of computational investigations of the dynamics within inhibitor films as a complementary approach to the traditional focus on inhibitor-substrate interactions, leading to deeper insights into the mechanisms of corrosion inhibition mechanisms.

Quorum sensing inhibitors applications: A new prospect for mitigation of microbiologically influenced corrosion.

Quorum sensing (QS) is a process of bacterial communication that involves the use of biochemical signals and adjusts the expression of specific genes as a response to the bacterial cell density within an environment. This process is employed by both Gram-positive and Gram-negative bacteria to regulate different physiological functions. In both cases, QS involves production, detection and responses to signalling chemicals, termed auto-inducers. Expression of virulence factors and formation of biofilms are the typical processes controlled by QS, which, therefore, inspires the exploration of QS as a plausible solution to mitigating the increasing microbial resistance to antibiotics. QS inhibitors (QSIs) from different origins have been recognised as a promising solution to biofilm related challenges in a large variety of applications. Though QSIs have demonstrated some strength in tackling biofouling, a key focus in the literature on QSIs based strategies has been to control microbially influenced corrosion. This article reviews the principles of QS, its mechanistic roles in biofilm formation and the feasibility of QSIs to mitigate biofilm related challenges in a number of commercial applications. The potential of QSIs in microbially influenced corrosion for future applications is also discussed.

Effect of inhalation on oropharynx collapse via flow visualisation.

Computational fluid dynamics (CFD) modelling has made significant contributions to the analysis and treatment of obstructive sleep apnoea (OSA). While several investigations have considered the flow field within the airway and its effect on airway collapse, the effect of breathing on the pharynx region is still poorly understood. We address this gap via a combined experimental and numerical study of the flow field within the pharynx and its impacts upon airway collapse. Two 3D experimental models of the upper airway were constructed based upon computerised tomography scans of a specific patient diagnosed with severe OSA; (i) a transparent, rigid model for flow visualisation, and (ii) a semi-flexible model for understanding the effect of flow on pharynx collapse. Validated simulation results for this geometry indicate that during inhalation, negative pressure (with respect to atmospheric pressure) caused by vortices drives significant narrowing of the pharynx. This narrowing is strongly dependent upon whether inhalation occurs through the nostrils. Thus, the methodology presented here can be used to improve OSA treatment by improving the design methodology for personalised, mandibular advancement splints (MAS) that minimise OSA during sleep.

Experimental and DFT studies of gadolinium decorated graphene oxide materials for their redox properties and as a corrosion inhibition barrier layer on Mg AZ13 alloy in a 3.5% NaCl environment.

Magnesium alloys are broadly used worldwide in various applications; however, the serious disadvantage of these alloys are subject to corrosion and in aggressive/corrosive environments. A coating containing gadolinium-based composite materials can increase the alloy protection by strong electron transfer between the host alloy and the lanthanide-containing protective layer. This investigation aims to develop a Gd nanorod functionalised graphene oxide material as a corrosion inhibition barrier on the Mg alloy surface. The obtained functional materials were characterised by various spectroscopy techniques. The corrosion inhibition and composite material stability were studied by the electrochemical methods. The electrochemical stability was shown to increase with the applied current. The hydrogen evolution constantly increased and the corrosion inhibition significantly improved. Also, the computational studies of the material were performed, and their results support the experimental findings. Overall, the resultant composite material's corrosion resistance and cyclic stability are improved, and it could be used as a sodium-ion battery cathode material due to its high reversibility.

Synergistic Coating Strategy Combining Photodynamic Therapy and Fluoride-Free Superhydrophobicity for Eradicating Bacterial Adhesion and Reinforcing Corrosion Protection.

