Polyoxometalate multi-electron-transfer catalytic systems for water splitting

The viable production of solar fuels requires a visible-light-absorbing unit, a H2O (or CO2) reduction catalyst (WRC), and a water oxidation catalyst (WOC) that work in tandem to split water or reduce CO2 with H2O rapidly, selectively, and for long periods of time. Most catalysts and photosensitizers developed to date for these triadic systems are oxidatively, thermally, and/or hydrolytically unstable. Polyoxometalates (POMs) constitute a huge class of complexes with extensively tunable properties that are oxidatively, thermally, and (over wide and adjustable pH ranges) hydrolytically stable. POMs are some of the fastest and most stable WOCs to date under optimal conditions. This Microreview updates the very active POM WOC field; it reports the application of POMs as WRCs and initial self-assembling metal oxide semiconductor–photosensitizer–POM catalyst triad photoanodes. The complexities of investigating these POM systems, including but not limited to the study of POM-hydrated metal-ion–metal-oxide speciation processes, are outlined. The achievements and challenges in POM WOC, WRC, and triad research are outlined

Two-Dimensional, Pyrazine-Based Nonlinear Optical Chromophores with Ruthenium(II) Ammine Electron Donors

Six new nonlinear optical (NLO) chromophores with pyrazinyl-pyridinium electron acceptors have been synthesized by complexing a known pro-ligand with electron donating {Ru^(II)(NH_3)_5}^(2+) or trans-{Ru^(II)(NH_3)_4(py)}^(2+) (py = pyridine) centers. These cationic complexes have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. The visible d → π* metal-to-ligand charge-transfer (MLCT) absorptions gain intensity on increasing the number of Ru^(II) centers from one to two, but remain at constant energy. One or two Ru^(III/II) redox processes are observed which are reversible, quasi-reversible, or irreversible, while all of the ligand-based reductions are irreversible. Molecular first hyperpolarizabilities β have been determined by using hyper-Rayleigh scattering (HRS) at 1064 nm, and depolarization studies show that the NLO responses of the symmetric species are strongly two-dimensional (2D) in character, with dominant “off-diagonal” β_(zyy) components. Stark (electroabsorption) spectroscopic measurements on the MLCT bands also allow the indirect determination of estimated static first hyperpolarizabilities β_0. Both the HRS and the Stark-derived β_0 values increase on moving from mono- to bimetallic complexes, and substantial enhancements in NLO response are achieved when compared with one-dimensional (1D) and 2D monometallic Ru^(II) ammine complexes reported previously

Beyond solvent exclusion: i-Motif detecting capability and an alternative DNA light-switching mechanism in a ruthenium(II) polypyridyl complex

Cytosine-rich DNA can fold into secondary structures known as i-motifs. Mounting experimental evidence suggests that these non-canonical nucleic acid structures form in vivo and play biological roles. However, to date, there are no optical probes able to identify i-motif in the presence of other types of DNA. Herein, we report for the first time the interactions between the three isomers of [Ru(bqp)2]2+ with i-motif, G-quadruplex, and double-stranded DNA. Each isomer has vastly different light-switching properties: mer is “on”, trans is “off”, and cis switches from “off” to “on” in the presence of all types of DNA. Using emission lifetime measurements, we show the potential of cis to light up and identify i-motif, even when other DNA structures are present using a sequence from the promoter region of the death-associated protein (DAP). Moreover, separated cis enantiomers revealed Λ-cis to have a preference for the i-motif, whereas Δ-cis has a preference for double-helical DNA. Finally, we propose a previously unreported light-switching mechanism that originates from steric compression and electronic effects in a tight binding site, as opposed to solvent exclusion. Our work suggests that many published non-emissive Ru complexes could potentially switch on in the presence biological targets with suitable binding sites, opening up a plethora of opportunity in the detection of biological molecules

Development of a disposable screen-printed amperometric biosensor based on glutamate dehydrogenase, for the determination of glutamate in clinical and food applications

