Both chlorophyll f and chlorophyll d are red-shifted chlorophylls in oxygenic photosynthetic organisms, which extend photon absorbance into the near infrared region. This expands the range of light that can be used to drive photosynthesis. Quantitative determination of chlorophylls is a crucial step in the investigation of chlorophyll-photosynthetic reactions in the field of photobiology and photochemistry. No methods have yet been worked out for the quantitative determination of chlorophyll f. There is also no method available for the precise quantitative determination of chlorophyll d although it was discovered in 1943. In order to obtain the extinction coefficients (ε) of chlorophyll f and chlorophyll d, the concentrations of chlorophylls were determined by Inductive Coupled Plasma Mass Spectrometry according to the fact that each chlorophyll molecule contains one magnesium (Mg) atom. Molar extinction coefficient ε(chl f) is 71.11×10(3)Lmol(-1)A(707nm)cm(-1) and ε(chl d) is 63.68×10(3)Lmol(-1)A(697nm)cm(-1) in 100% methanol. This article is part of a Special Issue entitled: Photosynthesis Research for Sustainability: from Natural to Artificial.
Hierarchical morphologies in metal oxides are advantageous for many applications, including controlled drug release, photocatalysis, catalysis, synthetic biomaterials, and adsorption and separation technologies. In this study, agarose gel has been used as a template to prepare zirconium titanium mixed oxide pellets with bimodal porosity. Sol-gel chemistry conducted within the agarose gel produced "coral-like" interconnected networks of oxide nanoparticles with controllable quantities of zirconium and titanium. The materials were characterized using N(2) sorption, extended X-ray absorption fine structure, X-ray diffraction, TEM, SEM, zeta potential, and thermogravimetric analysis (to measure surface hydroxyl group density). The oxides were then tested for the adsorption of vanadyl and vanadate to determine which Zr mole fraction exhibited the highest capacity and fastest kinetics. The material containing 25 mol % Zr exhibited the highest surface area (322 +/- 8 m(2)/g) of the compositions investigated and also displayed a superior adsorption rate and capacity. Vanadate adsorption occurred with faster kinetics than did vanadyl adsorption. A comparative study demonstrated that the macro/meso pore structure had improved transport properties over a monomodal mesopore structure of similar Zr/Ti composition. The faster vanadate adsorption kinetics is attributed to enhanced surface accessibility in a hierarchical material.
A series of functional hybrid inorganic-organic adsorbent materials have been prepared through postsynthetic grafting of mesoporous zirconium titanate xerogel powders using a range of synthesized and commercial mono-, bis-, and tris-phosphonic acids, many of which have never before been investigated for the preparation of hybrid phases. The hybrid materials have been characterized using thermogravimetric analysis, diffuse reflectance infrared (DRIFT) and 31P MAS NMR spectroscopic techniques and their adsorption properties studied using a 153Gd radiotracer. The highest level of surface functionalization (molecules/nm2) was observed for methylphosphonic acid (∼3 molecules/nm2). The level of functionalization decreased with an increase in the number of potential surface coordinating groups of the phosphonic acids. Spectral decomposition of the DRIFT and 31P MAS NMR spectra showed that each of the phosphonic acid molecules coordinated strongly to the metal oxide surface but that for the 1,1-bis-phosphonic acids and tris-phosphonic acids the coordination was highly variable resulting in a proportion of free or loosely coordinated phosphonic acid groups. Functionalization of a porous mixed metal oxide framework with the tris-methylenephosphonic acid (ATMP-ZrTi-0.33) resulted in a hybrid with the highest affinity for 153Gd3+ in nitric acid solutions across a wide range of acid concentrations. The ATMP-ZrTi-0.33 hybrid material extracted 153Gd3+ with a Kd value of 1×10(4) in 0.01 M HNO3 far exceeding that of the other hybrid phases. The unfunctionalized mesoporous mixed metal oxide had negligible affinity for Gd3+ (Kd<100) under identical experimental conditions. It has been shown that the presence of free or loosely coordinated phosphonic acid groups does not necessarily translate to affinity for 153Gd3+. The theoretical cation exchange capacity of the ATMP-ZrTi-0.33 hybrid phase for Gd3+ has been determined to be about 0.005 mmol/g in 0.01 M HNO3. This behavior and that of the other hybrid phases suggests that the surface-bound ATMP ligand functions as a chelating ligand toward 153Gd3+ under these acidic conditions.
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