Imperial College London

ProfessorMaryRyan

Central FacultyOffice of the Provost

Interim Vice-Provost (Research and Enterprise)
 
 
 
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Contact

 

+44 (0)20 7594 6755m.p.ryan

 
 
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Location

 

B338Royal School of MinesSouth Kensington Campus

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Summary

 

Publications

Publication Type
Year
to

240 results found

Wang S, Gavalda-Diaz O, Luo T, Guo L, Lovell E, Wilson N, Gault B, Ryan MP, Giuliani Fet al., 2022, The effect of hydrogen on the multiscale mechanical behaviour of a La(Fe,Mn,Si)13-based magnetocaloric material, Journal of Alloys and Compounds, Vol: 906, Pages: 1-10, ISSN: 0925-8388

Magnetocaloric cooling offers the potential to improve the efficiency of refrigeration devices and hence cut the significant CO2 emissions associated with cooling processes. A critical issue in deployment of this technology is the mechanical degradation of the magnetocaloric material during processing and operation, leading to limited service-life. The mechanical properties of hydrogenated La(Fe,Mn,Si)13-based magnetocaloric material are studied using macroscale bending tests of polycrystalline specimens and in situ micropillar compression tests of single crystal specimens. The impact of hydrogenation on the mechanical properties are quantified. Understanding of the deformation/failure mechanisms is aided by characterization with transmission electron microscopy and atom probe tomography to reveal the arrangement of hydrogen atoms in the crystal lattice. Results indicate that the intrinsic strength of this material is ~3-6 GPa and is dependent on the crystal orientation. Single crystals under compressive load exhibit shearing along specific crystallographic planes. Hydrogen deteriorates the strength of La(Fe,Mn,Si)13 through promotion of transgranular fracture. The weakening effect of hydrogen on single crystals is anisotropic; it is significant upon shearing parallel to the {111} crystallographic planes but is negligible when the shear plane is {001}-oriented. APT analysis suggests that this is associated with the close arrangement of hydrogen atoms on {222} planes.

Journal article

Xu Z, Wang J, Guo Z, Xie F, Liu H, Yadegari H, Tebyetekerwa M, Ryan MP, Hu Y-S, Titirici M-Met al., 2022, The Role of Hydrothermal Carbonization in Sustainable Sodium-Ion Battery Anodes, ADVANCED ENERGY MATERIALS, ISSN: 1614-6832

Journal article

Gomez-Gonzalez MA, Rehkamper M, Han Z, Ryan MP, Laycock A, Porter AEet al., 2022, ZnO Nanomaterials and Ionic Zn Partition within Wastewater Sludge Investigated by Isotopic Labeling, Global Challenges, Vol: 6, ISSN: 2056-6646

The increasing commercial use of engineered zinc oxide nanomaterials necessitates a thorough understanding of their behavior following their release into wastewater. Herein, the fates of zinc oxide nanoparticles (ZnO NPs) and ionic Zn in a real primary sludge collected from a municipal wastewater system are studied via stable isotope tracing at an environmentally relevant spiking concentration of 15.2 µg g−1. Due to rapid dissolution, nanoparticulate ZnO does not impart particle-specific effects, and the Zn ions from NP dissolution and ionic Zn display indistinguishable behavior as they partition equally between the solid, liquid, and ultrafiltrate phases of the sludge over a 4-h incubation period. This work provides important constraints on the behavior of engineered ZnO nanomaterials in primary sludge—the first barrier in a wastewater treatment plant—at low, realistic concentrations. As the calculated solid–liquid partition coefficients are significantly lower than those reported in prior studies that employ unreasonably high spiking concentrations, this work highlights the importance of using low, environmentally relevant doses of engineered nanomaterials in experiments to obtain accurate risk assessments.

Journal article

Wang S, Lovell E, Guo L, Wilson N, Ryan MP, Giuliani Fet al., 2022, Environment-assisted crack nucleation in La(Fe,Mn,Si)13-based magnetocaloric materials, International Journal of Refrigeration, Vol: 135, Pages: 1-4, ISSN: 0140-7007

Cracking in La(Fe,Si)13-based magnetocaloric materials has been observed to predominantly form around La-rich (La2O3) particles and pose a threat to their long-term structural integrity. To understand the formation of these cracks, FIB cross-sectional polishing followed by SEM characterisation was employed to study local microstructural evolution after air exposure. Results suggest that volume expansion and internal degradation associated with a chemical reaction between La2O3 particles and water/moisture can lead to crack nucleation in the 1:13 phase adjacent to La-rich particles. This observation indicates that the formation of La-rich phase should be suppressed, or their size minimised during material processing to ensure the long-term structural integrity of La(Fe,Mn,Si)13 magnetocaloric materials.

