The Department of Natural Sciences is located on Thornton Science Park, a modern expressly-designed site that profits from a recently-completed multi-million pound renovation that has created a state-of-the-art teaching and research facility. The site was home to Shell UK’s exploration and research centre since the 1940s, and its takeover by the University heralded the opportunity to apply its legacy to the continuation of world-class innovation and research in the North West.

Recent Submissions

  • Structural speciation in chemical reactivity profiling of binary-ternary systems of Ni(II) with iminodialcohol and aromatic chelators

    Salifoglou, Athanasios; Papadopoulos, Theodoros; Reimann, M. K.; Pöttgen, R.; Salifoglou, A.; Matsia, S.; Kaoulla, A.; Menelaou, M.; Hatzidimitriou, A.; Aristotle University of Thessaloniki; University of Chester; Universität Münster; Cyprus University of Technology (Elsevier, 2021-11-10)
    The importance of structural speciation in the control of chemical reactivity in Ni(II) binary-ternary systems, involving (O,O,N)-containing substrates (1,1’-iminodi-2-propanol), and aromatic chelators (2,2’-bipyridine, 1,10-phenanthroline), prompted the systematic synthesis of new crystalline materials characterized by elemental analysis, FT-IR, UV-Visible, Luminescence, TGA, magnetic susceptibility, and X-ray crystallography. The structures contain mononuclear octahedral assemblies, the lattice architecture of which exemplifies reaction conditions under which conformational variants and solvent-associated lattice-imposed complexes are assembled. Transformations between complex species denote their association with reactivity pathways, suggesting alternate synthetic methodologies for their isolation. Theoretical work (Hirshfeld, Electrostatic Potential, DFT) signifies the impact of crystal structure on energy profiles of the generated species. The arisen physicochemical profiles of all compounds portray a well-configured interwoven network of pathways, projecting strong connection between structural speciation and Ni(II) reactivity patterns in organic-solvent media. The collective results provide well-defined parameterized profiles, poised to influence the synthesis of new Ni(II)-iminodialcohol materials with specified structural-magneto-optical properties.
  • Optomechanical switching of adsorption configurations of polar organic molecules by UV radiation pressure

    Arumugam, Kowsalya; Papadopoulos, Theodoros; Tang, Shu-Jung; National Tsing Hua University; Tokyo University of Science; National Synchrotron Radiation Research Center (NSRRC); University of Chester
    Using photoemission spectroscopy (PES), we have systematically investigated the behavior of polar organic molecule, chloroaluminum phthalocyanine (ClAlPc), adsorbed in the Cl-down configuration on the Ag(111) substrate at low temperature − 195 °C under UV irradiation with a range of different photon fluxes. Judging from the evolution of photoemission spectral line shapes of molecular energy states, we discovered that the Cl atoms are so robustly anchored at Ag(111) that the impinging photons cannot flip the ClAlPc molecules, but instead they crouch them down due to radiation pressure; we observe that the phthalocyanine (Pc) lobes bend down to interact with Ag atoms on the substrate and induce charge transfer from them. As photon flux is increased, radiation pressure on the Pc plane initiates tunneling of the Cl atom through the molecular plane to turn the adsorption configuration of ClAlPc from Cl-down to an upheld Cl-up configuration, elucidating an optomechanical way of manipulating the dipole direction of polar molecules. Finally, work function measurements provide a distinct signature of the resulting upheld Cl-up configuration as it leads to a large increase in vacuum level (VL), ~ 0.4 eV higher than that of a typical flat-on Cl-up configuration driven by thermal annealing.
  • The United Kingdom Ministry of Defence and the European Union's electrical and electronic equipment directives

    Powell-Turner, Julieanna; Antill, Peter; Fisher, Richard; Cranfield University
    The growth of the generation of Electrical and Electronic Equipment (EEE), and the use of hazardous substances in the production of these items, has required legislation to minimise the harm to the environment that their existing use, ultimate disposal and continued growth of the sector may pose. The European Union (EU) started to tackle this problem with the passing of two Directives in 2002, which focused on restricting the use of hazardous substances (RoHS - 2002/95/EC) and organising the recycling or disposal of discarded electronic and electrical equipment (WEEE - 2002/96/EC). These Directives have been recently recast and their scope widened; however, one exception to them remains items specifically designed for defence and military purposes. This paper looks at how and why these European Directives were passed, the impact they have had on defence in the United Kingdom (UK) up to the present moment, what impact the further extension of those directives might have on UK defence policy and how the UK Ministry of Defence (MOD) has begun to prepare for any extension, including the use of alternative products from the commercial market, and substituting less harmful materials. The paper reviews the information available to carry out future decision making and what level of decision making it can support. Where the data is insufficient, it makes recommendations on actions to take for improvement.
  • Will Future Resource Demand Cause Significant and Unpredictable Dislocations for the UK Ministry of Defence?

