Publications by authors named "James J Walsh"

Background: Bone marrow mesenchymal stem cell (BM-MSC)-derived extracellular vesicles (ExoFlo) convey the immunomodulatory and regenerative properties of intact BM-MSCs. This study aimed to determine the safety and efficacy of ExoFlo as treatment for moderate to severe ARDS in patients with severe COVID-19.

Research Question: Do two doses of ExoFlo safely reduce mortality in COVID-19-associated moderate to severe ARDS compared with placebo?

Study Design And Methods: A prospective phase 2 multicenter double-anonymized randomized placebo-controlled dosing trial was conducted at five sites across the United States with infusions of placebo, 10 mL of ExoFlo, or 15 mL of ExoFlo on days 1 and 4.

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The Dawson-type sulfate polyoxometalate (POM) [SWO] has successfully been entrapped in polypyrrole (PPy) films on glassy carbon electrode (GCE) surfaces through pyrrole electropolymerization. Films of varying POM loadings (i.e.

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The CO2 reduction reaction (CO2RR) at metal electrodes is altered in the presence of pyridine and related species. Thick films of poly(4-vinylpyridine) on Au electrodes result in large current enhancements at low applied potentials but do not enhance CO2RR at these potentials. Surface-enhanced Raman spectroelectrochemistry can probe CO2-surface interactions and reveals that desorption of CO2 as bicarbonate is retarded in the presence of 4-PVP, with implications for ion-transport limitations in thick film CO2RR.

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Survival times for prostate cancer have increased substantially, meaning more survivors will be discharged to General Practitioners' (GP) services. The detection of recurrence and monitoring of symptoms and long-term side-effects in prostate cancer survivors requires the active involvement of GPs in their follow-up care. In order to address this, the transition and discharge from hospital to primary care must be managed effectively.

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Immobilization of a Mn polypyridyl CO reduction electrocatalyst on nanocrystalline TiO electrodes yields an active heterogeneous system and also significantly triggers a change in voltammetric and catalytic behaviour, relative to in solution. A combination of spectroelectrochemical techniques are presented here to elucidate the mechanism of the immobilized catalyst in situ.

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A dye-sensitised CO reduction photocatalyst that operates in water is reported. Transient spectroscopy demonstrates that the facile co-immobilisation of a Ru dye and a Ni CO reduction electrocatalyst enables efficient on-particle electron transfer leading to photocatalytic activity that greatly exceeds the equivalent solution based system.

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Graphitic carbon nitride (g-CN) synthesised from a urea precursor is an excellent CO reduction photocatalyst using [Co(bpy)] as a co-catalyst. A five-fold increase in activity for the highly polymerised urea derived g-CN is achieved compared to alternative precursors. Transient absorption, time-resolved and steady-state emission studies indicate that the enhanced activity is related to both an increased driving force for photoelectron transfer and a greater availability of photogenerated charges.

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The development of selective electrocatalysts for CO reduction in water offers a sustainable route to carbon based fuels and feedstocks. However, molecular catalysts are typically studied in non-aqueous solvents, in part to avoid competitive H evolution. [Ni(cyclam)] () is one of the few known electrocatalysts that operate in water and 30 years after its report its activity remains a rarely surpassed benchmark.

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Immobilization of [Mn(bpy)(CO)3Br], (1) and [Mn(bpy((t)Bu)2)(CO)3Br] (2, where (bpy((t)Bu)2) = 4,4'-di-tert-butyl-2,2'-bipyridine) in Nafion/multi-walled carbon nanotubes (MWCNT) on glassy carbon yielded highly active electrodes for the reduction of CO2 to CO in aqueous solutions at pH 7. Films incorporating have significantly improved selectivity towards CO2, with CO : H2 ∼ 1 at -1.4 V vs.

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Objectives: According to vigilance-avoidance theory, repressors have an avoidant interpretive bias, i.e., they interpret ambiguous self-relevant situations in a nonthreatening fashion.

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The immobilisation of electrocatalysts for CO2 reduction onto light harvesting semiconductors is proposed to be an important step towards developing more efficient CO2 reduction photoelectrodes. Here, we report a low cost nickel cyclam complex covalently anchored to a metal oxide surface. Using transient spectroscopy we validate the role of surface immobilisation on enhancing the rate of photoelectron transfer.