Journal article

Aberdeen S, Hur CA, Cali E, Vandeperre L, Ryan MPet al., 2022, Acid resistant functionalised magnetic nanoparticles for radionuclide and heavy metal adsorption, Journal of Colloid and Interface Science, Vol: 608, Pages: 1728-1738, ISSN: 0021-9797

Coating superparamagnetic iron oxide NPs with SiO2 has been established in order to confer stability in acidic media. Acid stability tests were carried out between pH 1 and pH 7 to determine the effectiveness of the SiO2 passivating layer to protect the magnetic Fe3O4 core. Transmission Electron Microscopy (TEM) and zeta potential measurements have shown that uncoated Fe3O4 NPs exhibit rapid agglomeration and dissolution when exposed to acidic media, moving from a zeta potential of - 26 mV to a zeta potential of + 3 mV. In contrast, the SiO2 coating of the Fe3O4 NPs shows a very high degree of stability for over 14 months and the zeta potential of these NPs remained at ∼- 39 mV throughout the acid exposure and they showed no loss in magnetisaton. Due to the use of these NPs as a potential tool for heavy metal extraction, the stability of the surface functionalisation (in this case a phosphate complex) was also assessed. With a constant zeta potential of ∼ - 29 mV for POx-SiO2@Fe3O4 NP complex, the phosphate functionality was shown to be highly stable in the acidic conditions simulating the environment of certain nuclear wastes. ATR-FTIR was conducted after acid exposure confirming that the phosphate complex on the surface of the NPs remained present. Finally, preliminary sorption experiments were carried out with Pb(II), where the NP complexes shown complete removal of the heavy metals at pH 3 and pH 5.

Journal article

Barrio Hermida J, Pedersen A, Feng J, Sarma S, Wang M, Li A, Yadegari H, Luo H, Ryan M, Titirici M, Stephens Iet al., 2022, Metal coordination in C2N-like materials towards dual atom catalysts for oxygen reduction, Journal of Materials Chemistry A, ISSN: 2050-7488

Journal article

Sundaresan SM, Fothergill SM, Tabish TA, Ryan M, Xie Fet al., 2021, Aptamer biosensing based on metal enhanced fluorescence platform: A promising diagnostic tool, Applied Physics Reviews, Vol: 8, Pages: 1-14, ISSN: 1931-9401

Diagnosis of disease at an early, curable, and reversible stage allows more conservative treatment and better patient outcomes. Fluorescence biosensing is a widely used method to detect biomarkers, which are early indicators of disease. Importantly, biosensing requires a high level of sensitivity. Traditionally, these sensors use antibodies or enzymes as biorecognition molecules; however, these can lack the specificity required in a clinical setting, limiting their overall applicability. Aptamers are short, single stranded nucleotides that are receiving increasing attention over traditional recognition molecules. These exhibit many advantages, such as high specificity, making them promising for ultrasensitive biosensors. Metal enhanced fluorescence (MEF) utilizes plasmonic materials, which can increase the sensitivity of label-based fluorescent biosensors. The fluorescence enhancement achieved by placing metallic nanostructures in close proximity to fluorophores allows for detection of ultra-low biomarker concentrations. Plasmonic biosensors have been successfully implemented as diagnostic tools for a number of diseases, such as cancer, yet reproducible systems exhibiting high specificity and the ability to multiplex remain challenging. Similarly, while aptasensors have been extensively reported, few systems currently incorporate MEF, which could drastically improve biosensor sensitivity. Here, we review the latest advancements in the field of aptamer biosensing based on MEF that have been explored for the detection of a wide variety of biological molecules. While this emerging biosensing technology is still in its infant stage, we highlight the potential challenges and its clinical potential in early diagnosis of diseases.