    Antill, Peter; Powell-Turner, Julieanna; Cranfield University
    This paper focuses on the drivers which may affect future trends in material availability for defence, in particular, the availability of rare earth elements (REE). These drivers include resource concentration, tighter regulatory policy and its enforcement, export policies, their use in economic statecraft, increases in domestic demand, promoting greater efficiency in resource use, efforts to mitigate resource depletion and more efficient resource extraction while reducing its associated environmental impact. It looks at the effect these factors might have on global systems and supply chains, the impact on material insecurity and how this may exacerbate the issue of their use in UK military equipment. It finds that these drivers are likely to have an increasing impact on material availability (if measures are not taken to mitigate them), which will have consequences for the provision of military capability by the UK.
  • Design, Synthesis and Evaluation of New Bioactive Oxadiazole Derivatives as Anticancer Agents Targeting Bcl-2

    Hamdy, Rania; Elseginy, Samia; Ziedan, Noha; El-Sadek, Mohamed; Lashin, El-Said; Jones, Arwyn T; Westwell, Andrew D; University of Chester; Cardiff University; Zagazig University; Bristol University; University of Sharjah
    A series of 2-(1H-indol-3-yl)-5-substituted-1,3,4-oxadiazoles, 4a–m, were designed, synthesized and tested in vitro as potential pro-apoptotic Bcl-2 inhibitory anticancer agents based on our previously reported hit compounds. Synthesis of the target 1,3,4-oxadiazoles was readily accomplished through a cyclization reaction of indole carboxylic acid hydrazide 2 with substituted carboxylic acid derivatives 3a–m in the presence of phosphorus oxychloride. New compounds 4a–m showed a range of IC50 values concentrated in the low micromolar range selectively in Bcl-2 positive human cancer cell lines. The most potent candidate 4-trifluoromethyl substituted analogue 4j showed selective IC50 values of 0.52–0.88 μM against Bcl-2 expressing cell lines with no inhibitory effects in the Bcl-2 negative cell line. Moreover, 4j showed binding that was two-fold more potent than the positive control gossypol in the Bcl-2 ELISA binding affinity assay. Molecular modeling studies helped to further rationalize anti-apoptotic Bcl-2 binding and identified compound 4j as a candidate with drug-like properties for further investigation as a selective Bcl-2 inhibitory anticancer agent.
  • A promising laser nitriding method for the design of next generation orthopaedic implants: Cytotoxicity and antibacterial performance of titanium nitride (TiN) wear nano-particles, and enhanced wear properties of laser-nitrided Ti6Al4V surfaces

    Chan, Chi Wai; Quinn, James; Hussain, Issam; Carson, Louise; Smith, Graham; Lee, Seunghwan; Queen's University Belfast; University of Lincoln; University of Chester; Technical University of Denmark
    In this study, fibre laser nitriding in open air was applied to the Ti6Al4V alloy in order to improve the wear resistance, thus minimising the generation of wear debris from the surfaces for load-bearing applications. The recent technological advancement to perform the laser nitriding process in open air allows the opportunity to surface-harden any curved and/or specific areas in the hip implants. The laser nitriding process was modulated between the pulsed mode and continuous wave (CW) mode by varying the duty cycle between 60% (pulsed) and 100% (CW). Our experimental investigations were divided into two stages in sequential order: Firstly, to create crack-free, homogenous and golden laser-nitrided surfaces by the proper selection of duty cycle. Secondly, it was to analyse the properties (both physical and chemical) of the wear debris as well as to evaluate their cytotoxicity and antibacterial performance. The laser-nitrided surfaces were characterised and tested using a variety of techniques, incl. optical microscopy, SEM-EDX, XRD, surface roughness and Vickers hardness measurements, as well as tribological tests (i.e. ball-on-disk wear tests and DLS). The wear debris from the laser-nitrided surfaces (collected in the wear tests) were analysed using TEM, XPS and SEM-EDX. Their toxicity was evaluated using in-vitro cell culture with macrophages at two time points (24 h and 48 h). The antibacterial performance was tested in vitro against two of the most commonly implicated pathogens in orthopaedic infection, namely Staphylococcus aureus and Escherichia coli for 24 h. Our findings indicated that the wear resistance of the surfaces after laser nitriding was significantly improved and the amount of wear debris generated was also significantly reduced. The wear particles from the laser-nitrided surfaces were in the nano-sized scale range (0.01 µm to 0.04 µm or 10 nm to 40 nm). They were found to be less toxic towards RAW264.7 macrophages, yet display antimicrobial properties against Staphylococcus aureus, when compared with the larger particles (1.5 µm in size) from the untreated surfaces. It is envisioned that successful fabrication of the non-toxic and highly wear-resistant TiN layer in Ti6Al4V using the open-air laser nitriding technique can enable progress towards the development of metal-on-metal (MoM) hip implants fully made of Ti-based alloys
  • Versailles Project on Advanced Materials and Standards interlaboratory study on intensity calibration for x-ray photoelectron spectroscopy instruments using low-density polyethylene