Device-associated infection is one of the significant challenges in the biomedical industry and clinical management. Controlling the initial attachment of microbes upon the solid surface of biomedical devices is a sound strategy to minimize the formation of biofilms and infection. A synergistic coating strategy combining superhydrophobicity and bactericidal photodynamic therapy is proposed herein to tackle infection issues for biomedical materials. A multifunctional coating is produced upon pure Mg substrate through a simple blending procedure without involvement of any fluoride-containing agents, differing from the common superhydrophobic surface preparations. Superhydrophobic features of the coating are confirmed through water contact angle measurements (152.5 ± 1.9°). In vitro experiments reveal that bacterial-adhesion repellency regarding both Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) strains approaches over 96%, which is evidently ascribed to the proposed synergistic strategy, that is, superhydrophobic nature and microbicidal ability of photodynamic therapy. Electrochemical analysis indicates that the superhydrophobic coating provides pronounced protection against corrosion to underlying Mg with 80% reduction in the corrosion rate in minimum essential medium and retains the original surface features after 168 h exposure to neutral salt spray. The proof-of-concept research holds a great promise for tackling the notorious bacterial infection and poor corrosion resistance of Mg-based biodegradable materials in a simple, efficient, and environmentally benign manner.

Exposure, assessment and health hazards of particulate matter in metal additive manufacturing: A review.

Metal additive manufacturing (AM), also known as metal three-dimensional (3D) printing, is a new technology offering design freedom to create complex structures that has found increasing applications in industrial processes. However, due to the fine metal powders and high temperatures involved, the printing process is likely to generate particulate matter (PM) that has a detrimental impact on the environment and human health. Therefore, comprehensive assessement of the exposure and health hazards of PM pollution related to this technique is urgently required. This review provides general knowledge of metal AM and its possible particle release. The health issues of metal PM are described considering the exposure routes, adverse human health outcomes and influencing factors. Methods of evaluating PM exposure and risk assessment techniques are also summarized. Lastly, future research needs are suggested. The information and knowledge presented in this review will contribute to the understanding, assessment, and control of possible risks in metal AM and benefit the wider metal 3D printing community, which includes machine operators, consumers, R&D scientists, and policymakers.

Quantum dot (QD)-based probes for multiplexed determination of heavy metal ions.

Heavy metal contamination is a major global concern and additive toxicity resulting from the exposure to multiple heavy metal ions is more pronounced than that induced by a single metal species. Quantum dots (QDs) have demonstrated unique properties as sensing materials for heavy metal ions over the past two decades. With the rapid development and deep understanding on determination of single heavy metal ion using QD probes, this technology has been employed for sensing multiple metal ions. This review (with 97 refs.) summarizes the progress made in recent years in methods for multiplexed determination of heavy metal ions using QDs. Following an introduction into the importance of simultaneous quantitation of multiple heavy metal ions in environmentally relevant settings, the review discusses the applications of different types of QDs, i.e. chalcogenide, carbon, polymer and graphene in this field. Determination strategies based on fluorometric, colorimetric and electrochemical responses were reviewed including the testing mechanisms and differentiation between various metal ions. In addition, current state of the art sensor constructions, i.e. immobilization of QDs on solid substrate and sensor arrays have been highlighted. A concluding section describes the limitations, opportunities and future challenges of the QD probes. We also compiled a comprehensive table of currently available literature. The listed papers provided information in the following categories, i.e. type of QDs used, ligands or other components in the probe, metal ions tested, medium/substrate of the probe, transduction methods, discrimination mechanism, limit of detection (LOD) and concentration range. Graphic abstract.

Corrosion resistance of itaconic acid doped polyaniline /nanographene oxide composite coating.

Graphene oxide (GO) and polyaniline (PANI) are very unique materials with broad potential in corrosion protection coating. To achieve the maximum stability and anti-corrosion effect in a polar medium, firstly itaconic acid doped PANI (DP) was readily prepared by a one-step method, followed by forming a GO and DP composite (GODP). Characterization by Fourier transform infrared spectroscopy and ultraviolet-visible absorption spectra provides evidence for the successful doping of itaconic acid in PANI. X-ray diffraction analysis shows that the d-spacing of the GO sheets increases slightly with the intercalation of DP. The morphological studies show disordered structures in GODP compared with the original GO sheets due to the introduction of PANI molecules and the interaction of functional groups on the surface of the GO sheets. Thermogravimetric analysis reveals the good thermal stability of DP and GODP. Quantum calculation further confirms the successful doping of itaconic acid, and the effective complex of GO and DP, providing a quantitative understanding of the curing mechanism. The crosslinking interaction among the GODP, curing agent, and epoxy resin facilitates the formation of a compact coating, leading to excellent corrosion resistance toward Mg alloy.

