AuNP-Agglomerated monoliths in pipette tips for lectin affinity extraction of glycoproteins

• To in situ fabricate ethylene dimethacrylate porous polymer monoliths within the confines of a commercial 20 μL polypropylene pipette tips. • To enhance the monolith surface area by immobilising AuNPs and then functionalise the AuNPs with ECL lectin for selective extraction of galactosylated proteins from complex media

Highly Selective Fluorimetric Turn-Off Detection of Copper (II) by Two Different Mechanisms in Calix[4]arene-Based Chemosensors and Chemodosimeters

Isoxazolo‐pyrene tethered calix[4]arenes selectively detect copper(II) ions without interference from related perchlorate ions. The fluorescence emission of the probes, synthesised by nitrile oxide alkyne cycloaddition, and characterised by spectroscopic and crystallographic data, is rapidly reduced by Cu(II) ions. Detection limits are in the micromolar or sub‐micromolar range (0.3–3.6 μM) based on a 1 : 1 sensor:analyte interaction. Voltammetric behaviour and 1H NMR data provide new insights into the sensing mechanism which is dependent on the calixarene substitution pattern. When the calixarene lower rim is fully substituted, Cu(II) detection occurs through a traditional chelation mechanism. In contrast, for calixarenes 1,3‐disubstituted on the lower rim, detection takes place through a chemodosimetric redox reaction. The isolation of a calix[4]diquinone from the reaction with excess Cu(ClO4)2 provides confirmation that the sensor–analyte interaction culminates in irreversible sensor oxidation

Characterisation of isothiocyanic acid, HNCS, in the solid state: trapped by hydrogen bonding

The crystal structure of [Ph4P][NCS]·HNCS is reported. This is the first structural determination of isothiocyanic acid and hydrogen bonding between the NCS anion and HNCS fragment explored using computational chemistry

Novel class of Bi(iii) hydroxamato complexes: synthesis, urease inhibitory activity and activity against H. pylori.

Reaction of Bi(NO3)3 with benzohydroxamic acid (Bha) and salicylhydroxamic acid (Sha) gives the novel Bi(iii) complexes [Bi2(Bha-1H)2(μ-Bha-1H)2(η(2)-NO3)2] () and [Bi6(CH3OH)2(η(1)-NO3)2(η(2)-NO3)(OH2)2(Sha-1H)12](NO3)2 (). X-ray crystal structure of reveals two hydroxamato coordination modes; bidentate bridging (O, O\u27) and bidentate non-bridging (O, O\u27) and of reveals one coordination mode; bidentate bridging (O, O\u27). , specifically designed to and demonstrated to inhibit the activity of urease, exhibits excellent antibacterial activity against three strains of Helicobacter pylori with MIC ≥ 16 μg mL(-1)

The application of chiroptical spectroscopy (circular dichroism) in quantifying binding events in lanthanide directed synthesis of chiral luminescent self-assembly structures

The binding of asymmetrical and optically pure tridentate ligands (L = 1(S) and 1(R)) containing one carboxylic group and 2-naphthyl as an antenna to lanthanide ions (M = La(III) and Eu(III)) was studied in CH3CN, showing the successive formation of M:L, M:L2 and M:L3 stoichiometric species in solution. The europium complexes EuL3 were also synthesised, structurally characterised and their photophysical properties probed in CH3OH and CH3CN. The changes in the chiroptical properties of both 1(S) and 1(R) were used (by circular dichroism (CD) spectroscopy) to monitor the formation of these chiral selfassemblies in solution. While circularly polarised luminescence (CPL) showed the formation of Eu(1(S))3 and Eu(1(R))3 as enantiomers, with high luminescence dissymmetry factors (glum), fitting the CD changes allowed for binding constants to be determined that were comparable to those seen in the analyses of absorbance and luminescence changes

Structural variability of 4f and 5f thiocyanate complexes and dissociation of uranium(III)–thiocyanate bonds with increased ionicity

A series of complexes [Et4N][Ln(NCS)4(H2O)4] (Ln = Pr, Tb, Dy, Ho, Yb) have been structurally characterized, all showing the same structure, namely a distorted square antiprismatic coordination geometry, and the Ln–O and Ln–N bond lengths following the expected lanthanide contraction. When the counterion is Cs+, a different structural motif is observed and the eight-coordinate complex Cs5[Nd(NCS)8] isolated. The thorium compounds [Me4N]4[Th(NCS)7(NO3)] and [Me4N]4[Th(NCS)6(NO3)2] have been characterized, and high coordination numbers are also observed. Finally, attempts to synthesize a U(III) thiocyanate compound has been unsuccessful; from the reaction mixture, a heterocycle formed by condensation of five MeCN solvent molecules, possibly promoted by U(III), was isolated and structurally characterized. To rationalize the inability to isolate U(III) thiocyanate compounds, thin-layer cyclic voltammetry and IR spectroelectrochemistry have been utilized to explore the cathodic behavior of [Et4N]4[U(NCS)8] and [Et4N][U(NCS)5(bipy)2] along with a related uranyl compound [Et4N]3[UO2(NCS)5]. In all examples, the reduction triggers a rapid dissociation of [NCS]− ions and decomposition. Interestingly, the oxidation chemistry of [Et4N]3[UO2(NCS)5] in the presence of bipy gives the U(IV) compound [Et4N]4[U(NCS)8], an unusual example of a ligand-based oxidation triggering a metal-based reduction. The experimental results have been augmented by a computational investigation, concluding that the U(III)–NCS bond is more ionic than the U(IV)–NCS bond

