Measurement of storage time, estimation of ion number and study of absorption line profile in a Paul trap

Europium (Eu⁺) ions were confined in a Paul trap and detected by non-destructive method. Storage time of Eu⁺ ions achieved in vacuum was improved by orders of magnitude employing buffer gas cooling. The experimentally detected signal was fitted to the ion response signal and the total number of ions trapped was estimated. It is found that the peak signal amplitude as well as the product of FWHM and the peak signal amplitude is proportional to the total number of trapped ions. The trapped ion secular frequency was swept at different rates and its effect on the absorption line profile was studied both experimentally and theoretically.     

Low-temperature destruction of carbon tetrachloride over lanthanide oxide-based catalysts: from destructive adsorption to a catalytic reaction cycle

The catalytic destruction of carbon tetrachloride in the presence of steam, CCl(4) + 2 H(2)O-->4 HCl + CO(2), was investigated at 200-350 degrees C over a series of lanthanide (La, Ce, Pr and Nd) and alkaline-earth metal (Mg, Ca, Sr and Ba) oxide-based catalysts with kinetic experiments, Raman spectroscopy, X-ray photoelectron spectroscopy, IR spectroscopy, X-ray diffraction, and DFT calculations. This new catalytic reaction was achieved by combining destructive adsorption of CCl(4) on a basic oxide surface and concurrent dechlorination of the resulting partially chlorinated solid by steam. The combination of the two noncatalytic reactions into a catalytic cycle provided a rare opportunity in heterogeneous catalysis for studying the nature and extent of surface participation in the overall reaction chemistry. The reaction is proposed to proceed over a terminal lattice oxygen site with stepwise donation of chlorine atoms from the hydrocarbon to the surface and formation of the gas-phase intermediate COCl(2), which is readily readsorbed at the catalyst surface to form CO(2). In a second step, the active catalyst surface is regenerated by steam with formation of gas-phase HCl. Depending on the reaction conditions, the catalytic material was found to transform dynamically from the metal oxide state to the metal oxide chloride or metal chloride state due to the bulk diffusion of oxygen and chlorine atoms. A catalyst obtained from a 10 wt % La(2)O(3)/Al(2)O(3) precursor exhibited the highest destruction rate: 0.289 g CCl(4) h(-1) g(-1) catalyst at 350 degrees C, which is higher than that of any other reported catalyst system.     

Relative activity of La2O3, LaOCl, and LaCl3 in reaction with CCl4 studied with infrared spectroscopy and density functional theory calculations

Relative activity of La2O3, LaOCl, and LaCl3 in the destructive adsorption of CCl4 to CO2 was studied with density-functional theory calculations and temperature-programmed reaction experiments monitored with IR spectroscopy. Integral absorbance of the IR peak for phosgene, which is a reaction intermediate, was obtained as a function of temperature, and initial reaction temperatures were compared for different sample amounts of La2O3 and LaOCl. The initial reaction temperatures of about 390 K for La2O3 and 365 K for LaOCl were practically independent of the tested sample weights, and the lower temperature for LaOCl was attributed to a higher activity of surface sites on this material. Calculations suggest that CCl4 decomposition proceeds through a stepwise Cl donation from CCl4 to the surface and that the overall rate is controlled by the first step: CCl4 splitting into a Cl anion and CCl3 cation over an acid-base pair of surface sites. A lanthanum acid site in the pair initiates the split by interacting with one of the chlorine atoms in CCl4, and an oxygen base site stabilizes the remaining CCl3 fragment. Transition state estimates suggest that the relative activity of surface sites can be ranked in the following order: LaOCl > LaCl3 with a partially dechlorinated surface > La2O3. Surface Lewis acidity and basicity of these materials are summarized in terms of the vibrational frequency for adsorbed CO, energy of the lowest unoccupied molecular orbital, and proton affinity. Higher activity of LaOCl is attributed to the higher acidity of the lanthanum site, the higher basicity of the oxygen site, and the geometry of the acid-base pair of sites that allows them to interact with CCl4 simultaneously.     

