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

  • 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)
    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
  • Studies of black diamond as an antibacterial surface for gram negative bacteria: the interplay between chemical and mechanical bactericidal activity

    Dunseath, Olivia; Smith, E. J. W.; Al-Jeda, T.; Smith, J. A.; King, Sophie; May, Paul W.; Nobbs, Angela H.; Hazell, Gavin; Welch, Colin C.; Su, Bo; et al. (Nature, 2019-06-19)
    ‘Black silicon’ (bSi) samples with surfaces covered in nanoneedles of length ~5 μm were fabricated using a plasma etching process and then coated with a conformal uniform layer of diamond using hot filament chemical vapour deposition to produce ‘black diamond’ (bD) nanostructures. The diamond needles were then chemically terminated with H, O, NH2 or F using plasma treatment, and the hydrophilicity of the resulting surfaces were assessed using water droplet contact-angle measurements, and scaled in the order O > H ≈NH2 >F, with the F-terminated surface being superhydrophobic. The effectiveness of these differently terminated bD needles in killing the Gram-negative bacterium E. coli was semiquantified by Live/Dead staining and fluorescence microscopy, and visualised by environmental scanning electron microscopy. The total number of adhered bacteria was consistent for all the nanostructured bD surfaces at around 50% of the value for the flat diamond control. This, combined with a chemical bactericidal effect of 20–30%, shows that the nanostructured bD surfaces supported significantly fewer viable E. coli than flat surfaces. Moreover, the bD surfaces were particularly effective at preventing the establishment of bacterial aggregates – a precursor to biofilm formation. The percentage of dead bacteria also decreased as a function of hydrophilicity. These results are consistent with a predominantly mechanical mechanism for bacteria death based on the stretching and disruption of the cell membrane, combined with an additional effect from the chemical nature of the surface.
  • Next Generation Additive Manufacturing: Tailorable Graphene/Polylactic(acid) Filaments Allow the Fabrication of 3D Printable Porous Anodes for Utilisation within Lithium-Ion Batteries

    Foster, Christopher W.; Zou, Guo-Qiang; Jiang, Yunling; Down, Michael P.; Liauw, Christopher M.; Ferrari, Alejandro Garcia-Miranda; Ji, Xiaobo; Smith, Graham C.; Kelly, Peter J.; Banks, Craig E.; et al. (Wiley, 2019-04-02)
    Herein, we report the fabrication and application of Li-ion anodes for utilisation within Li-ion batteries, which are fabricated via additive manufacturing/3D printing (fused depo- sition modelling) using a bespoke graphene/polylactic acid (PLA) filament, where the graphene content can be readily tailored and controlled over the range 1–40 wt. %. We demon- strate that a graphene content of 20 wt. % exhibits sufficient conductivity and critically, effective 3D printability for the rapid manufacturing of 3D printed freestanding anodes (3DAs); simplifying the components of the Li-ion battery negating the need for a copper current collector. The 3DAs are physicochemcally and electrochemically characterised and possess sufficient conductivity for electrochemical studies. Critically, it is found that if the 3DAs are used in Li-ion batteries the specific capacity is very poor but can be significantly improved through the use of a chemical pre-treatment. Such treatment induces an increased porosity, which results in a 200-fold increase (after anode stabilisation) of the specific capacity (ca. 500 mAhg-1 at a current density of 40 mAg-1). This work significantly enhances the field of additive manufacturing/3D printed graphene based energy storage devices demonstrating that useful 3D printable batteries can be realised
  • A novel ‘bottom-up’ synthesis of few- and multi-layer graphene platelets with partial oxidation via cavitation

    Price, Richard J.; Ladislaus, Paul I.; Smith, Graham C.; Davies, Trevor J.; University of Chester (Price, Davies, Smith), Thomas Swan Ltd (Ladislaus) (Elsevier, 2019-03-28)
    The transient cavitation of diaromatic components such as 1-methylnaphthalene has been used to produce graphene platelets in a ‘bottom-up’ synthesis via the high temperature (>5000 K) conditions that are generated inside collapsing bubbles. Acoustic cavitation produced yields of 5.7×10−11 kgJ−1 at a production rate of 2.2×10−9 kgs−1. This can be improved by generating cavitation hydrodynamically, thus making commercial scale production viable. Hydrodynamic cavitation produced platelets with larger lateral dimensions (≥2 μm) than those formed by acoustic cavitation (10–200 nm). The partially oxidised nature of the platelets enables their covalent chemical functionalisation, which was achieved by combining suitable molecules in the reaction medium to affect a one-pot formation and functionalisation of graphene
  • The physicochemical investigation of hydrothermally reduced textile waste and application within carbon-based electrodes