Journal article

Alsalem MM, Camilla S, Ryan MP, Campbell KSet al., 2021, Understanding the Role of NaCl Concentration on the Corrosion of Carbon Steel and FeCO3 Formation in CO2-Containing Electrolytes, INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, Vol: 60, Pages: 12032-12048, ISSN: 0888-5885

Journal article

Gomez-Gonzalez MA, Koronfel MA, Pullin H, Parker JE, Quinn PD, Inverno MD, Scott TB, Xie F, Voulvoulis N, Yallop ML, Ryan MP, Porter AEet al., 2021, Nanoscale chemical imaging of nanoparticles under real-world wastewater treatment conditions, Advanced Sustainable Systems, Vol: 5, ISSN: 2366-7486

Understanding nanomaterial transformations within wastewater treatment plants is an important step to better predict their potential impact on the environment. Here, spatially resolved, in situ nano-X-ray fluorescence microscopy is applied to directly observe nanometer-scale dissolution, morphological, and chemical evolution of individual and aggregated ZnO nanorods in complex “real-world” conditions: influent water and primary sludge collected from a municipal wastewater system. A complete transformation of isolated ZnO nanorods into ZnS occurs after only 1 hour in influent water, but larger aggregates of the ZnO nanorods transform only partially, with small contributions of ZnS and Zn-phosphate (Zn3(PO4)2) species, after 3 hours. Transformation of aggregates of the ZnO nanorods toward mixed ZnS, Zn adsorbed to Fe-oxyhydroxides, and a large contribution of Zn3(PO4)2 phases are observed during their incubation in primary sludge for 3 hours. Discrete, isolated ZnO regions are imaged with unprecedented spatial resolution, revealing their incipient transformation toward Zn3(PO4)2. Passivation by transformation(s) into mixtures of less soluble phases may influence the subsequent bioreactivity of these nanomaterials. This work emphasizes the importance of imaging the nanoscale chemistry of mixtures of nanoparticles in highly complex, heterogeneous semi-solid matrices for improved prediction of their impacts on treatment processes, and potential environmental toxicity following release.

Journal article

Guo L, Thornton DB, Koronfel MA, Stephens IEL, Ryan MPet al., 2021, Degradation in lithium ion battery current collectors, JPhys Energy, Vol: 3, ISSN: 2515-7655

Lithium ion battery (LIB) technology is the state-of-the-art rechargeable energy storage technology for electric vehicles, stationary energy storage and personal electronics. However, a wide variety of degradation effects still contribute to performance limitations. The metallic copper and aluminium current collectors in an LIB can be subject to dissolution or other reactions with the electrolytes. Corrosion of these metal foils is significantly detrimental to the overall performance of an LIB, however the mechanisms of this degradation are poorly understood. This review summarises the key effects contributing to metal current collector degradation in LIBs as well as introduces relevant corrosion and LIB principles. By developing the understanding of these complex chemistries, LIB degradation can be mitigated, enabling safer operation and longer lifetimes.

Journal article

Yadegari H, Koronfel MA, Wang K, Thornton DB, Stephens IEL, Molteni C, Haynes PD, Ryan MPet al., 2021, Operando measurement of layer breathing modes in lithiated graphite, ACS Energy Letters, Vol: 6, Pages: 1633-1638, ISSN: 2380-8195

Despite their ubiquitous usage and increasing societal dependence on Li-ion batteries, there remains a lack of detailed empirical evidence of Li intercalation/deintercalation into graphite even though this process dictates the performance, longevity, and safety of the system. Here, we report direct detection and dissociation of specific crystallographic phases in the lithiated graphite, which form through a stepwise staging process. Using operando measurements, LiC18, LiC12, and LiC6 phases are observed via distinct low-frequency Raman features, which are the result of displacement of the graphite lattice by induced local strain. Density functional theory calculations confirm the nature of the Raman-active vibrational modes, to the layer breathing modes (LBMs) of the lithiated graphite. The new findings indicate graphene-like characteristics in the lithiated graphite under the deep charged condition due to the imposed strain by the inserted Li. Moreover, our approach also provides a simple experimental tool to measure induced strain in the graphite structure under full intercalation conditions.

Journal article

Alzahabi KH, Usmani O, Georgiou TK, Ryan MP, Robertson BD, Tetley TD, Porter AEet al., 2020, Approaches to treating tuberculosis by encapsulating metal ions and anti-mycobacterial drugs utilizing nano- and microparticle technologies, Emerging Topics in Life Sciences, Vol: 4, Pages: 581-600, ISSN: 2397-8554