    Reed, Benjamin; Cant, David; Spencer, Steve; Carmona-Carmona, Abraham; Bushell, Adam; Herrera-Gomez, Alberto; Kurokawa, Akira; Thissen, Andreas; Thomas, Andrew; Britton, Andrew; et al.
    We report the results of a Versailles Project on Advanced Materials and Standards interlaboratory study on the intensity scale calibration of x-ray photoelectron spectrometers using low-density polyethylene (LDPE) as an alternative material to gold, silver, and copper. An improved set of LDPE reference spectra, corrected for different instrument geometries using a quartz-monochromated Al Kα x-ray source, was developed using data provided by participants in this study. Using these new reference spectra, a transmission function was calculated for each dataset that participants provided. When compared to a similar calibration procedure using the NPL reference spectra for gold, the LDPE intensity calibration method achieves an absolute offset of ∼3.0% and a systematic deviation of ±6.5% on average across all participants. For spectra recorded at high pass energies (≥90 eV), values of absolute offset and systematic deviation are ∼5.8% and ±5.7%, respectively, whereas for spectra collected at lower pass energies (<90 eV), values of absolute offset and systematic deviation are ∼4.9% and ±8.8%, respectively; low pass energy spectra perform worse than the global average, in terms of systematic deviations, due to diminished count rates and signal-to-noise ratio. Differences in absolute offset are attributed to the surface roughness of the LDPE induced by sample preparation. We further assess the usability of LDPE as a secondary reference material and comment on its performance in the presence of issues such as variable dark noise, x-ray warm up times, inaccuracy at low count rates, and underlying spectrometer problems. In response to participant feedback and the results of the study, we provide an updated LDPE intensity calibration protocol to address the issues highlighted in the interlaboratory study. We also comment on the lack of implementation of a consistent and traceable intensity calibration method across the community of x-ray photoelectron spectroscopy (XPS) users and, therefore, propose a route to achieving this with the assistance of instrument manufacturers, metrology laboratories, and experts leading to an international standard for XPS intensity scale calibration.
  • Modified magnetic core-shell mesoporous silica nano-formulations with encapsulated quercetin exhibit anti-amyloid and antioxidant activity

    Halevas, Eleftherios; Mavroidi, Barbara; Nday, Christiane; Tang, Jianhua; Smith, Graham; Boukos, Nikos; Litsardakis, George; Pelecanou, Maria; Salifoglou, Athanasios; NCSR "Demokritos" Athens (Halevas, Mavroidi, Pelecanou), University of Chester (Tang, Smith), Aristotle University of Thessalonika (Litsardakis, Nday) (Elsevier, 2020-10-06)
    Targeted tissue drug delivery is a challenge in contemporary nanotechnologically driven therapeutic approaches, with the interplay interactions between nanohost and encapsulated drug shaping the ultimate properties of transport, release and efficacy of the drug at its destination. Prompted by the need to pursue the synthesis of such hybrid systems, a family of modified magnetic core-shell mesoporous silica nano-formulations was synthesized with encapsulated quercetin, a natural flavonoid with proven bioactivity. The new nanocarriers were produced via the sol-gel process, using tetraethoxysilane as a precursor and bearing a magnetic core of surface-modified monodispersed magnetite colloidal superparamagnetic nanoparticles, subsequently surface-modified with polyethylene glycol 3000 (PEG3k). The arising nano-formulations were evaluated for their textural and structural properties, exhibiting enhanced solubility and stability in physiological media, as evidenced by the loading capacity, entrapment efficiency results and in vitro release studies of their load. Guided by the increased bioavailability of quercetin in its encapsulated form, further evaluation of the biological activity of the magnetic as well as non-magnetic core-shell nanoparticles, pertaining to their anti-amyloid and antioxidant potential, revealed interference with the aggregation of β-amyloid peptide (Aβ) in Alzheimer’s disease, reduction of Aβ cellular toxicity and minimization of Aβ-induced Reactive Oxygen Species (ROS) generation. The data indicate that the biological properties of released quercetin are maintained in the presence of the host nanocarriers. Collectively, the findings suggest that the emerging hybrid nano-formulations can function as efficient nanocarriers of hydrophobic natural flavonoids in the development of multifunctional nanomaterials toward therapeutic applications.
  • Optimization of anti-wear and anti-bacterial properties of beta TiNb alloy via controlling duty cycle in open-air laser nitriding

