The agricultural production of ruminants is responsible for 24% global methane emissions, contributing 39% emissions this greenhouse gas from the sector. Strategies to mitigate ruminant methanogenesis include use methanogen inhibitors. For example, seaweeds Asparagopsis taxiformis and armata included at low levels in feed cattle sheep inhibit by up 98%, with evidence improvements utilisation efficiency. This has resulted an increasing interest demand these globally. In response, research...

The photostability of [RuII(bpy)2(4,4′-(PO3H2)2bpy)]Cl2 (bpy = 4,4′-bipyridine) on nanocrystalline TiO2 and ZrO2 films was investigated using a standard measurement protocol. Stability evaluated by monitoring visible light absorbance spectral changes, in real time, during 455 nm photolysis (30 fwhm, 475 mW/cm2) variety conditions relevant to dye-sensitized solar cells photoelectrosynthesis cells. Desorption (kdes) photochemical (kchem) processes were observed found be dependent upon solvent,...

The performance of dye-sensitized solar and photoelectrochemical cells is strongly dependent on the light absorption electron transfer events at semiconductor–small molecule interface. These processes as well photo/electrochemical stability are dictated not only by properties chromophore metal oxide but also structure dye molecule, number surface binding groups, their mode to surface. In this article, we report photophysical electrochemical a series six phosphonate-derivatized [Ru(bpy)3]2+...

Simple assembly: A "layer-by-layer" deposition of functionalized dyes/catalysts on the surfaces nanocrystalline oxides is introduced. The strategy general and offers considerable flexibility based phosphonate- or carboxylate-binding groups with ZrIV as bridging ions. resulting bilayer structures are capable supporting rapid intra-layer energy electron transfer (see picture).

Photoinduced formation, separation, and buildup of multiple redox equivalents are an integral part cycles for producing solar fuels in dye-sensitized photoelectrosynthesis cells (DSPECs). Excitation wavelength-dependent electron injection, intra-assembly transfer, pH-dependent back transfer on TiO2 were investigated the molecular assembly [((PO3H2-CH2)-bpy)2Rua(bpy-NH-CO-trpy)Rub(bpy)(OH2)]4+ ([TiO2–RuaII–RubII–OH2]4+; ((PO3H2-CH2)2-bpy =...

Water-stable, surface-bound chromophores, catalysts, and assemblies are an essential element in dye-sensitized photoelectrosynthesis cells for the generation of solar fuels by water splitting CO2 reduction to CO, other oxygenates, or hydrocarbons. Phosphonic acid derivatives provide a basis stable chemical binding on metal oxide surfaces. We report here efficient synthesis 4,4'-bis(diethylphosphonomethyl)-2,2'-bipyridine 4,4'-bis(diethylphosphonate)-2,2'-bipyridine, as well mono-, bis-,...

Ulva are hardy green seaweeds that contain the sulfated polysaccharide ulvan and grow in two distinct morphologies: foliose tubular. The authors hypothesise from tubular species more structurally complex than ulvans species. Herein, using standardised methods, glycosyl linkage positions sulfate ester substitutions of constituent monosaccharides isolated (U. lacinulata U. stenophylloides) prolifera ralfsii) were investigated. Comparison native with 80 100 °C desulfated counterparts indicated...

A rigid linear bis-bidentate quaterpyridine undergoes metal directed self-assembly with iron(II) salts yielding M4L6 host–guest complexes; selective anion binding for PF6− over BF4− is observed.

To probe light-induced redox equivalent separation and accumulation, we prepared ruthenium polypyridyl molecular assembly [(dcb)2Ru(bpy-Mebim2py)Ru(bpy)(OH2)]4+ (RuaII–RubII–OH2) with Rua as light-harvesting chromophore Rub water oxidation catalyst (dcb = 4,4′-dicarboxylic acid-2,2′-bipyridine; bpy-Mebim2py 2,2′-(4-methyl-[2,2′:4′,4″-terpyridine]-2″,6″-diyl)bis(1-methyl-1H-benzo[d]imidazole); bpy 2,2′-bipyridine). When bound to TiO2 in nanoparticle films, it undergoes MLCT excitation,...

