Publications
115 results found
Wilton-Ely JD, Toscani A, Marin-Hernandez C, et al., 2016, Chromo-fluorogenic probes for carbon monoxide detection, Chemical Communications, Vol: 52, Pages: 5902-5911, ISSN: 1364-548X
The sensing of carbon monoxide (CO) using electrochemical cells or semiconducting metal oxides has led to inexpensive alarms for the home and workplace. It is now recognised that chronic exposure to low levels of CO also poses a significant health risk. It is perhaps surprising therefore that the CO is used in cell-signalling pathways and plays a growing role in therapy. However, the selective monitoring of low levels of CO remains challenging, and it is this area that has benefited from the development of probes which give a colour or fluorescence response. This feature article covers the design of chromo-fluorogenic probes and their application to CO sensing in air, solution and in cells.
Wilton-Ely JD, Toscani A, Brown N, et al., 2015, Ruthenium(II) and Osmium(II) vinyl complexes as highly sensitive and selective chromogenic and fluorogenic probes for the sensing of carbon monoxide in air, Chemistry - A European Journal, Vol: 21, Pages: 14529-14538, ISSN: 0947-6539
The detection of carbon monoxide in solution and air has been achieved using simple, inexpensive systems based on the vinyl complexes [M(CH[DOUBLE BOND]CHR)Cl(CO)(BTD)(PPh3)2] (R=aryl, BTD=2,1,3-benzothiadiazole). Depending on the nature of the vinyl group, chromogenic and fluorogenic responses signalled the presence of this odourless, tasteless, invisible, and toxic gas. Solutions of the complexes in CHCl3 underwent rapid change between easily differentiated colours when exposed to air samples containing CO. More significantly, the adsorption of the complexes on silica produced colorimetric probes for the naked-eye detection of CO in the gas phase. Structural data for key species before and after the addition of CO were obtained by means of single X-ray diffraction studies. In all cases, the ruthenium and osmium vinyl complexes studied showed a highly selective response to CO with exceptionally low detection limits. Naked-eye detection of CO at concentrations as low as 5 ppb in air was achieved with the onset of toxic levels (i.e., 100 ppm), thus resulting in a remarkably clear colour change. Moreover, complexes bearing pyrenyl, naphthyl, and phenanthrenyl moieties were fluorescent, and greater sensitivities were achieved (through turn-on emission fluorescence) in the presence of CO both in solution and air. This behaviour was explored computationally using time-dependent density functional theory (TDDFT) experiments. In addition, the systems were shown to be selective for CO over all other gases tested, including water vapour and common organic solvents. Supporting the metal complexes on cellulose strips for use in an existing optoelectronic device allows numerical readings for the CO concentration to be obtained and provision of an alarm system.
Sherwood R, Gonzàlez de Rivera F, Wan JH, et al., 2015, Multimetallic complexes based on a diphosphine-dithiocarbamate "janus" ligand., Inorganic Chemistry, Vol: 54, Pages: 4222-4230, ISSN: 1520-510X
The HCl salt of the aminodiphosphine ligand HN(CH2CH2PPh2)2 reacts with [M(CO)4(pip)2] (M = Mo, W; pip = piperidine) to yield [M{κ(2)-HN(CH2CH2PPh2)2}(CO)4]. The molybdenum analogue readily loses a carbonyl ligand to form [Mo{κ(3)-HN(CH2CH2PPh2)2}(CO)3], which was structurally characterized. The same ligand backbone is used to form the new bifunctional ligand, KS2CN(CH2CH2PPh2)2, which reacts with nickel and cobalt precursors to yield [Ni{S2CN(CH2CH2PPh2)2}2] and [Co{S2CN(CH2CH2PPh2)2}3]. Addition of [AuCl(tht)] (tht = tetrahydrothiophene) to [Ni{S2CN(CH2CH2PPh2)2}2] leads to formation of the pentametallic complex, [Ni{S2CN(CH2CH2PPh2AuCl)2}2]. In contrast, addition of [PdCl2(py)2] (py = pyridine) to [Ni{S2CN(CH2CH2PPh2)2}2] does not lead to a trimetallic complex but instead yields the transmetalated cyclic compound [Pd{S2CN(CH2CH2PPh2)2}]2, which was structurally characterized. The