    Chang, Xianwen; Smith, Graham; Quinn, James; Carson, Louise; Chan, Chi-Wai; Lee, Seunghwan; Technical University of Denmark (Chang, Lee), University of Chester (Smith), Queens University Belfast (Quinn, Chan) (Elsevier, 2020-07-09)
    A multifunctional beta TiNb surface, featuring wear-resistant and antibacterial properties, was successfully created by means of open-air fibre laser nitriding. Beta TiNb alloy was selected in this study as it has low Young’s modulus, is highly biocompatible, and thus can be a promising prosthetic joint material. It is, however, necessary to overcome intrinsically weak mechanical properties and poor wear resistance of beta TiNb in order to cover the range of applications to loadbearing and/or shearing parts. To this end, open-air laser nitriding technique was employed. A control of single processing parameter, namely duty cycle (between 5% and 100%), led to substantially different structural and functional properties of the processed beta TiNb surfaces as analyzed by an array of analytical tools. The TiNb samples nitrided at the DC condition of 60% showed a most enhanced performance in terms of improving surface hardness, anti-friction, antiwear and anti-bacterial properties in comparison with other conditions. These findings are expected to be highly important and useful when TiNb alloys are considered as materials for hip/knee articular joint implants
  • UV phototransistors based upon spray coated and sputter deposited ZnO TFTs

    Kumar, Dinesh; Gomes, Tiago; Santos, Lucas; Smith, Graham; Kettle, Jeff; Bangor University (Kumar, Kettle), Sao Paulo State University (Gomes, Alves, Santos), University of Chester (Smith)
    A comparison of Zinc Oxide (ZnO) phototransistors prepared by spray and sputter coating process is presented. The work shows that spray coated layers provide significant advantages in sensor response over ZnO phototransistors made by physical vapour deposition and we show that spray deposited ZnO phototransistors can exhibit state-of-the-art performances for UV photodetectors. Topographic images of the samples surface shows that there is increase in surface roughness in spray coated samples indicating increasing grain sizes, which is considered the source of the greater sensor responsivity. X-ray photoelectron spectroscopy (XPS) is also used to understand the root cause of the greater UV responsivity. It was observed that sprayed ZnO TFTs are more sensitive to UV radiation due to higher adsorption of oxygen level. Responsivity and external quantum efficiency (EQE) of the sprayed and sputtered ZnO TFTs are also evaluated.
  • Graphene Oxide Bulk Modified Screen-Printed Electrodes Provide Beneficial Electroanalytical Sensing Capabilities

    Rowley-Neale, Samuel; Brownson, Dale; Smith, Graham; Banks, Craig; Manchester Metropolitan University; University of Chester (MDPI, 2020-03-19)
    We demonstrate a facile methodology for the mass production of graphene oxide (GO) bulk modified screen-printed electrodes (GO-SPEs) that are economical, highly reproducible and provide analytically useful outputs. Through fabricating GO-SPEs with varying percentage mass incorporations (2.5, 5, 7.5 and 10%) of GO, an electrocatalytic effect towards the chosen electroanalytical probes is observed, that increases with greater GO incorporated compared to bare/ graphite SPEs. The optimum mass ratio of 10% GO to 90% carbon ink displays an electroanalytical signal towards dopamine (DA) and uric acid (UA), which is ca. ×10 greater in magnitude than that achievable at a bare/unmodified graphite SPE. Furthermore, 10% GO-SPEs exhibit a competitively low limit of detection (3σ) towards DA at ca. 81 nM, which is superior to that of a bare/unmodified graphite SPE at ca. 780 nM. The improved analytical response is attributed to the large number of oxygenated species inhabiting the edge and defect sites of the GO nanosheets, which are available to exhibit electrocatalytic responses towards inner-sphere electrochemical analytes. Our reported methodology is simple, scalable, and cost effective for the fabrication of GO-SPEs, that display highly competitive LODs, and is of significant interest for use in commercial and medicinal applications
  • MoS2-graphene-CuNi2S4 nanocomposite an efficient electrocatalyst for the hydrogen evolution reaction