Facile synthesis of Tb-decorated graphene oxide: electrochemical stability, hydrogen storage, and corrosion inhibition of Mg AZ13 alloy in 3.5% NaCl medium.

Magnesium alloys have been broadly used due to their lightweight and high ductility. However, they are subject to corrosion which deteriorates their properties. To develop a novel corrosion inhibitor coating for Mg alloys, we performed functionalization of a graphene oxide (GO) matrix with Tb(iii) to improve the electrochemical behaviour and coating stability of a GO and Tb composite on the metal alloys in corrosive medium. The functionalized terbium GO material was characterized by microscopy, spectroscopy, and XRD techniques to confirm the non-covalent interactions on the active surface of the host material. The corrosion inhibition was found to be ca. 80% and electrochemical stability was observed to be high at a voltage of 900 mV. Computational studies also support the potential anti-corrosion applications of this material.

The Design and Synthesis of Fluorescent Coumarin Derivatives and Their Study for Cu2+ Sensing with an Application for Aqueous Soil Extracts.

A series of fluorescent coumarin derivatives 2a-e were systematically designed, synthesized and studied for their Cu2+ sensing performance in aqueous media. The sensitivities and selectivities of the on-to-off fluorescent Cu2+ sensing signal were in direct correlation with the relative arrangements of the heteroatoms within the coordinating moieties of these coumarins. Probes 2b and 2d exhibited Cu2+ concentration dependent and selective fluorescence quenching, with linear ranges of 0-80 µM and 0-10 µM, and limits of detection of 0.14 µM and 0.38 µM, respectively. Structural changes of 2b upon Cu2+ coordination were followed by fluorescence titration, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), mass spectrometry, and single crystal X-ray diffraction on the isolated Cu2+-coumarin complex. The results revealed a 1:1 stoichiometry between 2b and Cu2+, and that the essential structural features for Cu2+-selective coordination are the coumarin C=O and a three-bond distance between the amide NH and heterocyclic N. Probe 2b was also used to determine copper (II) levels in aqueous soil extracts, with recovery rates over 80% when compared to the standard soil analysis method: inductively coupled plasma-mass spectrometry (ICP-MS).

3D-QSAR for binding constants of ß-cyclodextrin host-guest complexes by utilising spectrophores as molecular descriptors.

The increasing use of cyclodextrins (CDs) as host-molecules for host-guest complexes and their remediation application in environmental science requires to establish easily accessible models of "quantitative structure-activity relationships" (QSARs) to predict the binding constants. A new open-source molecular descriptor, so called spectrophores, was utilised to build 3D-QSAR models which have R2 of 0.95 and RMSE of 0.20.

Evaluation of novel Griess-reagent candidates for nitrite sensing in aqueous media identified via molecular fingerprint searching.

The Griess reaction is the most often exploited colorimetric method for the quantitative analysis of nitrite in aqueous media. The application of the currently used reagents are associated with limitations (e.g. linear response range). Herein, molecular fingerprint searching on well-known Griess-reagents was used as a tool for the identification of structurally similar, new reagent candidate molecules. Rapid and high-throughput experimental evaluation of the newly identified Griess-reagent candidates revealed that 14 of the 18 tested reagent candidates had equal or superior response displaying broader linear ranges and/or increased response gradient against various nitrite concentrations in aqueous media when compared to the parent compounds at room temperature.

Praseodymium-decorated graphene oxide as a corrosion inhibitor in acidic media for the magnesium AZ31 alloy.