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[Mn(bpy)(CO)3Br] cast in a Nafion membrane is an active heterogeneous electrocatalyst with good selectivity for CO2 reduction to CO in neutral aqueous electrolyte. Addition of multi-walled carbon nanotubes (MWCNT) leads to a ∼10 fold current enhancement and stable CO : H2 yields (1 : 2) at -1.4 V vs.

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Spontaneously adsorbed monolayers have been formed on gold electrodes using a Keggin polyoxotungstate with covalently attached alkanethiol linkers of two different lengths. Films of both polyoxotungstates show two well-defined reduction processes associated with the polyoxotungstate centers where the ionic liquid, [BMIM][BF4], acts as supporting electrolyte. The surface coverages are both less than that expected for a close-packed monolayer.

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Highly luminescent metallopolymers have been prepared from condensation reactions between the primary alkyl amines contained within a poly(styrene-p-(aminomethyl)styrene) polymer backbone and carboxylic acid groups on [Ru(bpy)(2)(CAIP)](ClO(4))(2), where CAIP is 2-(4-carboxyphenyl)imidazo[4,5-f][1,10]phenanthroline. The photophysical properties of these metallopolymers including emission and absorption spectroscopy, luminescent lifetimes and time-resolved emission anisotropy show strong solvent and pH dependence. These properties are rather insensitive to the loading of the metal centres on the polymer backbone suggesting weak electronic interactions between adjacent centres and the polymer backbone.

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Thin films of the adduct formed from the electrostatic association of the metallopolymer, [Ru(bpy)(2)(PVP)(10)](2+), and the Dawson polyoxomolybdate α-[Mo(18)O(54)(SO(4))(2)](4-), POMo, have been formed on ITO electrodes using an alternate immersion approach. The Ru/POMo ratio is 4.5:1, which exceeds the 2:1 ratio expected on the basis of the charges of the Ru(2+) and POMo(4-) building blocks.

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The interaction of two luminescent metallopolymers; [Ru(bpy)(2)(PVP)(10)](2+) and [Ru(bpy)(2)(CAIP)co-poly(7)](+), where bpy is 2,2'-bipyridyl, PVP is polyvinylpyridine, and (CAIP)co-poly(7) is poly(styrene(6)-co-p-(aminomethyl)styrene) amide linked to 2-(4-carboxyphenyl)imidazo[4,5-f] [1,10]phenanthroline, with the Dawson polyoxomolybdate α-[Mo(18)O(54)(SO(4))(2)](4-) is described. Both metallopolymers undergo electrostatic association with the polyoxometalate. From both electronic and luminescence spectroscopy the thermodynamic products were determined to be {[Ru(bpy)(2)(PVP)(10)](4.

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Thin films of polyoxometalates that are sensitized with a Ru(II) metallopolymer generate significant photocurrents in the presence of benzyl alcohol and visible light. Significantly, the photocurrent generated by the tungstate based adduct, α-[P(2)W(18)O(62)](6-), is approximately seven fold larger than that found for the Dawson polyoxomolybdate α-[S(2)Mo(18)O(62)](4-).

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The spectroscopic and photophysical properties of [Ru(bpy)(3)](2)[[Mo(18)O(54)(SO(3))(2)], where bpy is 2,2'-bipyridyl and [Mo(18)O(54)(SO(3))(2)](4-) is either the α or β-sulfite containing polyoxomolybdate isomer, have been measured and compared with those for the well known but structurally distinct sulfate analogue, α-[Mo(18)O(54)(SO(4))(2)](4-). Electronic difference spectroscopy revealed the presence of new spectral features around 480 nm, although they are weak in comparison with the [Ru(bpy)(3)](2)[Mo(18)O(54)(SO(4))(2)] analogue. Surprisingly, Stern-Volmer plots of [Ru(bpy)(3)](2+) luminescence quenching by the polyoxometallate revealed the presence of both static and dynamic quenching for both α and β-[Mo(18)O(54)(SO(3))(2)](4-).

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This report describes the first case of naturally acquired inhalation anthrax in the United States since 1976. The patient's clinical course included adjunctive treatment with human anthrax immunoglobulin. Clinical correlation of serologic assays for the lethal factor component of lethal toxin and anti-protective antigen immunoglobulin G are also presented.

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