same product is obtained directly from [PdCl2(py)2] and KS2CN(CH2CH2PPh2)2. In contrast, the same reaction with [PtCl2(NCPh)2] yields the oligomer, [Pt{S2CN(CH2CH2PPh2)2}]n. Reaction of KS2CN(CH2CH2PPh2)2 with cis-[RuCl2(dppm)2] provides [Ru{S2CN(CH2CH2PPh2)2}(dppm)2](+), which reacts with [AuCl(tht)] to yield [Ru{S2CN(CH2CH2PPh2AuCl)2}(dppm)2](+). Addition of [M(CO)4(pip)2] (M = Mo, W) to the same precursor leads to formation of the bimetallic compounds [(dppm)2Ru{S2CN(CH2CH2PPh2)2}M(CO)4](+), while treatment with [ReCl(CO)5] yields [(dppm)2Ru{S2CN(CH2CH2PPh2)2}ReCl(CO)3](+). Reaction of KS2CN(CH2CH2PPh2)2 with [Os(CH═CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole) provides [Os(CH═CHC6H4Me-4){S2CN(CH2CH2PPh2)2}(CO)(PPh3)2], but reaction with the analogous ruthenium precursor fails to yield a clean product.
Lehner P, Staudinger C, Borisov SM, et al., 2015, Intrinsic artefacts in optical oxygen sensors--how reliable are our measurements?, Chemistry, Vol: 21, Pages: 3978-3986
Optical oxygen sensing is of broad interest in many areas of research, such as medicine, food processing, and micro- and marine biology. The operation principle of optical oxygen sensors is well established and these sensors are routinely employed in lab and field experiments. Ultratrace oxygen sensors, which enable measurements in the sub-nanomolar region (dissolved oxygen), are becoming increasingly important. Such sensors prominently exhibit phenomena that complicate calibration and measurements. However, these phenomena are not constrained to ultratrace sensors; rather, these effects are inherent to the way optical oxygen sensors work and may influence any optical oxygen measurement when certain conditions are met. This scenario is especially true for applications that deal with high-excitation light intensities, such as microscopy and microfluidic applications. Herein, we present various effects that we could observe in our studies with ultratrace oxygen sensors and discuss the reasons for their appearance, the mechanism by which they influence measurements, and how to best reduce their impact. The phenomena discussed are oxygen photoconsumption in the sensor material; depletion of the dye ground state by high-excitation photon-flux values, which can compromise both intensity and ratiometric-based measurements; triplet-triplet annihilation; and singlet-oxygen accumulation, which affects measurements at very low oxygen concentrations.
Toscani A, Helioevaara EK, Hena JB, et al., 2015, Multimetallic Alkenyl Complexes Bearing Macrocyclic Dithiocarbamate Ligands, Organometallics, Vol: 34, Pages: 494-505, ISSN: 1520-6041
Hurtubise VL, McArdle JM, Naeem S, et al., 2014, Multimetallic Complexes and Functionalized Nanoparticles Based on Unsymmetrical Dithiocarbamate Ligands with Allyl and Propargyl Functionality, INORGANIC CHEMISTRY, Vol: 53, Pages: 11740-11748, ISSN: 0020-1669
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- Citations: 19
Moragues ME, Toscani A, Sancenon F, et al., 2014, A Chromo-fluorogenic synthetic "Canary" for CO detection based on a Pyrenylvinyl Ruthenium(II) complex, Journal of the American Chemical Society, Vol: 136, Pages: 11930-11933, ISSN: 0002-7863
The chromo-fluorogenic detection of carbon monoxide in air has been achieved using a simple, inexpensive system based on ruthenium(II). This probe shows exceptional sensitivity and selectivity in its sensing behavior in the solid state. A color response visible to the naked eye is observed at 5 ppb of CO, and a remarkably clear color change occurs from orange to yellow at the onset of toxic CO concentrations (100 ppm) in air. Even greater sensitivity (1 ppb) can be achieved through a substantial increase in turn-on emission fluorescence in the presence of carbon monoxide, both in air and in solution. No response is observed with other gases including water vapor. Immobilization of the probe on a cellulose strip allows the system to be applied in its current form in a simple optoelectronic device to give a numerical reading and/or alarm.
