A consideration of the economic viability of hydrogen fuel production is important in the STEP (Solar Thermal Electrochemical Photo) production of hydrogen fuel. STEP is an innovative way to decrease costs and increase the efficiency of hydrogen fuel production, which is a synergistic process that can use concentrating photovoltaics (CPV) and solar thermal energy to drive a high temperature, low voltage, electrolysis (water-splitting), resulting in H2 at decreased energy and higher solar efficiency. This study provides evidence that the STEP system is an economically viable solution for the production of hydrogen. STEP occurs at both higher electrolysis and solar conversion efficiencies than conventional room temperature photovoltaic (PV) generation of hydrogen. This paper probes the economic viability of this process, by comparing four different systems: (1) 10% or (2) 14% flat plate PV driven aqueous alkaline electrolysis H2 production, (3) 25% CPV driven molten electrolysis H2 production, and (4) 35% CPV driven solid oxide electrolysis H2 production. The molten and solid oxide electrolysers are high temperature systems that can make use of light, normally discarded, for heating. This significantly increases system efficiency. Using levelized cost analysis, this study shows significant cost reduction using the STEP system. The total price per kg of hydrogen is shown to decrease from $5.74 to $4.96 to $3.01 to $2.61 with the four alternative systems. The advanced STEP plant requires less than one seventh of the land area of the 10% flat cell plant. To generate the 216 million kg H2/year required by 1 million fuel cell vehicles, the 35% CPV driven solid oxide electrolysis requires a plant only 9.6mi2 in area. While PV and electrolysis components dominate the cost of conventional PV generated hydrogen, they do not dominate the cost of the STEP-generated hydrogen. The lower cost of STEP hydrogen is driven by residual distribution and gate costs.

Purple acid phosphatases (PAPs) are a group of metallohydrolases that contain a dinuclear Fe(III)M(II) center (M(II) = Fe, Mn, Zn) in the active site and are able to catalyze the hydrolysis of a variety of phosphoric acid esters. The dinuclear complex [(H(2)O)Fe(III)(μ-OH)Zn(II)(L-H)](ClO(4))(2) (2) with the ligand 2-[N-bis(2-pyridylmethyl)aminomethyl]-4-methyl-6-[N'-(2-pyridylmethyl)(2-hydroxybenzyl) aminomethyl]phenol (H(2)L-H) has recently been prepared and is found to closely mimic the coordination environment of the Fe(III)Zn(II) active site found in red kidney bean PAP (Neves et al. J. Am. Chem. Soc. 2007, 129, 7486). The biomimetic shows significant catalytic activity in hydrolytic reactions. By using a variety of structural, spectroscopic, and computational techniques the electronic structure of the Fe(III) center of this biomimetic complex was determined. In the solid state the electronic ground state reflects the rhombically distorted Fe(III)N(2)O(4) octahedron with a dominant tetragonal compression aligned along the μ-OH-Fe-O(phenolate) direction. To probe the role of the Fe-O(phenolate) bond, the phenolate moiety was modified to contain electron-donating or -withdrawing groups (-CH(3), -H, -Br, -NO(2)) in the 5-position. The effects of the substituents on the electronic properties of the biomimetic complexes were studied with a range of experimental and computational techniques. This study establishes benchmarks against accurate crystallographic structural information using spectroscopic techniques that are not restricted to single crystals. Kinetic studies on the hydrolysis reaction revealed that the phosphodiesterase activity increases in the order -NO(2) ←Br ←H ←CH(3) when 2,4-bis(dinitrophenyl)phosphate (2,4-bdnpp) was used as substrate, and a linear free energy relationship is found when log(k(cat)/k(0)) is plotted against the Hammett parameter σ. However, nuclease activity measurements in the cleavage of double stranded DNA showed that the complexes containing the electron-withdrawing -NO(2) and electron-donating -CH(3) groups are the most active while the cytotoxic activity of the biomimetics on leukemia and lung tumoral cells is highest for complexes with electron-donating groups.

The low temperature magnetic circular dichroism (MCD) and electron paramagnetic resonance (EPR) spectra of Cu(II) doped Cs(2)ZrCl(6) are reported. The Cu(II) ion is incorporated as the square planar copper tetrachloride ion, CuCl(4) (2-), which substitutes at the Zr(IV) site in the Cs(2)ZrCl(6) lattice, with a complete absence of axial coordination. Both the EPR and MCD show highly resolved spectra from which it is possible to determine the superhyperfine coupling constants and excited state geometries respectively. The Franck-Condon intensity patterns suggest that there is a substantial relaxation of the host lattice about the impurity ion. For the lowest energy (2)B(1g)(x(2)-y(2))-->(2)B(2g)(xy) transition, both the magnetic dipole allowed electronic origin as well as vibronic false origins are observed. The high resolution of the spectra allowed the accurate determination of the odd parity vibrations that are active in the spectra. The opposite sign of the MCD of the two components of the (2)E(g)(xz,yz) excited state allows this splitting to be determined for the first time. Accurate and unambiguous spectral parameters for the CuCl(4) (2-) ion are important as it has become a benchmark transition metal complex for theoretical electronic structure calculations.