Tuberculosis (TB) is caused by a bacterial infection that affects a number of human organs, primarily the lungs, but also the liver, spleen, and spine, causing key symptoms of fever, fatigue, and persistent cough, and if not treated properly, can be fatal. Every year, 10 million individuals become ill with active TB resulting with a mortality approximating 1.5 million. Current treatment guidelines recommend oral administration of a combination of first-line anti-TB drugs for at least 6 months. While efficacious under optimum conditions, ‘Directly Observed Therapy Short-course’ (DOTS) is not without problems. The long treatment time and poor pharmacokinetics, alongside drug side effects lead to poor patient compliance and has accelerated the emergence of multi-drug resistant (MDR) organisms. All this, combined with the limited number of newly discovered TB drugs to treat MDR-TB and shorten standard therapy time, has highlighted the need for new targeted drug delivery systems. In this respect, there has been recent focus on micro- and nano-particle technologies to prepare organic or/and metal particles loaded with TB drugs to enhance their efficacy by targeted delivery via the inhaled route. In this review, we provide a brief overview of the current epidemiology of TB, and risk factors for progression of latent stage tuberculosis (LTBI) to the active TB. We identify current TB treatment regimens, newly discovered TB drugs, and identify studies that have used micro- or nano-particles technologies to design a reliable inhalation drug delivery system to treat TB more effectively.

Journal article

Michaeloudes C, Seiffert J, Chen S, Ruenraroengsak P, Bey L, Theodorou IG, Ryan M, Cui X, Zhang J, Shaffer M, Tetley T, Porter AE, Chung KFet al., 2020, Effect of silver nanospheres and nanowires on human airway smooth muscle cells: role of sulfidation, Nanoscale Advances, Vol: 2, Pages: 5635-5647, ISSN: 2516-0230

Background: The toxicity of inhaled silver nanoparticles on contractile and pro-inflammatory airway smooth muscle cells (ASMCs) that control airway calibre is unknown. We explored the oxidative activities and sulfidation processes of the toxic-inflammatory response. Method: Silver nanospheres (AgNSs) of 20 nm and 50 nm diameter and silver nanowires (AgNWs), short S-AgNWs, 1.5 μm and long L-AgNWs, 10 μm, both 72 nm in diameter were manufactured. We measured their effects on cell proliferation, mitochondrial reactive oxygen species (ROS) release and membrane potential, and also performed electron microscopic studies. Main results and findings: The greatest effects were observed for the smallest particles with the highest specific surface area and greatest solubility that were avidly internalised. ASMCs exposed to 20 nm AgNSs (25 μg mL−1) for 72 hours exhibited a significant decrease in DNA incorporation (−72.4%; p < 0.05), whereas neither the 50 nm AgNSs nor the s-AgNWs altered DNA synthesis or viability. There was a small reduction in ASMC proliferation for the smaller AgNS, although Ag+ at 25 μL mL−1 reduced DNA synthesis by 93.3% (p < 0.001). Mitochondrial potential was reduced by both Ag+ (25 μg mL−1) by 47.1% and 20 nm Ag NSs (25 μg mL−1) by 40.1% (*both at p < 0.05), but was not affected by 50 nm AgNSs and the AgNWs. None of the samples showed a change in ROS toxicity. However, malondialdehyde release, associated with greater total ROS, was observed for all AgNPs, to an extent following the geometric size (20 nm AgNS: 213%, p < 0.01; 50 nm AgNS: 179.5%, p < 0.01 and L-AgNWs by 156.2%, p < 0.05). The antioxidant, N-acetylcysteine, prevented the reduction in mitochondrial potential caused by 20 nm AgNSs. The smaller nanostructures were internalised and dissolved within the ASMCs with the formation of non-reactive silver sulphide (Ag2S) on their surface, but with very little uptake of L-AgNWs. When A

Journal article

Chen S, Greasley SL, Ong ZY, Naruphontjirakul P, Page SJ, Hanna J, Redpath AN, Tsigkou O, Rankin S, Ryan MP, Porter AE, Jones JRet al., 2020, Biodegradable zinc-containing mesoporous silica nanoparticles for cancer therapy, Materials Today, Vol: 6, Pages: 1-11, ISSN: 1369-7021

Triple-negative breast cancers are extremely aggressive with limited treatment options because of the reduced response of the cancerous cells to hormonal therapy. Here, monodispersed zinc-containing mesoporous silica nanoparticles (MSNPs-Zn) were produced as a tuneable biodegradable platform for delivery of therapeutic zinc ions into cells. We demonstrate that the nanoparticles were internalized by cells, and a therapeutic dose window was identified in which the MSNPs-Zn were toxic to breast cancer cells but not to healthy epithelial (MCF-10a) cells or to murine macrophages. A significant reduction in the viability of triple negative MDA-MB-231 and MCF-7 (ER+) breast cancer cells was seen following 24 h exposure to MSNPs-Zn. The more aggressive MDA-MB-231 cells, with higher metastatic potential, were more sensitive to MSNPs-Zn than the MCF-7 cells. MSNPs-Zn underwent biodegradation inside the cells, becoming hollow structures, as imaged by high-resolution transmission electron microscopy. The mesoporous silica nanoparticles provide a biodegradable vehicle for therapeutic ion release inside cells.

