A Time-Resolved Spectroscopic Investigation of a Novel BODIPY Copolymer and Its Potential Use as a Photosensitiser for Hydrogen Evolution.

A novel 4,4-difuoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) copolymer with diethynylbenzene has been synthesised, and its ability to act as a photosensitiser for the photocatalytic generation of hydrogen was investigated by time-resolved spectroscopic techniques spanning the ps- to ns-timescales. Both transient absorption and time-resolved infrared spectroscopy were used to probe the excited state dynamics of this photosensitising unit in a variety of solvents. These studies indicated how environmental factors can influence the photophysics of the BODIPY polymer. A homogeneous photocatalytic hydrogen evolution system has been developed using the BODIPY copolymer and cobaloxime which provides hydrogen evolution rates of 319 µmol h-1 g-1 after 24 h of visible irradiation.

Photoelectrocatalytic H2 evolution from integrated photocatalysts adsorbed on NiO.

A new approach to increasing the faradaic efficiency of dye-sensitised photocathodes for H2 evolution from water, using integrated photocatalysts, furnished with ester groups on the peripheral ligands, [Ru(decb)2(bpt)PdCl(H2O)](PF6)2 (1) and [Ru(decb)2(2,5-bpp)PtI(CH3CN)](PF6)2 (2), (decb = 4,4'-diethylcarboxy-2,2'-bipyridine, bpp = 2,2':5',2''-terpyridine, bpt = 3,5-bis(2-pyridyl)-1,2,4-triazole) is described. Overall, 1|NiO is superior to previously reported photocathodes, producing photocurrent densities of 30-35 µA cm-2 at an applied bias of -0.2 V vs. Ag/AgCl over 1 hour of continuous white light irradiation, resulting in the generation of 0.41 µmol h-1 cm-2 of H2 with faradaic efficiencies of up to 90%. Furthermore, surface analysis of the photocathodes before and after photoelectrocatalysis revealed that the ruthenium bipyridyl chromophore and Pd catalytic centre (1) were photochemically stable, highlighting the benefits of the approach towards robust, hybrid solar-to-fuel devices.

Hydrogen-Generating Ru/Pt Bimetallic Photocatalysts Based on Phenyl-Phenanthroline Peripheral Ligands.

Recent studies on hydrogen-generating supramolecular bimetallic photocatalysts indicate a more important role of the peripheral ligands than expected, motivating us to design a Ru/Pt complex with 4,7-diphenyl-1,10-phenanthroline peripheral ligands. Photoinduced intra- and inter-ligand internal conversion processes have been investigated using transient absorption spectroscopy, spanning the femto- to nanosecond timescale. After photoexcitation and ultrafast intersystem crossing, triplet states localised on either the peripheral ligands or on the bridging ligand/catalytic unit are populated in a non-equilibrated way. Time-resolved photoluminescence demonstrates that the lifetime for the Ru/Pt dinuclear species (795±8 ns) is significantly less than that of the mononuclear analogue (1375±20 ns). The photocatalytic studies show modest hydrogen turnover numbers, which is possibly caused by the absence of an excited state equilibrium. Finally, we identify challenges that must be overcome to further develop this class of photocatalysts and propose directions for future research.

Subtle Changes to Peripheral Ligands Enable High Turnover Numbers for Photocatalytic Hydrogen Generation with Supramolecular Photocatalysts.

The photocatalytic generation of hydrogen (H2) from protons by two cyclometalated ruthenium-platinum polypyridyl complexes, [Ru(bpy)2(2,5-bpp)PtIS](2+) (1) and [Ru(dceb)2(2,5-bpp)PtIS](2+) (2) [where bpy = 2,2'-bipyridine, 2,5-bpp = 2,2',5',2″-terpyridine, dceb = 4,4'-di(carboxyethyl)bipyridine, and S = solvent], is reported. Turnover numbers (TONs) for H2 generation were increased by nearly an order of magnitude by the introduction of carboxyethyl ester units, i.e., from 80 for 1P to 650 for 2P after 6 h of irradiation, with an early turnover frequency (TOF) increasing from 15 to 200 h(-1). The TON and TOF values for 2P are among the highest reported to date for supramolecular photocatalysts. The increase correlates with stabilization of the excited states localized on the peripheral ligands of the light-harvesting Ru(II) center.