A screen printed carbon electrode (SPCE) containing the electrocatalyst Meldola’s Blue (MB) has been investigated as the base transducer for a glutamate biosensor. The sandwich biosensor was fabricated by firstly depositing a chitosan (CHIT) layer onto the surface of the transducer (MB-SPCE), followed by glutamate dehydrogenase (GLDH): this device is designated GLDH-CHIT-MB-SPCE. NAD+ was added to buffer solutions prior to the measurement of glutamate. This biosensor was used in conjunction with amperometry in stirred solution at an applied potential of +0.1 V (vs. Ag/AgCl). Optimum conditions for the analysis of glutamate were found to be as follows: temperature, 35°C; buffer, pH 7; ionic strength, 75 mM; NAD+, 4 mM; CHIT 0.05% in 0.05 M HCl; GLDH, 30 U. The linear range of the biosensor was found to be 12.5 µM to 150 µM, the calculated limit of detection (based on three times signal to noise ratio) was 1.5 µM and the sensitivity was 0.44 nA/µM. The proposed biosensor was used to measure glutamate in serum before and after fortification with glutamate. The endogenous concentration of glutamate was found to be 1.68 mM and the coefficient of variation (CV) was 4.1%. The serum was then fortified with 2 mM of glutamate, and the resulting mean recovery was 96% with a CV of 3.3% (n = 6). An unfiltered beef OXO cube was analysed for monosodium glutamate (MSG) content. The endogenous content of MSG was 124.80 mg/g with a CV of 8.06%. The OXO cube solution was fortified with 0.935g (100 mM) of glutamate, the resulting mean recovery was 91% with a CV of 6.40 %

Behavioral differences between nonprofit and for-profit hospitals : an empirical study

This paper examines the theoretical and empirical differences between the behavior of nonprofit and for-profit hospitals. Considerations are extended to include the possibility of collusion when hospitals make strategic choices. The operating objectives of the firms take into account price, quantity, and quality. Defining the quality of hospital care is discussed and applied to the empirical work. The model predicts nonprofit hospitals will provide a higher level of quality and a lower price than for-profit hospitals. Theoretically, under a collusive outcome for nonprofits, price will increase but the change in quality is indeterminate relative to a competitive, non-collusive outcome. The empirical section offers evidence of differences between nonprofit and for-profit hospital behavior. Nonprofit hospitals do provide higher quality and a lower price when compared to their for-profit rivals. It seems the competitive forces extend to the area of quality. There is evidence that increased competition between nonprofits fosters quality competition. From the for-profit perspective, quality competition appears to be provoked in markets where the for-profit competes more directly against nonprofits. This paper provides theoretical and empirical analyses of hospital interactions and how these interactions change depending upon the type of control

Private providers in UK Higher Education: some policy options

This paper describes the present role of private providers in UK higher education, compares the position with that in the United States and then discusses some policy questions and policy options relating to their regulation and funding. This is made as a contribution to the debate that will lead up to and follow the Education White Paper

Syntheses and Properties of Two-Dimensional, Dicationic Nonlinear Optical Chromophores Based on Pyrazinyl Cores

Six new dicationic 2D nonlinear optical (NLO) chromophores with pyrazinyl-pyridinium electron acceptors have been synthesized by nucleophilic substitutions of 2,6-dichloropyrazine with pyridyl derivatives. These compounds have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Large red shifts in the intense, π → π* intramolecular charge-transfer (ICT) transitions on replacing −OMe with –Nme_2 substituents arise from the stronger π-electron donor ability of the latter. Each compound shows a number of redox processes which are largely irreversible. Single crystal X-ray structures have been determined for five salts, including two nitrates, all of which adopt centrosymmetric packing arrangements. Molecular first hyperpolarizabilities β have been determined by using femtosecond hyper-Rayleigh scattering at 880 and 800 nm, and depolarization studies show that the NLO responses of the symmetric species are strongly 2D, with dominant “off-diagonal” β_(zyy) components. Stark (electroabsorption) spectroscopic measurements on the ICT bands afford estimated static first hyperpolarizabilities β_0. The directly and indirectly derived β values are large, and the Stark-derived β_0 response for one of the new salts is several times greater than that determined for (E)-4′-(dimethylamino)-N-methyl-4-stilbazolium hexafluorophosphate. These Stark spectroscopic studies also permit quantitative comparisons with related 2D, binuclear RuII ammine complex salts