Journal article

Antonio EN, Wicking C, Filip S, Ryan MP, Heutz Set al., 2020, Role of iron speciation in oxidation and deposition at the hexadecane-iron interface, ACS Applied Materials and Interfaces, Vol: 12, Pages: 19140-19152, ISSN: 1944-8244

Interactions between iron surfaces and hydrocarbons are the basis for a wide range of materials synthesis processes and novel applications, including sensing. However, in diesel engines these interactions can lead to deposit formation that reduces performance, lowers efficiency, and increases emissions. Here, we present a global study to understand deposition at iron-hexadecane interfaces. We use a combination of spectroscopy, microscopy, and mass spectrometry to investigate surface reactions, bulk chemistry, and deposition processes. A dynamic equilibrium between the oxidation products, both at the surface and in solution, determines the deposition at the surface. Considering the solution and the surface in parallel, we find that the iron speciation affects the morphology, composition, and quantity of the deposit at the surface, as well as the oxidation of hexadecane. Fe(II) and Fe(III) both promote the decomposition of peroxides-intermediates in the oxidation of hexadecane-but through noncatalytic and catalytic mechanisms, respectively. In contrast, Fe(0) is proposed to initiate hexadecane autoxidation during its oxidation to Fe(III). We find that in all cases, the surfaces exclusively contain Fe(III) following heat treatment with hexadecane. Upon subsequent exposure at room temperature, Fe(III) species are found to promote oxidation; this finding is particularly concerning for hybrid vehicles where longer time periods are expected between engine operation. Our work provides a foundation for the development of strategies that disrupt the role of iron in the degradation of hexadecane to ultimately reduce oxidation and deposition in diesel engines.

Journal article

Hadden JHL, Ryan MP, Riley DJ, 2020, Is nickel hydroxide charging only skin-deep?, ACS Applied Energy Materials, Vol: 3, Pages: 2803-2810, ISSN: 2574-0962

The depth of charging in Ni(OH)2-coated electrodes treated with paraffin wax to remove porosity has been investigated using time-of-flight secondary-ion mass spectrometry after charging and discharging in deuterated solvent at pH 14. The proportion of deuterium uptake was found to be dependent on the number of charge/discharge cycles, showing that the measured deuterium signal was indeed dependent on the electrochemical redox activity of the sample. Sputter craters were characterized using atomic force microscopy to find the sputter rate. This then allowed the maximum depth of charging to be found to be approximately 20 nm. This confirmed a surface “skin” in which charging occurs with the rest of the bulk inactive.

Journal article

Rodrigues RL, Xie F, Porter AE, Ryan MPet al., 2020, Geometry-induced protein reorientation on the spikes of plasmonic gold nanostars, NANOSCALE ADVANCES, Vol: 2, Pages: 1144-1151, ISSN: 2516-0230

Journal article

Guo L, Lovell E, Tang Q, Boldrin DC, Tang CC, Day SJ, Cohen LF, Ryan MPet al., 2020, Fine control of Curie temperature of magnetocaloric alloys La(Fe,Co,Si)(13) using electrolytic hydriding, Scripta Materialia, Vol: 175, Pages: 33-37, ISSN: 1359-6462

This work demonstrates precision control of hydrogen content in La(Fe,Co,Si)13Hδ for the development of environmentally friendly magnetocaloric-based cooling technologies, using an electrolytic hydriding technique. We show the Curie temperature, a critical parameter which directly governs the temperature window of effective cooling, can be varied easily and reproducibly in 1 K steps within the range 274 K to 402 K. Importantly, both partially (up to 10%) and fully hydrided compositions retain favorable entropy change values comparable to that of the base composition. Crucially, we show in these second-order phase transition compounds, partial hydriding is stable and not susceptible against phase separation.

