Metal oxidation states in biological water splitting

A central question in biological water splitting concerns the oxidation states of the manganese ions that comprise the oxygen-evolving complex of photosystem II. Understanding the nature and order of oxidation events that occur during the catalytic cycle of five S_i states (i = 0–4) is of fundamental importance both for the natural system and for artificial water oxidation catalysts. Despite the widespread adoption of the so-called “high-valent scheme”—where, for example, the Mn oxidation states in the S₂ state are assigned as III, IV, IV, IV—the competing “low-valent scheme” that differs by a total of two metal unpaired electrons (i.e. III, III, III, IV in the S₂ state) is favored by several recent studies for the biological catalyst. The question of the correct oxidation state assignment is addressed here by a detailed computational comparison of the two schemes using a common structural platform and theoretical approach. Models based on crystallographic constraints were constructed for all conceivable oxidation state assignments in the four (semi)stable S states of the oxygen evolving complex, sampling various protonation levels and patterns to ensure comprehensive coverage. The models are evaluated with respect to their geometric, energetic, electronic, and spectroscopic properties against available experimental EXAFS, XFEL-XRD, EPR, ENDOR and Mn K pre-edge XANES data. New 2.5 K ⁵⁵Mn ENDOR data of the S₂ state are also reported. Our results conclusively show that the entire S state phenomenology can only be accommodated within the high-valent scheme by adopting a single motif and protonation pattern that progresses smoothly from S₀ (III, III, III, IV) to S₃ (IV, IV, IV, IV), satisfying all experimental constraints and reproducing all observables. By contrast, it was impossible to construct a consistent cycle based on the low-valent scheme for all S states. Instead, the low-valent models developed here may provide new insight into the over-reduced S states and the states involved in the assembly of the catalytically active water oxidizing cluster.     

Improving the water resistance of epoxy–anhydride matrices by the incorporation of bentonite

Epoxy–anhydride‐based polymers are commonly used as a matrix in pipeline systems exposed to water during their in‐service life. Water absorption at moderate temperatures and/or at long exposure times could lead to irreversible hydrolysis reaction decreasing considerably the polymer overall performance. A strategy to enhance the barrier properties of epoxy resins is to add nanofillers to traditional matrices. In this work, we added bentonite and chemically modified bentonite to this purpose. Water absorption of the resulting materials at three different temperatures (22°C, 80°C, and 93°C) was studied, and simultaneously, the evolution during the immersion tests of glass transition temperature and flexural modulus was recorded. Long‐term gravimetric results showed that composites with chemically modified bentonite produce a delay on the hydrolysis of epoxy–anhydride matrix, which is a relevant result, because of the tough application and uses of the system, from the technological point of view. Copyright © 2016 John Wiley & Sons, Ltd.     

Using liquid crystals as a readout system in urinary albumin assays

Detecting human serum albumin (HSA) in urine samples is a standard procedure for the diagnosis of kidney problems and the prognosis of patients with chronic kidney diseases (CKDs). In this study, we developed a HSA assay by incorporating a thin layer of liquid crystals (LCs) as a readout system such that the presence of HSA in urine samples can be detected as optical signals. In combination with dilution protocols, this assay can be used to estimate the concentration range of HSA simply by counting the number of bright spots. Our results show that the assay can detect HSA at concentrations as low as 15 μg mL(-1). It is anticipated that this assay can provide a faster and simpler alternative for the diagnosis and prognosis of patients with kidney diseases.     

Vectorized ferrocenes with estrogens and vitamin D2: synthesis, cytotoxic activity and docking studies

Three ferrocene complexes vectorized with estrogens and vitamin D(2) were synthesized and fully characterized by spectroscopic, electrochemical and computational methods. The synthesis of these esters was accomplished by reacting ferrocenoyl chloride with the corresponding ROH groups (R = ergocalciferol, estradiol, estrone). The cytotoxicity of these complexes in HT-29 colon cancer and MCF-7 breast cancer cell lines was investigated in vitro. Only ferrocenoyl 17β-hydroxy-estra-1,3,5(10)-trien-3-olate showed good cytotoxic activity in both cell lines, exceeding those of ferrocenium and ferrocene. In MCF-7, ferrocenoyl 17β-hydroxy-estra-1,3,5(10)-trien-3-olate exhibited remarkable IC(50), in the low micromolar range. This may be attributed to the presence of the estradiol vector. Docking studies between alpha-estrogen receptor ligand binding site and ferrocenoyl 17β-hydroxy-estra-1,3,5(10)-trien-3-olate revealed some key hydrophobic interactions that might explain the cytotoxic activity of this ester.     