    Adarakatti, Prashanth Shivappa; Mahanthappa, Mallappa; Hughes, Jack; Rowley-Neale, Samuel; Smith, Graham; S, Ashoka; Banks, Craig; Manchester Metropolitan University, University of Chester, Bengaluru
    We present a facile methodology for the synthesis of a novel 2D-MoS2, graphene and CuNi2S4 (MoS2-g-CuNi2S4) nanocomposite that displays highly efficient electrocatalytic activity towards the production of hydrogen. The intrinsic hydrogen evolution reaction (HER) activity of MoS2 nanosheets was significantly enhanced by increasing the affinity of the active edge sites towards Hþ adsorption using transition metal (Cu and Ni2) dopants, whilst also increasing the edge sites exposure by anchoring them to a graphene frame- work. Detailed XPS analysis reveals a higher percentage of surface exposed S at 17.04%, of which 48.83% is metal bonded S (sulfide). The resultant MoS2-g-CuNi2S4 nanocomposites are immobilized upon screen-printed electrodes (SPEs) and exhibit a HER onset potential and Tafel slope value of -0.05 V (vs. RHE) and 29.3 mV dec-1, respectively. These values are close to that of the polycrystalline Pt electrode (near zero potential (vs. RHE) and 21.0 mV dec-1, respectively) and enhanced over a bare/unmodified SPE (-0.43 V (vs. RHE) and 149.1 mV dec-1, respectively). Given the efficient, HER activity displayed by the novel MoS2-g-CuNi2S4/SPE electrochemical platform and the comparatively low associated cost of production for this nanocomposite, it has potential to be a cost-effective alternative to Pt within electrolyser technologies.
  • The past, present and future of indoor air chemistry

    Bekö, Gabriel; Carslaw, Nicola; Fauser, Patrick; Kauneliene, Violeta; Nehr, Sascha; Phillips, Gavin; Saraga, Dikaia; Schoemaecker, Coralie; Wierzbicka, Aneta; Querol, Xavier; et al. (Wiley, 2020-04-25)
    This is an editorial contribution to the Journal Indoor Air on the future direction of indoor air chemistry research.
  • A single parameter approach to enhance the microstructural and mechanical properties of beta Ti-Nb alloy via open-air fiber laser nitriding

    Chan, Chi-Wai; Chang, Xianwen; Bozorgzadeh, Mohammad Amin; Smith, Graham C; Lee, Seunghwan; Queen's University Belfast, Technical University of Denmark, University of Chester (Elsevier, 2019-12-13)
    In this study, the idea of applying open-air laser nitriding to improve the microstructural and mechanical properties of beta Ti-45 at.% Nb alloy was demonstrated. Surface cracking after laser nitriding is one of the main reasons impeding direct translation of the laser nitriding technique from the laboratories to industries as cracks can be the weak points to initiate mechanical and corrosion failures in long-term usage. With proper selection of duty cycle (DC) between 40% (modulated mode) and 100% (continuous wave, CW mode) to control the laser energy input and laser-material-gas interaction time, the cracking problems of laser nitriding can be alleviated and even solved. A crack-free and uniformly gold-coloured nitrided surface was successfully obtained at the DC of 40% in this study. The morphology, microstructure, composition and mechanical properties of the nitrided samples were studied and analysed by optical microscopy (OM), scanning electron microscopy (SEM), SEM-energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and Vickers micro-hardness tests. The OM results indicated that minimum overlapping between the laser tracks would give desirable results to obtain the crack-free surface. The measurements from the SEM micrographs indicated the depth of the laser-nitrided areas ranged between 22 and 43 µm. The XRD findings showed that a clear conversion of the TiNb surface to a nitride as a result of laser nitriding was observed. The maximum hardness, as measured by the Vickers method in cross-sections, lay in the range of 780 to 870 HV after laser nitriding. To summarise, control of DC to obtain a crack free and quality surface via fiber laser nitriding in open air is a simpler and quicker approach in comparison with the conventional substrate preheating and nitrogen (N) dilution approaches. The single-parameter approach is more efficient than parameter optimisation via design of experiments (DOE) employed in conventional methods.
  • Additively Manufactured Graphitic Electrochemical Sensing Platforms