Quadratic and Cubic Nonlinear Optical Properties of Salts of Diquat-Based Chromophores with Diphenylamino Substituents

A series of chromophoric salts has been prepared in which 4-(diphenylamino)phenyl (Dpap) electron donor groups are connected to electron-accepting diquaternized 2,2′-bipyridyl (diquat) units. The main aim is to combine large quadratic and cubic nonlinear optical (NLO) effects in potentially redox-switchable molecules with 2D structures. The chromophores have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. The visible absorption spectra are dominated by intense π → π* intramolecular charge-transfer (ICT) bands, and all of the compounds show two reversible or quasireversible diquat-based reductions and partially reversible Dpap oxidations. Single crystal X-ray structures have been obtained for one salt and for the precursor compound (E)-4-(diphenylamino)cinnamaldehyde, both of which adopt centrosymmetric space groups. First hyperpolarizabilities β have been measured by using hyper-Rayleigh scattering (HRS) with a 800 nm laser, and Stark (electroabsorption) spectroscopy of the ICT bands affords estimated static first hyperpolarizabilities β_0. The directly and indirectly derived β values are large and generally increased substantially for the bis-Dpap derivatives when compared with their monosubstituted analogues. Polarized HRS studies show that the NLO responses of the disubstituted species are dominated by “off-diagonal” β_(zyy) components. Lengthening the diquaternizing alkyl unit lowers the electron-acceptor strength and therefore increases the ICT energies and decreases the E_(1/2) values for diquat reduction. However, compensating increases in the ICT intensity prevent significant decreases in the Stark-based β_0 responses. Cubic NLO properties have been measured by using the Z-scan technique over a wavelength range of 520−1600 nm, revealing relatively high two-photon absorption cross-sections of up to 730 GM at 620 nm for one of the disubstituted chromophores

Investigation of polyviologens as oxygen indicators in food packaging

A triggered oxygen indicator, formulated from a combination of electrochrome, titanium dioxide and EDTA, was evaluated for use in modified atmosphere packaging. Methylene blue was not an ideal electrochrome due to its slow reduction to the leuco form and fast subsequent oxidation by oxygen present at low concentrations, >0.1%. Polyviologen electrochromes showed much faster reduction after exposure to UV light. Thionine and 2,2?-dicyano-1,1?-dimethylviologen dimesylate, which have more anodic reduction potentials compared to methylene blue, can be used to produce oxygen indicators with decreased sensitivity to oxygen. These indicators can be used to detect oxygen even when levels increase up to 4.0%

Pyridinium p-DSSC Dyes: An old acceptor learns new tricks

A family of six (five new) thiophenyl bridged triarylamine-donor based dyes with pyridine anchoring groups have been synthesized and studied as sensitizers for the p-type dye-sensitized solar cell (p-DSSC). They comprise bis-dicyano acceptor systems with a single pyridyl binder incorporated directly into the triarylamine (1), or separated by a phenyl group (2); a mono-dicyano with two phenyl pyridine binders (3); and respective homologues 4 to 6 with pyridinium acceptors. In all cases, compared to their dicyano counterparts, the pyridinium based dyes have higher extinction coefficients and smaller HOMO-LUMO gaps that give broader spectrum absorption. Thus, despite lower dye uptake, devices based on pyridiniums 4 and 6 have identical power conversion efficiencies (η) to the equivalent dicyano systems 1 and 3. However, the best performing device (η = 0.06%) is based on the known bis-acceptor dicyano system 2, as the large size and double positive charge of 5 leads to a substantial disadvantage in loading on NiO. Absorbed-photon-to-current efficiencies for 5 are competitive with or higher than those of 2, implying a better per dye performance consistent with the absorption profile, and DFT calculations suggesting better charge separation. Thus, pyridiniums may provide a new, and easily accessible high performance acceptor for p-DSSC dyes, but are likely better paired with anionic binding groups such as carboxylates