Estimation of Surface Structure and Carbon Monoxide Oxidation Site of Shape‐Controlled Pt Nanoparticles

Surface structures of shape‐controlled Pt nanoparticles have been estimated using cyclic voltammetry (CV) and infrared reflection absorption spectroscopy (IRAS). Cubic and cuboctahedral Pt nanoparticles are prepared using a capping polymer. These nanoparticles give CVs similar to those of single crystal electrodes of Pt in sulfuric acid solution. The CV of cubic nanoparticles is similar to that of the Pt(510) [=5(100)–(110)] electrode, while the CV of cuboctahedral nanoparticles is reproduced well with the convolution of Pt(766) [=13(111)–(100)] and Pt(17 1 1) [=9(100)–(111)] electrodes. These results suggest that the planes of the cubic and cuboctahedral nanoparticles are composed of step‐terrace and atomically flat terraces, respectively. Adsorbed carbon monoxide (CO) on the shape‐controlled nanoparticles gives the IR bands that are assigned to on‐top and bridged CO. The band of on‐top CO is deconvoluted to two bands: the higher and the lower frequency bands are assigned to the CO on the plane and the edges of the nanoparticles, respectively. On‐top CO adsorbed on the edges is oxidized at more negative potential than that on the planes. Edge sites of the nanoparticles promote CO oxidation.     

Thermal expansion and spontaneous strain of KMnF3 near the 186 K-structural phase transition

Abstract

By means of high-angle double-crystal X-ray diffractometry (HADOX), the thermal expansivity of KMnF₃ has been determined. The linear thermal expansion coefficient along each crystallographic axis exhibits a divergent anomaly at the structural phase transition at 186 K. The critical exponents of these coefficients are determined: in the cubic phase α = 0.21 ± 3, and in the tetragonal phase α′ = 0.19 ± 3 for the a axis and α″ = 0.35 ± 3 for the c axis.

In addition, the critical exponent of the spontaneous strain, c/a ? 1, is determined to be 0.4248 ± 8, which is smaller than that of the order parameter 2β = 0.5714 ± 12. These values are reasonable if the transition occurs in the vicinity of a tricritical point.     

Investigation of the surface reactivity of a sol-gel derived glass in the ternary system SiO2-CaO-P2O5

A new glass formulation, with the molar composition 60% SiO₂-35% CaO-5% P₂O₅, was synthesized using the sol-gel process, for applications as biomaterial in orthopaedic or maxillo facial surgery. Pellets, made of glass powder, were uniaxially compacted and soaked in simulated body fluid (SBF) for up to 7 days at 37 °C to evaluate glass bioactivity. Ionic exchanges at the interface glass-SBF were evaluated by studying evolutions of calcium, phosphorus and silicon concentrations in SBF using ICP-OES. Changes in glass surface, and the formation of crystalline phases were analyzed using XRD, SEM, EDS and FTIR methods.Results form ICP-OES showed a high reactivity of the glass surface with a very high and continuous release of calcium, a limited glass dissolution and an uptake of phosphorous from SBF. Results from both FTIR and XRD analysis indicated that the glass surface was progressively covered by two different phases: CaCO₃ as calcite and a carbonated apatite layer. The formation of these phases, following two different schemas, was observed after 2 h of immersion and confirmed after 7 days. SEM micrographs and EDS analysis demonstrated that the main phase, a carbonated apatite, was present as micro-spheroids and the secondary phase, calcite, was materialized by agglomerates which have diameters up to 10-15 μm. These results are in accordance with a bioactive feature of the glass studied.     

Flame-spread limit from interactive burning droplets in microgravity

This research conducted microgravity experiments on the flame spread over droplet-cloud elements with strong droplet interaction aboard Kibo on the ISS. The droplet-cloud element represents a local droplet pattern appearing in randomly distributed droplet clouds near the group-combustion-excitation limit and consists of small-droplet-spacing droplets and large-droplet-spacing droplets. As droplet-cloud elements, we used four n-decane droplets, Droplets C, B, A and L, placed at fiber intersections of two-dimensional SiC-fiber lattice with a 4-mm fiber interval in a combustion chamber. The flame spreads over the droplet-cloud element in order of Droplets C, B, A and L. The position of Droplet L relative to Droplet A was varied to investigate the flame-spread-limit distribution around burning Droplet A. The position of Droplet B relative to Droplet A was varied to investigate the effect of two-droplet interaction between Droplets B and A on the flame spread to Droplet L. The position of Droplet C relative to Droplet B was also varied to investigate the effect of three-droplet interaction among Droplets C, B and A. The results shows that in the case with the strong interaction by two or three interactive droplets, the high-temperature region is enlarged by the droplet interaction, centers near the center of mass of the interactive droplets and plays an important role in the flame-spread-limit distribution. Since the burning lifetime of Droplet A is finite, the flame-spread time from burning Droplet A to Droplet L is limited by burning lifetime of Droplet A and is less than 80% of the burning lifetime of Droplet A, which increases with the interactive effect. The flame-spread-limit distance from the center of mass of the interactive droplets increases with the burning lifetime.     