The Cu(II) doped MgO system is known to display features indicating behavior intermediate between static and dynamic Jahn-Teller effects at low temperature. The system is interesting as there is a low barrier between equivalent Jahn-Teller distortions in the cubic host lattice. In order to study the geometry of the Cu(II) ion in this system, we have recorded the low temperature magnetic circular dichroism (MCD) and X-ray absorption fine structure (XAFS) spectra. The spectra have been interpreted in terms of the Cu(II) centers distorting the host lattice such that the CuO6 center is a tetragonally elongated octahedron.

Purple acid phosphatases (PAPs) are a group of heterovalent binuclear metalloenzymes that catalyze the hydrolysis of phosphomonoesters at acidic to neutral pH. While the metal ions are essential for catalysis, their precise roles are not fully understood. Here, the Fe(III)Ni(II) derivative of pig PAP (uteroferrin) was generated and its properties were compared with those of the native Fe(III)Fe(II) enzyme. The k cat of the Fe(III)Ni(II) derivative (approximately 60 s −1 ) is approximately 20% of that of native uteroferrin, and the Ni(II) uptake is considerably faster than the reconstitution of full enzymatic activity, suggesting a slow conformational change is required to attain optimal reactivity. An analysis of the pH dependence of the catalytic properties of Fe(III)Ni(II) uteroferrin indicates that the μ-hydroxide is the likely nucleophile. Thus, the Ni(II) derivative employs a mechanism similar to that proposed for the Ga(III)Zn(II) derivative of uteroferrin, but different from that of the native enzyme, which uses a terminal Fe(III)-bound nucleophile to initiate catalysis. Binuclear Fe(III)Ni(II) biomimetics with coordination environments similar to the coordination environment of uteroferrin were generated to provide both experimental benchmarks (structural and spectroscopic) and further insight into the catalytic mechanism of hydrolysis. The data are consistent with a reaction mechanism employing an Fe(III)-bound terminal hydroxide as a nucleophile, similar to that proposed for native uteroferrin and various related isostructural biomimetics. Thus, only in the uteroferrin-catalyzed reaction are the precise details of the catalytic mechanism sensitive to the metal ion composition, illustrating the significance of the dynamic ligand environment in the protein active site for the optimization of the catalytic efficiency.

Using fathers’ and mothers’ reports of expectations (measured prenatally) and father involvement (measured postnatally), we examined how both parents influence the likelihood that new fathers would be involved in instrumental (feeding, bathing, and changing the infant) and affective (playing and reading to the infant) caregiving activities. The study employed a longitudinal design with 68 couples participating in both the prenatal (e.g., approximately three months before the infant was born) and postnatal (e.g., between three to six months after the birth of the infant) phases of the study. Results indicate that both parents’ expectations are substantial predictors of instrumental involvement (as reported by both fathers and mothers), and that fathers’ expectations are stronger than mothers’ expectations for predicting affective involvement. Limitations follow.

Summary 1.Diaphragmatic herniae although common are not prone to strangulation. 2.The rarity of volvulus of the stomach in hiatus hernia is discussed. 3.In the radiological investigation of the acute abdomen the importance of an accurate history, physical findings, and relevant past history is stressed. 4.The necessity for the use of contrast media in high intestinal obstruction is discussed with special reference to water-soluble contrast media (gastrografin). 5.The definition, classification, and types of volvulus of the stomach are described. The predisposing factors and symptomatology are discussed and two cases associated with hiatus hernia are presented. 6.The differential diagnosis of the lower left thoracic opacity with an air-fluid level seen on plain films of the abdomen is discussed. Summary 1.Diaphragmatic herniae although common are not prone to strangulation. 2.The rarity of volvulus of the stomach in hiatus hernia is discussed. 3.In the radiological investigation of the acute abdomen the importance of an accurate history, physical findings, and relevant past history is stressed. 4.The necessity for the use of contrast media in high intestinal obstruction is discussed with special reference to water-soluble contrast media (gastrografin). 5.The definition, classification, and types of volvulus of the stomach are described. The predisposing factors and symptomatology are discussed and two cases associated with hiatus hernia are presented. 6.The differential diagnosis of the lower left thoracic opacity with an air-fluid level seen on plain films of the abdomen is discussed.