Enhancing the Water Splitting Efficiency of Sn‐Doped Hematite Nanoflakes by Flame Annealing

The effect of flame annealing on the water‐splitting properties of Sn decorated hematite (α‐Fe₂O₃) nanoflakes has been investigated. It is shown that flame annealing can yield a considerable enhancement in the maximum photocurrent under AM 1.5 (100 mW cm^?2) conditions compared to classic furnace annealing treatments. Optimizing the annealing time (10 s at 1000 °C) leads to a photocurrent of 1.1 mA cm^?2 at 1.23 V (vs. RHE) with a maximum value 1.6 mA cm^?2 at 1.6 V (vs. RHE) in 1 M KOH. The improvement in photocurrent can be attributed to the fast direct heating that maintains the nanoscale morphology, leads to optimized Sn decoration, and minimizes detrimental substrate effects.     

A Capelli type theorem for multiplicative convolutions of polynomials

We prove a Capelli type theorem on the canonical decomposition for multiplicative convolutions of polynomials. We derive then some irreducibility criteria for convolutions of polynomials in several variables over a given field. The irreducibility conditions are expressed only in terms of the degrees of the polynomials in convolution, the degrees of their coefficients, and the degrees of some suitable divisors of the resulting leading coefficient. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Tautological rings of stable map spaces

We find a set of generators and relations for the system of extended tautological rings associated to the moduli spaces of stable maps in genus zero, admitting a simple geometrical interpretation. In particular, when the target is Pn, these give a complete presentation for the cohomology and Chow rings in the cases with/without marked points.     

Role of the adsorption phenomenon on the ionic equilibrium distribution and on the transient effects in electrolytic cells

We analyze the influence of the adsorption of ions at the interfaces on the transient phenomena occurring in an electrolytic cell submitted to a steplike external voltage. In the limit of small amplitude of the applied voltage, where the equation of the problem can be linearized, we obtain an analytical solution for the bulk and surface densities of ions and for the electrical potential. We also obtain, in this limit, the relaxation time for the transient phenomena.     

Cohomology rings and formality properties of nilpotent groups

We analyze k-stage formality and relate resonance with this type of formality properties. For instance, we show that, for a finitely generated nilpotent group that is k-stage formal, the resonance varieties are trivial up to degree k. We also show that the cohomology ring, truncated up to degree k+1, of a finitely generated nilpotent, k-stage formal group is generated in degree 1; this criterion is necessary and sufficient for a finitely generated, 2-step nilpotent group to be k-stage formal. We compute resonance varieties for Heisenberg-type groups and deduce the degree of partial formality for this class of groups.     

Separations of antifungal compounds in capillary electrophoresis with two anionic cyclodextrins

CD‐CZE methods were developed for complete stereoisomeric separations of a series of six γ‐lactam analogues, of which some were neutral, or cationic depending on the background electrolyte nature. The tested cyclodextrin was the versatile sulfobutylether‐ β‐CD, used either in a phosphate buffer using capillaries dynamically coated with polyethylene oxide or in a borate buffer using uncoated capillaries. Long‐end and short‐end modes and concentration variations of chiral selectors allowed finding conditions of complete separation of four out of the six derivatives (i.e., 1 , 2 , 3, and 4 ) in short run times, confirming their broad range of applications. To separate the two last compounds, the highly sulfated‐ γ‐CD was examined as chiral selector in acidic phosphate conditions. The enantiomers of the γ‐lactam analogues 5 and 6 were baseline resolved with 5.5 and 4%, respectively as concentration in the buffer.     

Artificial metalloenzyme for enantioselective sulfoxidation based on vanadyl-loaded streptavidin

Nature's catalysts are specifically evolved to carry out efficient and selective reactions. Recent developments in biotechnology have allowed the rapid optimization of existing enzymes for enantioselective processes. However, the ex nihilo creation of catalytic activity from a noncatalytic protein scaffold remains very challenging. Herein, we describe the creation of an artificial enzyme upon incorporation of a vanadyl ion into the biotin-binding pocket of streptavidin, a protein devoid of catalytic activity. The resulting artificial metalloenzyme catalyzes the enantioselective oxidation of prochiral sulfides with good enantioselectivities both for dialkyl and alkyl-aryl substrates (up to 93% enantiomeric excess). Electron paragmagnetic resonance spectroscopy, chemical modification, and mutagenesis studies suggest that the vanadyl ion is located within the biotin-binding pocket and interacts only via second coordination sphere contacts with streptavidin.     

Artificial transfer hydrogenases based on the biotin-(strept)avidin technology: fine tuning the selectivity by saturation mutagenesis of the host protein

Incorporation of biotinylated racemic three-legged d6-piano stool complexes in streptavidin yields enantioselective transfer hydrogenation artificial metalloenzymes for the reduction of ketones. Having identified the most promising organometallic catalyst precursors in the presence of wild-type streptavidin, fine-tuning of the selectivity is achieved by saturation mutagenesis at position S112. This choice for the genetic optimization site is suggested by docking studies which reveal that this position lies closest to the biotinylated metal upon incorporation into streptavidin. For aromatic ketones, the reaction proceeds smoothly to afford the corresponding enantioenriched alcohols in up to 97% ee (R) or 70% (S). On the basis of these results, we suggest that the enantioselection is mostly dictated by CH/pi interactions between the substrate and the eta6-bound arene. However, these enantiodiscriminating interactions can be outweighed in the presence of cationic residues at position S112 to afford the opposite enantiomers of the product.     

A simple gamma-backbone modification preorganizes peptide nucleic acid into a helical structure

Peptide nucleic acid (PNA) is a synthetic analogue of DNA and RNA, developed more than a decade ago in which the naturally occurring sugar phosphate backbone has been replaced by the N-(2-aminoethyl) glycine units. Unlike DNA or RNA in the unhybridized state (single strand) which can adopt a helical structure through base-stacking, although highly flexible, PNA does not have a well-defined conformational folding in solution. Herein, we show that a simple backbone modification at the gamma-position of the N-(2-aminoethyl) glycine unit can transform a randomly folded PNA into a helical structure. Spectroscopic studies showed that helical induction occurs in the C- to N-terminal direction and is sterically driven. This finding has important implication not only on the future design of nucleic acid mimics but also on the design of novel materials, where molecular organization and efficient electronic coupling are desired.