Two near-UV and visible chromophores of CpCo(Dithiolene) complexes with pyridinium-dicyanomethylide group

Tetracyanoethylene oxide (TCNEO) reacted with [CpCo(dithiolene)] (Cp = η⁵-cyclopentadienyl) complexes having 4-pyridyl or 3-pyridyl group to undergo a dicyanomethylation to the nitrogen atom on the pyridyl group. The reaction of [CpCo(S₂C₂(⁴Py)₂)] (1) with TCNEO formed both the monodicyanomethylated [CpCo(S₂C₂(⁴Py)(⁴Py-C(CN)₂))] (1a) and bisdicyanomethylated [CpCo(S₂C₂(⁴Py-C(CN)₂)₂)] (1b). [CpCo(S₂C₂(²Py)(⁴Py))] (2) reacted with TCNEO to give [CpCo(S₂C₂(²Py)(⁴Py-C(CN)₂))] (2a) but no dicyanomethylation occurred on the 2-pyridyl group. 2 reacted with excess TCNEO to form the only dicyanomethylated acetylene derivative ²Py-CC-(⁴Py-C(CN)₂) (2c), followed by a dissociation of the CpCoS₂ fragment. The monodicyanomethylated [CpCo(S₂C₂(ⁿPy-C(CN)₂)(2-thienyl))] (n = 4 (4a) or 3 (5a)) complexes were also prepared from [CpCo(S₂C₂(ⁿPy)(2-thienyl))] (n = 4 (4) or 3 (5)) and TCNEO. 1b was structurally characterized by X-ray diffraction study. The all dicyanomethylated [CpCo(dithiolene)] complexes showed the dithiolene LMCT absorption in the range of 605-644 nm (ε = 7000-9200 M⁻¹ cm⁻¹) and very strong absorption due to their pyridinium-dicyanomethylide moieties in near-UV region (e.g. 1b: λ_max = 470 nm, ε = 43,400 M⁻¹ cm⁻¹). The CV of the all dicyanomethylated complexes exhibited two reduction waves. The first reduction is due to Co^III/Co^II and the second one is due to the reduction of the pyridinium-dicyanomethylide moiety. The reduced 1b⁻ is stable enough for several minutes according to the visible spectroelectrochemical measurement. The ESR spectrum of 1b⁻ indicated eight hyperfine splittings due only to the interaction with the nuclear spin of cobalt (I = 7/2).     

2-Hydroxy-5,5-dialkyl-δ-valerolactone derivatives as chiral dopants for practical ferroelectric liquid crystals

2-Hydroxy-5,5-dialkyl-δ-valerolactone derivatives have shown interesting properties as a chiral dopant for ferroelectric liquid crystals. In small amounts these compounds induce high magnitudes of spontaneous polarization and long helical pitches in the chiral nematic phase (N*). Alkyl chains attached at the C-5 position play an important role in these properties. Here we discuss the stereochemistry and ferroelectric properties of these lactones and compare them with those of 2-hydroxy-5-alkyl-δ-valerolactone derivatives reported previously. The ring structure of 5,5-dialkyl-δ-valerolactone is found to be a rigid 'pseudo-chair' conformation by *H NMR studies.     

Photochemical dechlorination of DDT catalyzed by a hydrophobic vitamin B12 and a photosensitizer under irradiation with visible light

Dechlorination of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) was catalyzed by a hydrophobic vitamin B(12), heptamethyl cobyrinate perchlorate, with a visible light irradiation system containing a [Ru(ii)(bpy)(3)]Cl(2) photosensitizer, and the hydrophobic vitamin B(12) showed high catalytic efficiency and stability during the reaction.     

Towards oligosaccharide library synthesis by fluorous mixture method

The synthesis of an oligosaccharide library by a fluorous tag method is reported here. Several acceptors and donors were mixed and glycosylated. The reaction mixture was purified by chromatography over fluorous HPLC to provide disaccharides in order of increasing fluorine content of the tag. This method could be applied to oligosaccharide libraries consisting of two sets of structural isomers.     

Minimizing a monotone concave function with laminar covering constraints

Let V be a finite set with |V|=n. A family F⊆2^V is called laminar if for all two sets X,Y∈F, X∩Y≠∅ implies X⊆Y or X⊇Y. Given a laminar family F, a demand function , and a monotone concave cost function , we consider the problem of finding a minimum-cost such that x(X)?d(X) for all X∈F. Here we do not assume that the cost function F is differentiable or even continuous. We show that the problem can be solved in O(n²q) time if F can be decomposed into monotone concave functions by the partition of V that is induced by the laminar family F, where q is the time required for the computation of F(x) for any . We also prove that if F is given by an oracle, then it takes Ω(n²q) time to solve the problem, which implies that our O(n²q) time algorithm is optimal in this case. Furthermore, we propose an algorithm if F is the sum of linear cost functions with fixed setup costs. These also make improvements in complexity results for source location and edge-connectivity augmentation problems in undirected networks. Finally, we show that in general our problem requires Ω(2^n/2q) time when F is given implicitly by an oracle, and that it is NP-hard if F is given explicitly in a functional form.     

Stereo-controlled synthesis of prelasalocid, a key precursor proposed in the biosynthesis of polyether antibiotic lasalocid A

In the biosynthesis of a polyether ionophore antibiotic, lasalocid A, the cyclic ether skeleton composed of a tetrahydrofuran linked to a tetrahydropyran could be constructed by oxidative cyclization of linear dodecaketide diene precursor. Hence, we hypothesized a prelasalocid having (E,E)-trisubstituted olefins as the dodecaketide biosynthetic precursor. A stereo-controlled synthetic route to the prelasalocid has been devised in a highly convergent manner entailing installation of a variety of substituents at the trisubstituted olefins.