    Foster, Christopher W; El Bardisy, Hadil M; Down, Michael P; Keefe, Edmund M; Smith, Graham C; Banks, Craig E; Manchester Metropolitan University (Foster, El Bardisy, Down, Keefe, Banks), University of Chester (Smith) (Elsevier, 2020-02-01)
    Additive manufacturing (AM)/3D printing technology provides a novel platform for the rapid prototyping of low cost 3D platforms. Herein, we report for the first time, the fabrication, characterisation (physicochemical and electrochemical) and application (electrochemical sensing) of bespoke nanographite (NG)-loaded (25 wt. %) AM printable (via fused deposition modelling) NG/PLA filaments. We have optimised and tailored a variety of NG-loaded filaments and their AM counterparts in order to achieve optimal printability and electrochemical behaviour. Two AM platforms, namely AM macroelectrodes (AMEs) and AM 3D honeycomb (macroporous) structures are benchmarked against a range of redox probes and the simultaneous detection of lead (II) and cadmium (II). This proof-of-concept demonstrates the impact that AM can have within the area of electroanalytical sensors.
  • Magnetic cationic liposomal nanocarriers for the efficient drug delivery of a curcumin-based vanadium complex with anticancer potential

    Halevesa, Eleftherios; Mavroidi, Barbara; Moschona, Alexandra; Hadjispyrou, Spyros; Salifoglou, Athanasios; Pelecanou, Maria; Litsardakis, George; Pantazaki, Anastasia; Swanson, Claudia H.; Smith, Graham C.; et al. (Elsevier, 2019-07-15)
    In this work novel magnetic cationic liposomal nanoformulations were synthesized for the encapsulation of a crystallographically defined ternary V(IV)-curcumin-bipyridine (VCur) complex with proven bioactivity, as potential anticancer agents. The liposomal vesicles were produced via the thin film hydration method employing N-[1-(2,3-dioleoyloxy)propyl]-N,N,N-trimethylammonium (DOTAP) and egg phosphatidylcholine lipids and were magnetized through the addition of citric acid surface-modified monodispersed magnetite colloidal magnetic nanoparticles. The obtained nanoformulations were evaluated for their structural and textural properties and shown to have exceptional stability and enhanced solubility in physiological media, demonstrated by the entrapment efficiency and loading capacity results and the in vitro release studies of their cargo. Furthermore, the generated liposomal formulations preserved the superparamagnetic behavior of the employed magnetic core maintaining the physicochemical and morphological requirements for targeted drug delivery applications. The novel nanomaterials were further biologically evaluated for their DNA interaction potential and were found to act as intercalators. The findings suggest that the positively charged magnetic liposomal nanoformulations can generate increased concentration of their cargo at the DNA site, offering a further dimension in the importance of cationic liposomes as nanocarriers of hydrophobic anticancer metal ion complexes for the development of new multifunctional pharmaceutical nanomaterials with enhanced bioavailability and targeted antitumor activity.
  • Self-assembled nanostructures in ionic liquids facilitate charge storage at electrified interfaces

    Mao, Xianwen; Brown, Paul; Cervinka, Citrad; Hazell, Gavin; Li, Hua; Ren, Yinying; Chen, Di; Atkin, Rob; Eastoe, Julian; Grillo, Isabelle; et al. (Springer Nature, 2019-08-12)
    Driven by the potential applications of ionic liquids (ILs) in many emerging electrochemical technologies, recent research efforts have been directed at understanding the complex ion ordering in these systems, to uncover novel energy storage mechanisms at IL–electrode interfaces. Here, we discover that surface-active ILs (SAILs), which contain amphiphilic structures inducing self-assembly, exhibit enhanced charge storage performance at electrified surfaces. Unlike conventional non amphiphilic ILs, for which ion distribution is dominated by Coulombic interactions, SAILs exhibit significant and competing van der Waals interactions owing to the non-polar surfactant tails, leading to unusual interfacial ion distributions. We reveal that, at an intermediate degree of electrode polarization, SAILs display optimum performance, because the low-charge-density alkyl tails are effectively excluded from the electrode surfaces, whereas the formation of non-polar domains along the surface suppresses undesired overscreening effects. This work represents a crucial step towards understanding the unique interfacial behaviour and electrochemical properties of amphiphilic liquid systems showing long-range ordering, and offers insights into the design principles for high-energy-density electrolytes based on spontaneous self-assembly behaviour.
  • The effect of irradiation impinging on disparate anchoring configurations of polar-organic molecules adsorbed on bulk and thin-film metal surfaces