    Randviir, Edward P.; Kanou, Omar; Liauw, Christopher M.; Miller, Gary; Andrews, Hayley; Smith, Graham C.; Manchester Metropolitan University; University of Chester (Royal Society of Chemistry, 2019-04-10)
    Textile waste is on the rise due to the expanding global population and the fast fashion market. Large volumes of textile waste are increasing the need for new methods for recycling mixed fabric materials. This paper employs a hydrothermal conversion route for a polyester/cotton mix in phosphoric acid to generate carbon materials (hydrochars) for electrochemical applications. A combination of characterization techniques revealed the reaction products were largely comprised of two major components. The first is a granular material with a surface C : O ratio of 2 : 1 interspersed with phosphorous and titanium proved using energy dispersive X-ray spectroscopy, and the other is a crystalline material with a surface C : O ratio of 3 : 2 containing no phosphorous or titanium. The latter material was found via X-ray diffraction and differential scanning calorimetry to be terephthalic acid. Electrochemical experiments conducted using the hydrochar as a carbon paste electrode demonstrates an increase in current response compared to carbon reference materials. The improved current responses, intrinsically related to the surface area of the material, could be beneficial for electrochemical sensor applications, meaning that this route holds promise for the development of a cheap recycled carbon material, using straightforward methods and simple laboratory reagents.
  • New Quinoline-Based Heterocycles as Anticancer Agents Targeting Bcl-2

    Hamdy, Rania; Elseginy, Samia A.; Ziedan, Noha I.; Jones, Arwyn T.; Westwell, Andrew D. (MDPI, 2019-04-02)
    The Bcl-2 protein has been studied as an anticancer drug target in recent years, due to its gatekeeper role in resisting programmed cancer cell death (apoptosis), and the design of BH3 domain mimetics has led to the clinical approval of Venetoclax (ABT-199) for the treatment of chronic lymphocytic leukaemia. In this work we extend our previous studies on the discovery of indole-based heterocycles as Bcl-2 inhibitors, to the identification of quinolin-4-yl based oxadiazole and triazole analogues. Target compounds were readily synthesized via a common aryl-substituted quinolin-4-carbonyl-N-arylhydrazine-1-carbothioamide (5a⁻b) intermediate, through simple variation of the basic cyclisation conditions. Some of the quinoline-based oxadiazole analogues (e.g. compound 6i) were found to exhibit sub-micromolar anti-proliferative activity in Bcl-2-expressing cancer cell lines, and sub-micromolar IC50 activity within a Bcl2-Bim peptide ELISA assay. The Bcl-2 targeted anticancer activity of 6i was further rationalised via computational molecular modelling, offering possibilities to extend this work into the design of further potent and selective Bcl-2 inhibitory heteroaromatics with therapeutic potential.
  • Chemical ionization quadrupole mass spectrometer with an electrical discharge ion source for atmospheric trace gas measurement

    Eger, Philipp G.; Helleis, Frank; Schuster, Gerhard; Phillips, Gavin J.; Lelieveld, Jos; Crowley, John N.; Max Planck Institute for Chemistry; University of Chester (Copernicus Publications, 2019-03-26)
    We present a chemical ionization quadrupole mass spectrometer (CI-QMS) with a radio-frequency (RF) discharge ion source through N2∕CH3I as a source of primary ions. In addition to the expected detection of PAN, peracetic acid (PAA) and ClNO2 through well-established ion–molecule reactions with I− and its water cluster, the instrument is also sensitive to SO2, HCl and acetic acid (CH3C(O)OH) through additional ion chemistry unique to our ion source. We present ionization schemes for detection of SO2, HCl and acetic acid along with illustrative datasets from three different field campaigns underlining the potential of the CI-QMS with an RF discharge ion source as an alternative to 210Po. The additional sensitivity to SO2 and HCl makes the CI-QMS suitable for investigating the role of sulfur and chlorine chemistry in the polluted marine and coastal boundary layer.
  • Nanodiamond based surface modified screen-printed electrodes for the simultaneous voltammetric determination of dopamine and uric acid.

    Baccarin, Marina; Rowley-Neale, Samuel J.; Cavalheiro, Éder T. G.; Smith, Graham C.; Banks, Craig E. (2019-02-22)
    The electroanalytical detection of the neurotransmitter dopamine (DA) in the presence of uric acid (UA) is explored for the first time using commercially procured nanodiamonds (NDs). These are electrically wired via surface modification upon screen-printed graphite macroelectrodes (SPEs). The surface coverage of the NDs on the SPEs was explored in order to optimize electroanalytical outputs to result in well-resolved signals and in low limits of detection. The (electro)analytical outputs are observed to be more sensitive than those achieved at bare (unmodified) SPEs. Such responses, previously reported in the academic literature have been reported to be electrocatalytic and have been previously attributed to the presence of surface sp2 carbon and oxygenated species on the surface of the NDs. However, XPS analysis reveals the commercial NDs to be solely composed of nonconductive sp3 carbon. The low/negligible electroconductivity of the NDs was further confirmed when ND paste electrodes were fabricated and found to exhibit no electrochemical activity. The electroanalytical enhancement, when using NDs electronically wired upon SPEs, is attributed not to the NDs themselves being electrocatalytic, as reported previously, but rather changes in mass transport where the inert NDs block the underlying electroactive SPEs and create a random array of graphite microelectrodes. The electrode was applied to simultaneous sensing of DA and UA at pH 5.5. Figures of merit include (a) low working potentials of around 0.27 and 0.35 V (vs. Ag/AgCl); and (b) detection limits of 5.7 × 10-7 and 8.9 × 10-7 M for DA and UA, respectively. Graphical abstract The electroanalytical enhancement of screen-printed electrodes modified with inert/non-conductive nanodiamonds is due to a change in mass transfer where the inert nanodiamonds facilitate the production of a random microelectrode array.

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