Activity evaluation of carbon paste electrodes loaded with pt nanoparticles prepared in different radiolytic conditions

Three Pt-based catalysts prepared in different radiolytic conditions and supported on graphite powder were packed into a carbon paste electrode configuration. They were compared to each other, to the commercial (Pt) deposited on activated carbon powder (Johnson Matthey) and to pure Vulcan XC-72 for their respective abilities toward the hydrogen evolution reaction (HER). The Tafel parameters were determined for all these electrodes. From the I–V curves and their quantitative treatment, the following order of activity emerged unambiguously and reads: (PtCO)₂ (fcc structure) > (PtCO)₁ (Chini cluster) > (Pt)_neat > (Pt)_JM (Johnson Matthey) ≫ (Vulcan XC-72). As expected, all the Pt-loaded electrodes were more efficient than Vulcan XC-72. The classification appears to be linked with the mean nanoparticle size, and for comparable sizes, with the surface morphology of the materials. The results and the stability of the electrodes suggest that the small particle sizes and the good dispersity on the carbon support were maintained during the HER.     

Nucleosides and Nucleotides. Part 21. Synthesis of a Tridecanucleoside Dodecaphosphate Incorporating the Unnatural Base 2 (1 H)-Pyridone

The modified nucleoside Π_d (1) was used in the synthesis of the oligonucleotide d (TpTpΠpCpGpTpCpApApApApTpC). Diester methodology being unsatisfactory, the triester synthesis was investigated with the unnatural nucleoside. An improved method of nucleoside phosphorylation was developed for the synthesis of the fully-protected nucleotide 2e. This molecule could be cleanly and selectively deprotected, and allowed the efficient synthesis of the desired oligonucleotide.     

Cover Picture

The cover picture shows in the background the whole cell of a methanotrophic bacterium on which are superimposed components of methane monooxygenase (the structure of the hydroxylase component (top), one of the two four-helix bundles that house the catalytic diiron centers (left)) and a schematic diagram of the catalytic cycle by which the enzyme converts dioxygen and methane into methanol and water. More about this unusual enzyme system is reported by Lippard et al. on p. 2782 ff.     

Stereo- and regioselectivity in asymmetric synthesis of α-amino substituted benzocyclic compounds

The enantiomerically pure chiral benzocyclic amines 6–8 were obtained by asymmetric transamination of the corresponding prochiral ketones 9a–c. The method involves: (a) formation of chiral imines 10a–c from the prochiral ketones 9a–c and the inexpensive chiral auxiliary (R)- or (S)-phenylethylamine (PEA); (b) asymmetrically induced reduction of these imines to the diastereomeric amines 11a–c and 12a–c; (c) catalytic hydrogenation to remove the benzylic fragment of the chiral PEA auxiliary. The stereoselectivity of the imine reduction, as well as the regioselectivity of the catalytic hydrogenation, are strongly dependent on the size of the saturated ring condensed with the benzene ring. This approach was used to develop a convenient, high yielding, and stereoselective route to several practically important optically active α-amino substituted benzocyclic compounds.     

Preparation of Layer Structure-Controlled Ru-Sn-Al2O3 Catalysts and Their Reactivity

In order to achieve functional group selective hydrogenation, the layer structure of Ru-Sn-Al2O3 catalysts was controlled by using sol-gel, powder impregnation and combined sol-gel impregnation methods. The properties of the catalysts and effectiveness in hydrogenation of dimethyl terephthalate were examined. The surface Sn contents of the catalysts characterized by X-ray photoelectron spectroscopy depended on the preparation method, in spite of almost the same bulk Ru and Sn compositions measured by X-ray fluorescence analyses. TPR and CO adsorption of the catalysts also depended on the preparation method. With regard to the conversion rate of dimethyl terephthalate and the rate of product conversion from methyl 4-hydroxy methylbenzoate to p-xylene via methyl p-toluate, Ru impregnation catalysts had higher rates than the other catalysts.     

Biosynthesis of isoprenoids. purification and properties of IspG protein from Escherichia coli

[Structure: see text]. The IspG protein is known to catalyze the transformation of 2-C-methyl-d-erythritol 2,4-cyclodiphosphate into 1-hydroxy-2-methyl-2-(E)-butenyl 4-diphosphate in the nonmevalonate pathway of isoprenoid biosynthesis. We have found that the apparent IspG activity in the cell extracts of recombinant Escherichia coli cells as observed by a radiochemical assay can be enhanced severalfold by coexpression of the isc operon which is involved in the assembly of iron-sulfur clusters. The recombinant protein was isolated by affinity chromatography under anaerobic conditions. With a mixture of flavodoxin, flavodoxin reductase, and NADPH as the reducing agent, stringent assay methods based on photometry or on 13C NMR detection of multiply 13C-labeled substrate/product ratios afforded catalytic activities greater than 60 nmol mg(-1) min(-1) for the protein "as isolated" (i.e., without reconstitution of any kind). Lower apparent activities were found using photoreduced deazaflavin as an artifactual electron donor, whereas dithionite was unable to serve as an artificial electron donor. The apparent Michaelis constant for 2-C-methyl-D-erythritol 2,4-cyclodiphosphate was 700 microM. The enzyme was inactivated by EDTA and could be reactivated by Mn2+. The pH optimum was at 9.0. The protein contained 2.4 iron ions and 4.4 sulfide ions per subunit. The replacement of any of the three conserved cysteine residues afforded mutant proteins which were devoid of catalytic activity and contained less than 6% of Fe2+ and less than 23% of S2- as compared to the wild-type protein. Sequence comparison indicates that putative IspG proteins of plants, the apicomplexan protozoan Plasmodium falciparum, and bacteria from the Bacteroidetes/Chlorobi group contain an insert of about 170-320 amino acid residues as compared with eubacterial enzymes.     