    Papadopoulos, Theodoros A.; Metz, Sebastian; Tang, Shu-Jung; University of Chester; Daresbury Laboratory; National Tsing-Hua University (Elsevier, 2019-07-11)
    The behavior of polar metal organic molecules, chloroaluminum phthalocyanine (ClAlPc), upon ultraviolet (UV) irradiation was investigated to evaluate the stability of the adsorption process on the Ag(111) thin film and bulk crystal. Angle-resolved photoelectron spectroscopy (ARPES) was mainly employed to measure the molecular energy states (MES) and vacuum level (VL) shift for 1-ML ClAlPc in the Cl-down configuration. A consistent trend was observed showing that ClAlPc in the Cl-down configuration is energetically more stable on the Ag thin-film surface than on the corresponding surface of the Ag bulk crystal. The intermediate adsorption state in tilted configuration during the irradiation impinging is identified by large positive VL shifts and broad spectra line shapes to infer a flipping mechanism from Cl-down to Cl-up configuration. Strain on the Ag thin films from the underlying mismatched Ge(111) substrate is considered to cause enlarged hollow sites on the Ag(111) thin-films, that anchor the Cl-down configuration more tightly on the thin-film surfaces, as confirmed by density functional theory (DFT) calculations.
  • Evidence of Lipid Exchange in Styrene Maleic Acid Lipid Particle (SMALP) Nanodisc Systems

    Hazell, Gavin; Arnold, Thomas; Tognoloni, Cecilia; Barker, Robert; Clifton, Luke; Steinke, Nina-Juliane; Edler, Karen; University of Chester, University of Bath, University of Dundee, ISIS, Diamond Light Source (American Chemical Society, 2016-10-14)
    Styrene-alt-maleic Acid lipid particles (SMALPs) are self-assembled discoidal structures composed of a polymer belt and a segment of lipid bilayer, which are capable of encapsulating membrane proteins directly from the cell membrane. Here we present evidence of the exchange of lipids between such “nanodiscs” and lipid monolayers adsorbed at either solid-liquid or air-liquid interfaces. This behavior has important implications for the potential uses of nanodiscs, including the potential to control lipid composition within nanodiscs containing membrane proteins
  • Next-Generation Additive Manufacturing of Complete Standalone Sodium-Ion Energy Storage Architectures

    Down, Michael P.; Martinez-Perinan, Emiliano; Foster, Christopher W.; Lorenzo, Encarnacion; Smith, Graham C.; Banks, Craig E.; Manchester Metropolitan University (Down, Martinez-Perinan, Foster, Banks), Universidad Autonoma Madrid (Lorenzo), University of Chester (Smith) (Wiley, 2019-02-10)
    The first entirely AM/3D-printed sodium-ion (full-cell) battery is reported herein, presenting a paradigm shift in the design and prototyping of energy- storage architectures. AM/3D-printing compatible composite materials are developed for the first time, integrating the active materials NaMnO2 and TiO2 within a porous supporting material, before being AM/3D- printed into a proof-of-concept model based upon the basic geometry of commercially existing AA battery designs. The freestanding and completely AM/3D-fabricated device demonstrates a respectable performance of 84.3 mAh g-1 with a current density of 8.43 mA g-1; note that the structure is typically comprised of 80% thermoplastic, but yet, still works and functions as an energy-storage platform. The AM/3D-fabricated device is critically benchmarked against a battery developed using the same active materials, but fabricated via a traditional manufacturing method utilizing an ink-based/doctor-bladed methodology, which is found to exhibit a specific capacity of 98.9 mAh m-2 (116.35 mAh g-1). The fabrication of fully AM/3D-printed energy-storage architectures compares favorably with traditional approaches, with the former providing a new direction in battery manufacturing. This work represents a paradigm shift in the technological and design considerations in battery and energy-storage architectures

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