In the present work, Pr-decorated graphene oxide was synthesized and tested as a corrosion barrier layer in acidic media for the magnesium AZ31 alloy. The morphology, composition and structure of Pr-decorated graphene oxide sheets were characterized via HRTEM, FESEM, Raman, XRD, DLS, UV and FTIR studies. The corrosion inhibition efficiency on the alloy surface was monitored via microstructural and electrochemical methods. The results indicate that Pr-decorated graphene oxide provides improved protection for the Mg AZ31 alloy compared to conventional epoxy coatings. The proposed mechanism arises from a combination of the barrier activities of the composite, GO + Pr, and the epoxy coating on the Mg alloy in acidic media.

Recent Progress and Required Developments in Atmospheric Corrosion of Galvanised Steel and Zinc.

This paper reviews the progress in atmospheric corrosion of zinc since 2009. It firstly summarises the state of the art in 2009, then outlines progress since 2009, and then looks at the significance of this progress and the areas the need more research. Within this framework, it looks at climate effects, oxide formation, oxide properties, pitting, laboratory duplication of atmospheric corrosion, and modelling. The major findings are that there have been major advances in the fields understanding of the structure of corrosion patina, in particular their layered structure and the presence of compact layers, local corrosion attacks have been found to be a significant process in atmospheric corrosion and experiments under droplets are leading to new understanding of the criticality of drop size in regulating atmospheric corrosion processes. Further research is indicating that zinc oxide within corrosion products may promote the oxygen reduction reaction (ORR) and that, in porous oxides, the ORR would control pore chemistry and may promote oxide densification. There is a strong need for more research to understand more deeply the formation and properties of these layered oxides as well as additional research to refine and quantify our emerging understanding of corrosion under droplets.

Effect of Pseudomonas fluorescens on Buried Steel Pipeline Corrosion.

Buried steel infrastructure can be a source of iron ions for bacterial species, leading to microbiologically influenced corrosion (MIC). Localized corrosion of pipelines due to MIC is one of the key failure mechanisms of buried steel pipelines. In order to better understand the mechanisms of localized corrosion in soil, semisolid agar has been developed as an analogue for soil. Here, Pseudomonas fluorescens has been introduced to the system to understand how bacteria interact with steel. Through electrochemical testing including open circuit potentials, potentiodynamic scans, anodic potential holds, and electrochemical impedance spectroscopy it has been shown that P. fluorescens increases the rate of corrosion. Time for oxide and biofilms to develop was shown to not impact on the rate of corrosion but did alter the consistency of biofilm present and the viability of P. fluorescens following electrochemical testing. The proposed mechanism for increased corrosion rates of carbon steel involves the interactions of pyoverdine with the steel, preventing the formation of a cohesive passive layer, after initial cell attachment, followed by the formation of a metal concentration gradient on the steel surface.

Modeling corrosion inhibition efficacy of small organic molecules as non-toxic chromate alternatives using comparative molecular surface analysis (CoMSA).

Traditionally many structural alloys are protected by primer coatings loaded with corrosion inhibiting additives. Strontium Chromate (or other chromates) have been shown to be extremely effectively inhibitors, and find extensive use in protective primer formulations. Unfortunately, hexavalent chromium which imbues these coatings with their corrosion inhibiting properties is also highly toxic, and their use is being increasingly restricted by legislation. In this work we explore a novel tridimensional Quantitative-Structure Property Relationship (3D-QSPR) approach, comparative molecular surface analysis (CoMSA), which was developed to recognize "high-performing" corrosion inhibitor candidates from the distributions of electronegativity, polarizability and van der Waals volume on the molecular surfaces of 28 small organic molecules. Multivariate statistical analysis identified five prototypes molecules, which are capable of explaining 71% of the variance within the inhibitor data set; whilst a further five molecules were also identified as archetypes, describing 75% of data variance. All active corrosion inhibitors, at a 80% threshold, were successfully recognized by the CoMSA model with adequate specificity and precision higher than 70% and 60%, respectively. The model was also capable of identifying structural patterns, that revealed reasonable starting points for where structural changes may augment corrosion inhibition efficacy. The presented methodology can be applied to other functional molecules and extended to cover structure-activity studies in a diverse range of areas such as drug design and novel material discovery.