A unique example of incorporation a tetrahalometalate anion in small supramolecular cage is described which tetrahedral type [Fe4L6]8+ selectively encapsulates [FeIIICl4]− over [FeIICl4]2− its central cavity to yield discrete, mixed oxidation state, Fe(II)/Fe(III) assembly. This unusual outcome has been achieved using two alternative synthetic strategies.

The synthesis and analysis of a new amide-linked, dinuclear [Ru(bpy)2(bpy-ph-NH-CO-trpy)Ru(bpy)(OH2)]4+ (bpy = 2,2′-bipyridine; bpy-ph-NH-CO-trpy 4-(2,2′:6′,2″-terpyridin-4′-yl)-N-[(4′-methyl-2,2′-bipyridin-4-yl)methyl]benzamide) assembly that incorporates both light-harvesting chromophore water oxidation catalyst are described. With the saturated methylene linker present, individual properties retained including catalysis relatively slow energy transfer from excited state to catalyst.

The capture and storage of solar energy requires chromophores that absorb light throughout the spectrum. We report here synthesis, characterization, electrochemical, photophysical properties a series Ru(II) polypyridyl complexes type [Ru(bpy)2(N–N)]2+ (bpy = 2,2′-bipyridine; N–N is bidentate ligand). In this series, nature ligand was altered, either through increased conjugation or incorporation noncoordinating heteroatoms, as way to use electronic tune redox potentials, absorption spectra,...

The intestinal microbial community (microbiota) is dynamic and variable amongst individuals plays an essential part in gut health homeostasis. Dietary components can modulate the structure of microbiota. In recent years, substantial efforts have been made to find novel dietary with positive effects on structure. Natural algal polysaccharides carotenoids reported possess various functions biological relevance their impact microbiota currently a topic interest. This study, therefore, reports...

A rare ruthenium(II) triple helicate of the type [Ru2L3]4+ (L=5,5′′′-dimethyl-2,2′:5′,5′′:2′′,2′′′-quaterpyridine) was synthesized in an unusually high yield by using microwave heating ethylene glycol (see scheme). Efficient separation into its P and M isomers DNA affinity chromatography indicated selective binding P-[Ru2L3]4+ with various sequences. Detailed facts importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or...

As an extension of prior studies involving the linear quaterpyridine ligand, 5,5′′′-dimethyl-2,2′:5′,5′′:2′′,2′′′-quaterpyridine 1, synthesis related expanded derivatives 2 and 3 incorporating dimethoxy-substituted 1,4-phenylene tetramethoxy-substituted 4,4′-biphenylene bridges between pairs 2,2′-bipyridyl groups has been carried out via double-Suzuki coupling reactions 5-bromo-5′-methyl-2′-bipyridine appropriate di-pinacol-diboronic esters using microwave heating. Reaction with selected...

The biomass composition of kelp varies within species both spatially and temporally. However, this variation in quality has not yet been investigated for the native Ecklonia radiata New Zealand, where is a target emerging seaweed aquaculture industry. In study we quantified spatial temporal E. biomass, collected from 12 sites around North Island Zealand months across full year at single site (n = 138). High was detected most components, including alginate (range: 16.6 - 22.7% DW, n 12),...

Knowledge of electronic structures and transport mechanisms in dye-sensitized semiconductors is motivated by their ubiquity photoelectrochemical cells. In this work, optical spectroscopies are used to uncover the elementary dynamics initiated light absorption at such molecule–semiconductor interfaces (e.g., electron transfer nuclear relaxation). These processes explored a family ruthenium bipyridyl complexes aqueous solutions, wherein phosphonate groups bind molecules TiO2 nanocrystalline...