Journal article

Parra-Puerto A, Ng KL, Fahy K, Goode AE, Ryan MP, Kucernak Aet al., 2019, Supported transition metal phosphides: Activity survey for HER, ORR, OER and corrosion resistance in acid and alkaline electrolytes, ACS Catalysis, Vol: 9, Pages: 11515-11529, ISSN: 2155-5435

Carbon supported MxPy (M = Ni, Co, W, Cr and Mo) were prepared via pyrolysis using a very simple and scalable method utilizing non-toxic metal and phosphorous precursors. The electrochemical hydrogen evolution (HER), oxygen reduction (ORR), and oxygen evolution (OER) reactions and corrosion resistance under both acid and alkaline conditions were examined for all these catalysts and compared to the benchmark catalysts Pt/C (HER/ORR) and IrO2(OER). The highest activities were found in alkaline solutions for Co2P for HER and ORR and Ni2P for OER. Good activity for these was also found in acid for some of these reactions, although the catalysts suffered from susceptibility to corrosion. Co2P was further studied in an alkaline environment as it shows high catalytic activity towards the oxygen reduction reaction (ORR) without significant hysteresis. The onset potential (at 0.5 mA cm-2) obtained was 0.8 V and a Tafel slope value of 38 mV dec-1 with a maximum kinetic mass activity of 2870 A gCo-1 at 0.7 V (RHE). Utilising high resolution transmission electron microscopy (HRTEM) it is possible to observe high-surface area needle-like single crystal cobalt oxide structures on the surfaces of the Co2P particles at the beginning of the ORR. Hence the high rates of initial corrosion of the Co2P identified appear to be associated with the dissolution and precipitation of Cobalt oxide on the particle surface. The as-synthesised Co2P/C also shows good performance in an 8-hour stability test for the Oxygen Evolution Reaction (OER), carried out at 1.6 V vs. RHE in alkaline conditions, with negligible drop in current density over time. Interestingly, in an acidic environment the catalyst is very active towards 2-electron- oxygen reduction leading to H2O2 with high selectivity (85%). It is intriguing that the pH dependence on this catalyst towards the ORR is similar to that seen for gold.

Journal article

Scatigno GG, Dong P, Ryan MP, Wenman MRet al., 2019, The effect of salt loading on chloride-induced stress corrosion cracking of 304L austenitic stainless steel under atmospheric conditions, Materialia, Vol: 8, Pages: 1-11, ISSN: 2589-1529

The effect of salt loading on chloride-induced stress corrosion cracking in 304 L was studied at atmospheric pressure. Stress relieved samples were uniaxially pre-strained to 5% and were loaded with nine levels of MgCl2, investigating Cl− deposition levels from 1.7 × 10−4 to 3.1 x 10−2 g cm−2. Samples were subject to 60 MPa stress, 90 °C at 70% relative humidity, for 480 h. A direct correlation between chloride deposition and the density of cracking and corrosion was observed between 5.7 × 10−4 and 1.96 × 10−2 g cm−2. Crack propagation rates were constant between salt loadings of 5.7 × 10−4 and 2.4 × 10−2 g cm−2 at 1–2 µm h−1.

Journal article

Gomez-Gonzalez MA, Koronfel MA, Goode AE, Al-Ejji M, Voulvoulis N, Parker JE, Quinn PD, Scott TB, Xie F, Yallop ML, Porter AE, Ryan MPet al., 2019, Spatially resolved dissolution and speciation changes of ZnO nanorods during short-term in situ incubation in a simulated wastewater environment, ACS Nano, Vol: 13, Pages: 11049-11061, ISSN: 1936-0851

Zinc oxide engineered nanomaterials (ZnO ENMs) are used in a variety of applications worldwide due to their optoelectronic and antibacterial properties with potential contaminant risk to the environment following their disposal. One of the main potential pathways for ZnO nanomaterials to reach the environment is via urban wastewater treatment plants. So far there is no technique that can provide spatiotemporal nanoscale information about the rates and mechanisms by which the individual nanoparticles transform. Fundamental knowledge of how the surface chemistry of individual particles change, and the heterogeneity of transformations within the system, will reveal the critical physicochemical properties determining environmental damage and deactivation. We applied a methodology based on spatially resolved in situ X-ray fluorescence microscopy (XFM), allowing observation of real-time dissolution and morphological and chemical evolution of synthetic template-grown ZnO nanorods (∼725 nm length, ∼140 nm diameter). Core-shell ZnO-ZnS nanostructures were formed rapidly within 1 h, and significant amounts of ZnS species were generated, with a corresponding depletion of ZnO after 3 h. Diffuse nanoparticles of ZnS, Zn3(PO4)2, and Zn adsorbed to Fe-oxyhydroxides were also imaged in some nonsterically impeded regions after 3 h. The formation of diffuse nanoparticles was affected by ongoing ZnO dissolution (quantified by inductively coupled plasma mass spectrometry) and the humic acid content in the simulated sludge. Complementary ex situ X-ray absorption spectroscopy and scanning electron microscopy confirmed a significant decrease in the ZnO contribution over time. Application of time-resolved XFM enables predictions about the rates at which ZnO nanomaterials transform during their first stages of the wastewater treatment process.