Phase separation of p53 precedes aggregation and is affected by oncogenic mutations and ligands

Mutant p53 tends to form aggregates with amyloid properties, especially amyloid oligomers inside the nucleus, which are believed to cause oncogenic gain-of-function (GoF). The mechanism of the formation of the aggregates in the nucleus remains uncertain. The present study demonstrated that the DNA-binding domain of p53 (p53C) underwent phase separation (PS) on the pathway to aggregation under various conditions. p53C phase separated in the presence of the crowding agent polyethylene glycol (PEG). Similarly, mutant p53C (M237I and R249S) underwent PS; however, the process evolved to a solid-like phase transition faster than that in the case of wild-type p53C. The data obtained by microscopy of live cells indicated that transfection of mutant full-length p53 into the cells tended to result in PS and phase transition (PT) in the nuclear compartments, which are likely the cause of the GoF effects. Fluorescence recovery after photobleaching (FRAP) experiments revealed liquid characteristics of the condensates in the nucleus. Mutant p53 tended to undergo gel- and solid-like phase transitions in the nucleus and in nuclear bodies demonstrated by slow and incomplete recovery of fluorescence after photobleaching. Polyanions, such as heparin and RNA, were able to modulate PS and PT in vitro. Heparin apparently stabilized the condensates in a gel-like state, and RNA apparently induced a solid-like state of the protein even in the absence of PEG. Conditions that destabilize p53C into a molten globule conformation also produced liquid droplets in the absence of crowding. The disordered transactivation domain (TAD) modulated both phase separation and amyloid aggregation. In summary, our data provide mechanistic insight into the formation of p53 condensates and conditions that may result in the formation of aggregated structures, such as mutant amyloid oligomers, in cancer. The pathway of mutant p53 from liquid droplets to gel-like and solid-like (amyloid) species may be a suitable target for anticancer therapy.

Mutant p53 tends to form aggregates with amyloid properties, especially amyloid oligomers inside the nucleus, which are believed to cause oncogenic gain-of-function (GoF).     

On hydrogen activation in the hydroformylation of olefins with Rh4(CO)12 or Co2(CO)8 as catalyst precursors

In the hydroformylation of ethylene with approximately equimolar H₂/D₂ mixtures and Rh₄(CO)₁₂ or Co₂(CO)₈ as the catalyst precursor about 50% of propionaldehyde-d₁ was formed. The propionaldehyde-d₀/d₂ ratio was ～ 3 for rhodium and ～ 2.6 for the cobalt catalyst. On the basis of the results and assuming that there is no rapid M(H)₂/M(D)₂ scrambling, activation of hydrogen through M(H)₂ or M(H)₂(olefin) complexes can be excluded.     

CHARGE TRANSFER ACROSS PIGMENTED BILAYER LIPID MEMBRANE AND ITS INTERFACES

Abstract— The technique of forming bilayer lipid membranes (BLM) has made it possible to study photoreactions of pigments in an environment that is much closer to those in photosynthetic and visual membranes. A pigmented BLM system with Mg²⁺-porphyrins as membrane-bound pigments and with ferricyanide and ferrocyanide as the aqueous electron acceptor and donor, respectively, was used to illustrate the photoelectric effects due to coupled interfacial charge transfer reactions.
The steady-state continuous photoresponse was studied by means of the voltage clamp method and a null current method. The independence of the pigment conductance channel and the ionic conductance channel was demonstrated. A tunable voltage clamp method was used to study the transient pulsed photoresponses. Such a measurement permits us to characterize the photosystem in terms of an equivalent circuit model which contains a novel chemical capacitance. Molecular interpretation of this equivalent circuit model was given.
A microscopic model based on the Gouy–Chapman theory and chemical kinetics calculation leads to an equivalent circuit which is also equivalent to the previous one. Generalization of this microscopic model further leads to a physical mechanism of the generation of the early receptor potential (ERP) in visual membranes. Relevance of pigmented BLM research to photosynthesis and other disciplines was also discussed.     

Formation of Zn(1-x)MnxS nanowires within mesoporous silica of different pore sizes

Arrays of highly ordered Zn(1-x)MnxS quantum wires with x ranging from 0.01 to 0.3 and with lateral dimensions of 3, 6, and 9 nm were synthesized within mesoporous SiO2 host structures of the MCM-41 and SBA-15 type. The hexagonal symmetry of these arrays (space group p6m) and the high degree of order was confirmed by X-ray diffraction and transmission electron microscopy (TEM) studies. Physisorption measurements show the progressive filling of the pores of the SiO2 host structures, while TEM and Raman studies reveal the wire-like character of the incorporated Zn(1-x)MnxS nanostructures. X-ray absorption near-edge structure, extended X-ray absorption fine structure, photoluminescence excitation (PLE), and electron paramagnetic resonance studies confirm the good crystalline quality of the incorporated Zn(1-x)MnxS guest species and, in particular, that the Mn2+ ions are randomly distributed and are situated on tetrahedrally coordinated cation sites of the Zn(1-x)MnxS wires for all x up to 0.3. The amount of Mn2+ ions loosely bound to the surface of the Zn(1-x)MnxS nanowires is less than 4% of the total Mn content even for the 3 nm nanostructures up to the highest Mn content of x = 0.3. The effects of the reduction of the lateral dimensions on electronic properties of the diluted magnetic semiconductor were studied by PLE spectroscopy. Due to the quantum confinement of the excitons in the wires an increase of the direct band gap with decreasing particle size is observed.