Inkjet Printable Organic-Inorganic Hybrids Based On Polyaniline

Polyaniline (PANI) is an organic polymer that has generated significant interest as an electrically conductive material component, and is used in applications such as sensors and flexible displays. A significant number of PANI-based devices have been prepared using inkjet printing; a fabrication technique favoured for its additive patterning ability and its efficient use of material. Combining precious metals and conducting organic polymers through compositing provides combinatorial materials, potentially possessing both the properties of the metallic component and the conducting polymer, as well as unique ensuing properties due to the compositing itself. The type of research is critical for driving innovation in materials research. Exploiting an established oxidative polymerisation protocol for producing stable nanodispersions of PANI was used where the standard oxidant was replaced with HAuCl4 or AgNO3 at a range of monomer:oxidant ratios to produce a range of composite dispersions. The morphology and populations of the metallic structures (including spherical nanoparticles and nano-whiskers), as well as the quality of the PANI were shown to be influenced by the concentration and type of oxidant used. This area of research is currently in its infancy where the research is focusing on demonstrating composite synthesis rather than the application of these materials for device fabrication. However, anticipated applications of these composite materials include noble metal deposition, electro-catalysis, neural tissue engineering, sensors, photovoltaic cells and memory devices

Formation of stoichiometric and non-stoichiometric ionic liquid and cocrystal multicomponent phases of lidocaine with azelaic acid by changing counterion ratios

Tuning of physicochemical properties of ionic liquids and crystalline materials is a challenge that opens up unlimited possibilities for expanding applications and controlling biological activity of pharmaceutical multicomponent phases incorporating active pharmaceutical ingredients (APIs) with counterions or coformers. In this work we have investigated the effect of changing lidocaine (LID) and azelaic acid (AZE) ratios on the physicochemical properties of their corresponding multicomponent systems using a thermodynamics-based approach. Microscopy, X-ray diffraction analysis, infrared spectroscopy, nuclear magnetic resonance, and thermogravimetric analysis provided complimentary characterisation. Mechanochemical synthesis of LID:AZE systems at a range of stoichiometries yielded at least two distinct liquid phases and two distinct crystalline phases, one of which involved a unique 2:3 LID:counterion composition not observed previously. Furthermore, to the best of our knowledge the formation of oligomeric ionic liquids involving dicarboxylic acids is also being reported for the first time. This work highlights the need for a careful characterisation of multicomponent systems, especially for pharmaceutical applications

Characterisation and fundamental insight into the formation of new solid state, multicomponent systems of propranolol

The physiochemical properties of acidic or basic active pharmaceutical ingredients (APIs) can be optimised by forming salts with different counterions. The aim of this work was to synthesise a novel salt of propranolol (PRO) using sebacic acid (SEBA) as the counterion and to gain mechanistic understanding of not only the salt formation, but also its eutectic phase formation with SEBA. Thermal analysis showed a solid-state reaction occurring be-tween PRO and SEBA leading to the formation of dipropranolol sebacate (DPS) melting at app. 170 ◦C and the eutectic composed of DPS and SEBA melting at app. 103 ◦C, comprising 0.33 mol fraction of PRO as determined by the Tammann plot. X-ray diffraction and Fourier-transform infrared spectroscopy (FTIR) confirmed the identity of the new multicomponent phases of PRO. DPS can be conveniently obtained by heat-induced crys-tallisation, grinding and conventional solvent crystallisation. Detailed analysis by FTIR revealed H-bond in-teractions between DPS and SEBA at the inter-phase in the eutectic. Bravais, Friedel, Donnay and Harker crystal morphology coupled with full interaction maps analysis allowed to understand further the nature of interactions which led to formation of the eutectic phase. This work contributes to furthering research on multicomponent pharmaceutical systems to harness their full potential

Highly Selective Fluorimetric Turn-Off Detection of Copper(II) by Two Different Mechanisms in Calix[4]arene-Based Chemosensors and Chemodosimeters

Isoxazolo-pyrene tethered calix[4]arenes selectively detect copper(II) ions without interference from related perchlorate ions. The fluorescence emission of the probes, synthesised by nitrile oxide alkyne cycloaddition, and characterised by spectroscopic and crystallographic data, is rapidly reduced by Cu(II) ions. Detection limits are in the micromolar or sub-micromolar range (0.3–3.6 μM) based on a 1:1 sensor:analyte interaction. Voltammetric behaviour and 1 H NMR data provide new insights into the sensing mechanism which is dependent on the calixarene substitution pattern. When the calixarene lower rim is fully substituted, Cu(II) detection occurs through a traditional chelation mechanism. In contrast, for calixarenes 1,3-disubstituted on the lower rim, detection takes place through a chemodosimetric redox reaction. The isolation of a calix[4] diquinone from the reaction with excess Cu(ClO4)2 provides confirmation that the sensor–analyte interaction culminates in\ud irreversible sensor oxidation