Journal article

Gu Y, Li J, Wang L, Xie M, Wu X, Xie F, Ryan MPet al., 2019, Template-Free Cu Electrodeposition to Prepare Cu-Micro-Brush Electrodes for Electrochemical CO2 Reduction, CHEMISTRYSELECT, Vol: 4, Pages: 10995-11001, ISSN: 2365-6549

Journal article

Leo BF, Fearn S, Gonzalez-Carter D, Theodorou I, Ruenraroengsak P, Goode A, Mcphail D, Dexter DT, Shaffer MSP, Chung KF, Porter AE, Ryan MPet al., 2019, Label-free TOF-SIMS imaging of sulfur producing enzymes inside microglia cells following exposure to silver nanowires, Analytical Chemistry, Vol: 91, Pages: 11098-11107, ISSN: 0003-2700

There are no methods sensitive enough to detect enzymes within cells, without the use of analyte labelling. Here we show that it is possible to detect protein ion signals of three different H2S-synthesizing enzymes inside microglia after pre-treatment with silver nanowires (AgNW) using time of flight-secondary ion mass spectrometry (TOF-SIMS). Protein fragment ions, including the fragment of amino acid (C4H8N+ - 70 amu), fragments of the sulfur producing cystathionine-containing enzymes and the Ag+ ion signal could be detected without the use of any labels; the cells were mapped using the C4H8N+ amino acid fragment. Scanning electron microscopy imaging and energy dispersive x-ray chemical analysis showed that the AgNWs were inside the same cells imaged by TOF-SIMS and transformed chemically into crystalline Ag2S within cells in which the sulfur producing proteins were detected. The presence of these sulfur producing cystathionine-containing enzymes within the cells was confirmed by Western Blots and confocal microscopy images of fluorescently labelled antibodies against the sulfur producing enzymes. Label-free ToF-SIMS is very promising for the label-free identification of H2S-contributing enzymes and their cellular localization in biological systems. The technique could in future be used to identify which of these enzymes are most contributory.

Journal article

Ruenraroengsak P, Kiryushko D, Theodorou IG, Klosowski MM, Taylor ER, Niriella T, Palmieri C, Yagüe E, Ryan MP, Coombes RC, Xie F, Porter AEet al., 2019, Frizzled-7-targeted delivery of zinc oxide nanoparticles to drug-resistant breast cancer cells, Nanoscale, Vol: 11, Pages: 12858-12870, ISSN: 2040-3364

There is a need for novel strategies to treat aggressive breast cancer subtypes and overcome drug resistance. ZnO nanoparticles (NPs) have potential in cancer therapy due to their ability to potently and selectively induce cancer cell apoptosis. Here, we tested the in vitro chemotherapeutic efficacy of ZnONPs loaded via a mesoporous silica nanolayer (MSN) towards drug-sensitive breast cancer cells (MCF-7: estrogen receptor-positive, CAL51: triple-negative) and their drug-resistant counterparts (MCF-7TX, CALDOX). ZnO-MSNs were coated on to gold nanostars (AuNSs) for future imaging capabilities in the NIR-II range. Electron and confocal microscopy showed that MSN-ZnO-AuNSs accumulated close to the plasma membrane and were internalized by cells. High-resolution electron microscopy showed that MSN coating degraded outside the cells, releasing ZnONPs that interacted with cell membranes. MSN-ZnO-AuNSs efficiently reduced the viability of all cell lines, and CAL51/CALDOX cells were more susceptible than MCF7/MCF-7-TX cells. MSN-ZnO-AuNSs were then conjugated with the antibody to Frizzled-7 (FZD-7), the receptor upregulated by several breast cancer cells. We used the disulphide (S-S) linker that could be cleaved with a high concentration of glutathione normally observed within cancer cells, releasing Zn2+ into the cytoplasm. FZD-7 targeting resulted in approximately three-fold amplified toxicity of MSN-ZnO-AuNSs towards the MCF-7TX drug-resistant cell line with the highest FZD-7 expression. This study shows that ZnO-MSs are promising tools to treat triple-negative and drug-resistant breast cancers and highlights the potential clinical utility of FZD-7 for delivery of nanomedicines and imaging probes specifically to these cancer types.