Cecchini MP, Turek VA, Demetriadou A, et al., 2014, Heavy Metal Sensing Using Self-Assembled Nanoparticles at a Liquid–Liquid Interface, Advanced Optical Materials
Lin YH, Duclaux L, de Rivera FG, et al., 2014, The Pentynoate Ligand as a Building Block for Multimetallic Systems, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Vol: 2014, Pages: 2065-2072, ISSN: 1434-1948
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- Citations: 11
Naeem S, Serapian SA, Toscani A, et al., 2014, Ring-Closing Metathesis and Nanoparticle Formation Based on Diallyldithiocarbamate Complexes of Gold(I): Synthetic, Structural, and Computational Studies, INORGANIC CHEMISTRY, Vol: 53, Pages: 2404-2416, ISSN: 0020-1669
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- Citations: 32
Sung S, Holmes H, Wainwright L, et al., 2014, Multimetallic Complexes and Functionalized Gold Nanoparticles Based on a Combination of d- and f-Elements, INORGANIC CHEMISTRY, Vol: 53, Pages: 1989-2005, ISSN: 0020-1669
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- Citations: 30
Eminov S, Wilton-Ely JDET, Hallett JP, 2014, Highly selective and near-quantitative conversion of fructose to 5-hydroxymethylfurfural using mildly acidic ionic liquids, ACS Sustainable Chemistry & Engineering, Vol: 2, Pages: 978-981, ISSN: 2168-0485
Naeem S, Ribes A, White AJP, et al., 2013, Multimetallic Complexes and Functionalized Nanoparticles Based on Oxygen- and Nitrogen-Donor Combinations, INORGANIC CHEMISTRY, Vol: 52, Pages: 4700-4713, ISSN: 0020-1669
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- Citations: 17
Collinson J-M, Wilton-Ely JDET, Diez-Gonzalez S, 2013, Reusable and highly active supported copper(I)-NHC catalysts for Click chemistry, CHEMICAL COMMUNICATIONS, Vol: 49, Pages: 11358-11360, ISSN: 1359-7345
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- Citations: 79
Champion MJD, Solanki R, Delaude L, et al., 2012, Synthesis and catalytic application of palladium imidazol(in)ium-2-dithiocarboxylate complexes, DALTON TRANSACTIONS, Vol: 41, Pages: 12386-12394, ISSN: 1477-9226
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- Citations: 28
Patel P, Naeem S, White AJP, et al., 2012, Synthesis and reactivity of dialkyldithiophosphate complexes of ruthenium(II), RSC ADVANCES, Vol: 2, Pages: 999-1008
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- Citations: 10
Naeem S, White AJP, Hogarth G, et al., 2011, Multifunctional Dithiocarbamates: Synthesis and Ring-Closing Metathesis of Diallyldithiocarbamate Complexes (vol 29, pg 2547, 2010), ORGANOMETALLICS, Vol: 30, Pages: 2068-2069, ISSN: 0276-7333
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- Citations: 7
Chia EY, Naeem S, Delaude L, et al., 2011, Gold(I) complexes bearing mixed-donor ligands derived from N-heterocyclic carbenes, DALTON TRANSACTIONS, Vol: 40, Pages: 6645-6658, ISSN: 1477-9226
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- Citations: 16
Naeem S, Thompson AL, White AJP, et al., 2011, Dithiocarboxylate complexes of ruthenium(II) and osmium(II), DALTON TRANSACTIONS, Vol: 40, Pages: 3737-3747, ISSN: 1477-9226
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- Citations: 35
Oliver K, White AJP, Hogarth G, et al., 2011, Multimetallic complexes of group 10 and 11 metals based on polydentate dithiocarbamate ligands, DALTON TRANSACTIONS, Vol: 40, Pages: 5852-5864, ISSN: 1477-9226