Theoretical evaluation of structural models of the S2 state in the oxygen evolving complex of Photosystem II: protonation states and magnetic interactions

Protonation states of water ligands and oxo bridges are intimately involved in tuning the electronic structures and oxidation potentials of the oxygen evolving complex (OEC) in Photosystem II, steering the mechanistic pathway, which involves at least five redox state intermediates S(n) (n = 0-4) resulting in the oxidation of water to molecular oxygen. Although protons are practically invisible in protein crystallography, their effects on the electronic structure and magnetic properties of metal active sites can be probed using spectroscopy. With the twin purpose of aiding the interpretation of the complex electron paramagnetic resonance (EPR) spectroscopic data of the OEC and of improving the view of the cluster at the atomic level, a complete set of protonation configurations for the S(2) state of the OEC were investigated, and their distinctive effects on magnetic properties of the cluster were evaluated. The most recent X-ray structure of Photosystem II at 1.9 ? resolution was used and refined to obtain the optimum structure for the Mn(4)O(5)Ca core within the protein pocket. Employing this model, a set of 26 structures was constructed that tested various protonation scenarios of the water ligands and oxo bridges. Our results suggest that one of the two water molecules that are proposed to coordinate the outer Mn ion (Mn(A)) of the cluster is deprotonated in the S(2) state, as this leads to optimal experimental agreement, reproducing the correct ground state spin multiplicity (S = 1/2), spin expectation values, and EXAFS-derived metal-metal distances. Deprotonation of Ca(2+)-bound water molecules is strongly disfavored in the S(2) state, but dissociation of one of the two water ligands appears to be facile. The computed isotropic hyperfine couplings presented here allow distinctions between models to be made and call into question the assumption that the largest coupling is always attributable to Mn(III). The present results impose limits for the total charge and the proton configuration of the OEC in the S(2) state, with implications for the cascade of events in the Kok cycle and for the water splitting mechanism.     

Evaluation of a glycerol derived biofuel by thermal analysis

This work describes thermal analysis evaluation of a glycerol derived compound (fatty acid esters of (2,2-dimethyl-1,3-dioxolan-4-yl) methanol) developed to work as a biofuel. Mixtures of these ketal–glyceryl esters with fatty acid methyl esters typical of soybean biodiesel were prepared and evaluated in relation to biodiesel critical thermal properties such as temperature of crystallization, thermal stability and volatilization measured by differential scanning calorimetry and thermogravimetric analysis. The volatility of the products containing fatty acid methyl esters and (2,2-dimethyl-1,3-dioxolan-4-yl) methyl esters could be predicted by thermogravimetric analyses conducted in nitrogen that avoided time consuming distillation and greatly reduced material expenditure.     

Charge transfer properties of Tröger base derivatives

Two triarylamine centers bridged through an aliphatic bridge feature unexpected charge transfer properties, bearing an important electronic coupling between them in the absence of a π linker; EPR, electrochemistry, electronic spectroscopy and first principles molecular calculations are combined to study the electronic structure of this compound.     

Effect of the aliphatic chain length on electrical double layer formation at the liquid/vacuum interface in the [C(n)mim][BF4] ionic liquid series

Neutral impact collision ion scattering spectroscopy (NICISS) was used to determine the surface structure of three ionic liquids, 1-hexyl-3-methylimidazolium [C(6)mim], 1-octyl-3-methylimidazolium [C(8)mim], 1-decyl-3-methylimidazolium [C(10)mim] tetrafluoroborates [BF(4)]. Concentration depth profiles of the elements in an ionic liquid (IL) homologous series with a common anion were obtained. We show that separation between the oppositely charged ions is seen for all three ionic liquids, resulting in an electrical double layer formation. The surface charge shifts from more positive to more negative with increasing aliphatic chain length.