Journal article

Pang JS, Theodorou IG, Centeno A, Petrov PK, Alford NM, Ryan MP, Xie Fet al., 2019, Tunable three-dimensional plasmonic arrays for large near-infrared fluorescence enhancement, ACS Applied Materials and Interfaces, Vol: 11, Pages: 23083-23092, ISSN: 1944-8244

Metal-enhanced fluorescence (MEF), resulting from the near-field interaction of fluorophores with metallic nanostructures, has emerged as a powerful tool for dramatically improving the performance of fluorescence-based biomedical applications. Allowing for lower autofluorescence and minimal photoinduced damage, the development of multifunctional and multiplexed MEF platforms in the near-infrared (NIR) windows is particularly desirable. Here, a low-cost fabrication method based on nanosphere lithography is applied to produce tunable three-dimensional (3D) gold (Au) nanohole–disc arrays (Au-NHDAs). The arrays consist of nanoscale glass pillars atop nanoholes in a Au thin film: the top surfaces of the pillars are Au-covered (effectively nanodiscs), and small Au nanoparticles (nanodots) are located on the sidewalls of the pillars. This 3D hole–disc (and possibly nanodot) construct is critical to the properties of the device. The versatility of our approach is illustrated through the production of uniform and highly reproducible Au-NHDAs with controlled structural properties and tunable optical features in the NIR windows. Au-NHDAs allow for a very large NIR fluorescence enhancement (more than 400 times), which is attributed to the 3D plasmonic structure of the arrays that allows strong surface plasmon polariton and localized surface plasmon resonance coupling through glass nanogaps. By considering arrays with the same resonance peak and the same nanodisc separation distance, we show that the enhancement factor varies with nanodisc diameter. Using computational electromagnetic modeling, the electric field enhancement at 790 nm was calculated to provide insights into excitation enhancement, which occurs due to an increase in the intensity of the electric field. Fluorescence lifetime measurements indicate that the total fluorescence enhancement may depend on controlling excitation enhancement and therefore the array morphology. Our findings provide important in

Journal article

Sk MH, Qi J, Al-Qahtani N, Abdullah AM, Laycock N, Ryan MP, Williams DEet al., 2019, Effect of Trace H2S on the Scale Formation Behavior in a Predominant CO2 Environment under Hydrodynamic Control: Role of Cr/Mo Micro-Alloying in Plain Carbon Steel (vol 166, C3233, 2019), JOURNAL OF THE ELECTROCHEMICAL SOCIETY, Vol: 166, Pages: X3-X3, ISSN: 0013-4651

Journal article

Sk MH, Qi J, Abdullah AM, Laycock N, Ryan MP, Williams DEet al., 2019, Effect of Trace H2S on the Scale Formation Behavior in a Predominant CO2 Environment under Hydrodynamic Control: Role of Cr/Mo Micro-Alloying in Plain Carbon Steel, JOURNAL OF THE ELECTROCHEMICAL SOCIETY, Vol: 166, Pages: C3233-C3240, ISSN: 0013-4651

Journal article

Koronfel MA, Goode AE, Gomez-Gonzalez MA, Nelson Weker J, Simões TA, Brydson R, Quinn P, Toney MF, Hart A, Porter AE, Ryan MPet al., 2019, Chemical Evolution of CoCrMo Wear Particles: an In-Situ Characterisation Study, The Journal of Physical Chemistry C, ISSN: 1932-7447

Journal article

Hadden JHL, Ryan MP, Riley DJ, 2019, Examining the charging behaviour of nickel hydroxide nanomaterials, Electrochemistry Communications, Vol: 101, Pages: 47-51, ISSN: 1388-2481

To investigate the depth of charging at the material surface, batches of nickel hydroxide nanoparticles were hydrothermally synthesised in the range 3–450 nm. Any surfactant added was removed post synthesis using ozone. The capacity per gram (Cs) increased and the capacity per unit area (CA) was constant with decreasing particle size down to 20 nm. Further reduction in particle size resulted in a decrease in both CS and CA, suggesting the Ni(OH)2 is charged to a depth in the order of 10 nm at the charging rate studied. The results obtained have implications in the design of Ni(OH)2 electrodes in charge storage applications.

Journal article

Guo L, Lovell E, Wilson N, Burdett P, Cohen LF, Ryan MPet al., 2019, The electrochemical behaviour of magnetocaloric alloys La(Fe,Mn,Si)13Hx under magnetic field conditions, Chemical Communications, Vol: 55, Pages: 3642-3645, ISSN: 1359-7345

The degradation mechanism of La(Fe,Mn,Si)13Hx has been examined under conditions representative of the complex operating parameters of a refrigeration cycle. The magnetic field effects are found to be dominated by magneto-transport and are most significant when the material is in its paramagnetic state - resulting in significantly accelerated corrosion rates.

Journal article

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