Supramolecular bimetallic assemblies for photocatalytic hydrogen generation from water.

A series of supramolecular assemblies of the type [Ru(L-L)2(L'-L)MX2)](n+) are reported where L-L is 2,2'-bipyridine (bipy), 4,4'-di-tetra-butyl-bipyridine (tbbipy) or 4,4'-diethoxycarbonyl-2,2'-bipyridine (dceb), L-L' is tetrapyrido[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]phenazine (tpphz), 2,2':5',2''-terpyridine (2,5-bpp), 2,2':6',2''-terpyridine, (2,6-bpp), 2,5-di(pyridine-2-yl)pyrazine (2,5-dpp) or 2,3-di(pyridine-2-yl)pyrazine (2,3-dpp), and MX2 is PdCl2, PtCl2 or PtI2. The photocatalytic behaviour with respect to hydrogen generation of these compounds and their ultrafast photophysical properties are discussed as a function of the nature of the peripheral ligands, the bridging ligands and the catalytic centre. The results obtained show how differences in the chemical composition of the photocatalysts can affect intramolecular photoinduced electron transfer processes and the overall photocatalytic efficiency.

An observational study of material durability of three World Health Organization-recommended long-lasting insecticidal nets in eastern Chad.

A total of 876 nets (229 Interceptor(®), 363 Olyset(®), and 284 PermaNet(®)) were collected 14 months post-distribution of long-lasting insecticidal nets (LLINs) from 811 households of internally displaced and host communities in Dar Sila District in eastern Chad to examine their physical condition. Holes were recorded by using three hole categories (average diameter = 2, 3.5, and 15 cm) and a Proportionate Hole Index (pHI). A total of 69.5% were in poor or very poor condition. There was no significant difference in the performance between the polyester 75 denier LLINs, but they had 4.22 times the odds of having a pHI ≥ 175 (poor or very poor condition) than polyethylene 150 denier LLINs; and 39.2% were unserviceable (pHI ≥ 300) compared with only 7.7% of the polyethylene LLINs. These results provide the first comparative data on LLIN material durability to guide procurement and replacement practice, and to inform urgently needed changes in LLIN international minimum specifications and product standards.

Adherence to prescribed artemisinin-based combination therapy in Garissa and Bunyala districts, Kenya.

BACKGROUND: Following the development of resistance to anti-malarial mono-therapies, malaria endemic countries in Africa now use artemisinin-based combination therapy (ACT) as recommended first-line treatment for uncomplicated malaria. Patients' adherence to ACT is an important factor to ensure treatment efficacy, as well as to reduce the likelihood of parasite resistance to these drugs. This study reports adherence to a specific ACT, artemether-lumefantrine (AL), under conditions of routine clinical practice in Kenya. METHOD: The study was undertaken in Garissa and Bunyala districts among outpatients of five government health facilities. Patients treated with AL were visited at home four days after having been prescribed the drug. Respondents (patients ≥ 15 years and caregivers of patients < 15 years) were interviewed using a standardized questionnaire, AL blister packs were physically inspected and the adherence status of patients was then recorded. Multivariate logistic regression modelling was used to determine predictors of adherence. RESULTS: Of the 918 patients included in the study, 588 (64.1%) were 'probably adherent', 291 (31.7%) were 'definitely non-adherent' and 39 (4.2%) were 'probably non-adherent'. Six factors were found to be significant predictors of adherence: patient knowledge of the ACT dosing regimen (odds ratio (OR) = 1.76; 95% CI = 1.32-2.35), patient age (OR = 1.65; 95% CI = 1.02-1.85), respondent age (OR = 1.37; 95% CI = 1.10-2.48), whether a respondent had seen AL before (OR = 1.46; 95% CI = 1.08-1.98), whether a patient had reported dislikes to AL (OR = 0.62 95% CI = 0.47-0.82) and whether a respondent had waited more than 24 hours to seek treatment (OR = 0.73; 95% CI = 0.54-0.99). CONCLUSION: Overall, adherence to AL was found to be low in both Garissa and Bunyala districts, with patient knowledge of the AL dosing regimen found to be the strongest predictor of adherence. Interventions aimed at increasing community awareness of the AL dosing regimen, use of child friendly formulations and improving health workers' prescribing practices are likely to ensure higher adherence to AL and eventual treatment success.