Quantum-confined bandgap narrowing of TiO2 nanoparticles by graphene quantum dots for visible-light-driven applications.

We for the first time report a quantum-confined bandgap narrowing mechanism through which the absorption of two UV absorbers, namely the graphene quantum dots (GQDs) and TiO2 nanoparticles, can be easily extended into the visible light range in a controllable manner. Such a mechanism may be of great importance for light harvesting, photocatalysis and optoelectronics.

Enhanced quantum efficiency from a mosaic of two dimensional MoS2 formed onto aminosilane functionalised substrates.

Developing scalable methods of growing two dimensional molybdenum disulphide (2D MoS2) with strong optical properties, on any desired substrates, is a necessary step towards industrial uptake of this material for optical applications. In this study, Si/SiO2 substrates were functionalised using self-assembled monolayers of three different aminosilanes with various numbers of amine groups and molecular lengths as underlayers for enhancing the adherence of the molybdenum precursor. The tetrahedral [MoS4](2-) anion groups from the molybdenum precursor were bonded on these silanised Si/SiO2 substrates afterwards. The substrates were then treated with a combined thermolysis and sulphurisation step. The results showed that silanisation of the substrates using the longest chains and the largest number of amine groups provided a good foundation to grow quasi 2D MoS2 made from adjacent flakes in a mosaic formation. Microscopy and spectroscopy investigations revealed that these quasi 2D MoS2 formed using this long chain aminosilane resulted in flakes with lateral dimensions in micron and submicron ranges composed of adjoining MoS2 pieces of 20 to 60 nm in lateral dimensions, dominantly made of 3 to 5 MoS2 fundamental layers. The obtained quasi 2D MoS2 shows a high internal quantum efficiency of 2.6% associated with the quantum confinement effect and high stoichiometry of the adjoining nanoflakes that form the structure of the sheets. The synthesis technique in this study is reliable and facile and offers a procedure to form large, scalable and patternable quasi 2D MoS2 sheets on various substrates with enhanced optical properties for practical applications.

The dual roles of functional groups in the photoluminescence of graphene quantum dots.

The photoluminescent properties of graphene nanoparticle (named graphene quantum dots) have attracted significant research attention in recent years owing to their profound application potential. However, the photoluminescence (PL) origin of this class of nanocarbons is still unclear. In this paper, combining direct experimental evidence enabled by a facile size-tunable oxygenated graphene quantum dots (GQDs) synthesis method and theoretical calculations, the roles of the aromatic core, functional groups and disordered structures (i.e. defects and sp(3) carbon) in the PL of oxygenated GQDs are elucidated in detail. In particular, we found that the functional groups on GQDs play dual roles in the overall emission: (1) they enable π* → n and σ* → n transitions, resulting in a molecular type of PL, spectrally invariable with change of particle size or excitation energy; (2) similar to defects and sp(3) carbon, functional groups also induce structural deformation to the aromatic core, leading to mid-gap states or, in other words, energy traps, causing π* → mid-gap states → π transitions. Therefore, functional groups contribute to both the blue edge and the red shoulder of GQDs' PL spectra. The new insights on the role of functional groups in PL of fluorescent nanocarbons will enable better designs of this new class of materials.

The effect of fluorophore incorporation on fluorescence enhancement in colloidal photonic crystals.

The significant effect of photonic crystals (PhCs) on fluorophore emission has recently received intense interest. However, so far little attention has been paid on the influence of the fluorophore incorporation method on the performance of PhCs, particularly in practical applications. In this study, rhodamine B is immobilised on polystyrene spheres using a diffusion-swelling method, which are self-assembled into three-dimensional colloidal photonic crystal films. This immobilization method has resulted in 230-fold fluorescence enhancement compared to control films, the greatest fluorescence enhancement of RhB immobilised on monolithic colloidal photonic crystals compared to other immobilization methods such as infiltration and electrostatic charge-facilitated dye attachment on the particle surface. We further demonstrate the stability of dye attachment and the relationship between fluorescence intensity enhancement and the pseudo bandgap position relative to a fluorophore fluorescence peak.