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- Citations: 50
Anastasiadis C, Hogarth G, Wilton-Ely JDET, 2010, Functionalised dithiocarbamate complexes: Complexes based on indoline, indole and substituted piperazine backbones - X-ray crystal structure of [Ni(S<sub>2</sub>CNC<sub>3</sub>H<sub>6</sub>C<sub>6</sub>H<sub>4</sub>)<sub>2</sub>], INORGANICA CHIMICA ACTA, Vol: 363, Pages: 3222-3228, ISSN: 0020-1693
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- Citations: 30
Naeem S, White AJP, Hogarth G, et al., 2010, Multifunctional Dithiocarbamates: Synthesis and Ring-Closing Metathesis of Diallyldithiocarbamate Complexes, ORGANOMETALLICS, Vol: 29, Pages: 2547-2556, ISSN: 0276-7333
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- Citations: 51
Naeem S, Delaude L, White AJP, et al., 2010, The Use of Imidazolium-2-dithiocarboxylates in the Formation of Gold(l) Complexes and Gold Nanoparticles, INORGANIC CHEMISTRY, Vol: 49, Pages: 1784-1793, ISSN: 0020-1669
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- Citations: 62
Naeem S, Ogilvie E, White AJP, et al., 2010, The functionalisation of ruthenium(II) and osmium(II) alkenyl complexes with amine- and alkoxy-terminated dithiocarbamates, DALTON TRANSACTIONS, Vol: 39, Pages: 4080-4089, ISSN: 1477-9226
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- Citations: 28
Chaudhry BR, Wilton-Ely JDET, Tabor AB, et al., 2010, Effect of peptide orientation on electron transfer, PHYSICAL CHEMISTRY CHEMICAL PHYSICS, Vol: 12, Pages: 9996-9998, ISSN: 1463-9076
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- Citations: 20
Naeem S, Thompson AL, Delaude L, et al., 2010, Non-innocent Behaviour of Dithiocarboxylate Ligands Based on N-Heterocyclic Carbenes, CHEMISTRY-A EUROPEAN JOURNAL, Vol: 16, Pages: 10971-10974, ISSN: 0947-6539
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- Citations: 35
Hogarth G, Rainford-Brent E-JC-RCR, Kabir SE, et al., 2009, Functionalised dithiocarbamate complexes: Synthesis and molecular structures of 2-diethylaminoethyl and 3-dimethylaminopropyl dithiocarbamate complexes [M{S<sub>2</sub>CN(CH<sub>2</sub>CH<sub>2</sub>NEt<sub>2</sub>)<sub>2</sub>}<i><sub>n</sub></i>] and [M{S<sub>2</sub>CN(CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>NMe<sub>2</sub>)<sub>2</sub>}<i><sub>n</sub></i>] (<i>n</i>=2, M = Ni, Cu, Zn, Pd; <i>n</i>=3, M = Co), INORGANICA CHIMICA ACTA, Vol: 362, Pages: 2020-2026, ISSN: 0020-1693
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- Citations: 65
Knight ER, Leung NH, Thompson AL, et al., 2009, Multimetallic Arrays: Bi-, Tri-, Tetra-, and Hexametallic Complexes Based on Gold(I) and Gold(III) and the Surface Functionalization of Gold Nanoparticles with Transition Metals, INORGANIC CHEMISTRY, Vol: 48, Pages: 3866-3874, ISSN: 0020-1669
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- Citations: 50
Macgregor MJ, Hogarth G, Thompson AL, et al., 2009, Multimetallic Arrays: Symmetrical and Unsymmetrical Bi-, Tri-, and Tetrametallic Organometallic Complexes of Ruthenium(II) and Osmium(II), ORGANOMETALLICS, Vol: 28, Pages: 197-208, ISSN: 0276-7333
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- Citations: 45
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