Catalytic Platinum Nanoparticles Decorated with Subnanometer Molybdenum Clusters for Biomass Processing

The development of improved technologies for biomass processing into transportation fuels and industrial chemicals is hindered due to a lack of efficient catalysts for selective oxygen removal. Here we report that platinum nanoparticles decorated with subnanometer molybdenum clusters can efficiently catalyze hydrodeoxygenation of acetic acid, which serves as a model biomass compound. In contrast with monometallic Mo catalysts that are inactive and monometallic Pt catalysts that have low activities and selectivities, bimetallic Pt–Mo catalysts exhibit synergistic effects with high activities and selectivities. The maximum activity occurs at a Pt to Mo molar ratio of three. Although Mo atoms themselves are catalytically inactive, they serve as preferential binding anchors for oxygen atoms while a catalytic transformation proceeds on neighboring surface Pt atoms. Beyond biomass processing, Pt–Mo nanoparticles are promising catalysts for a wide variety of reactions that require a transformation of molecules with an oxygen atom and, more broadly, in other fields of science and technology that require tuning of surface–oxygen interactions.     

Infinitesimal algebras for the hypercomplex system SO(4)//SO(2)

Two infinitesimal objects are constructed for the hypercomplex system with base SO(4)//SO(2). It is proved that they are finitely generated algebras. Generators are found for both algebras and commutation relations between the generators established in each case. It is proved that these algebras are of the Poincaré -Birkhoff-Witt type.Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 42, No. 3, pp. 427–429, March, 1990.     

Adsorption and decomposition of cyclohexanone (C6H10O) on Pt(111) and the (2 × 2) and (√3 × √3)r30°-Sn/Pt(111) surface alloys

Adsorption and decomposition of cyclohexanone (C(6)H(10)O) on Pt(111) and on two ordered Pt-Sn surface alloys, (2 × 2)-Sn/Pt(111) and (√3 × √3)R30°-Sn/Pt(111), formed by vapor deposition of Sn on the Pt(111) single crystal surface were studied with TPD, HREELS, AES, LEED, and DFT calculations with vibrational analyses. Saturation coverage of C(6)H(10)O was found to be 0.25 ML, independent of the Sn surface concentration. The Pt(111) surface was reactive toward cyclohexanone, with the adsorption in the monolayer being about 70% irreversible. C(6)H(10)O decomposed to yield CO, H(2)O, H(2), and CH(4). Some C-O bond breaking occurred, yielding H(2)O and leaving some carbon on the surface after TPD. HREELS data showed that cyclohexanone decomposition in the monolayer began by 200 K. Intermediates from cyclohexanone decomposition were also relatively unstable on Pt(111), since coadsorbed CO and H were formed below 250 K. Surface Sn allowed for some cyclohexanone to adsorb reversibly. C(6)H(10)O dissociated on the (2 × 2) surface to form CO and H(2)O at low coverages, and methane and H(2) in smaller amounts than on Pt(111). Adsorption of cyclohexanone on (√3 × √3)R30°-Sn/Pt(111) at 90 K was mostly reversible. DFT calculations suggest that C(6)H(10)O adsorbs on Pt(111) in two configurations: by bonding weakly through oxygen to an atop Pt site and more strongly through simultaneously oxygen and carbon of the carbonyl to a bridged Pt-Pt site. In contrast, on alloy surfaces, C(6)H(10)O bonds preferentially to Sn. The presence of Sn, furthermore, is predicted to make the formation of the strongly bound C(6)H(10)O species bonding through O and C, which is a likely decomposition precursor, thermodynamically unfavorable. Alloying with Sn, thus, is shown to moderate adsorptive and reactive activity of Pt(111).     

Correction: Dermatan sulfate in tunicate phylogeny: Order-specific sulfation pattern and the effect of [→4IdoA(2-Sulfate)β-1→3GalNAc(4-Sulfate)β-1→] motifs in dermatan sulfate on heparin cofactor II activity

After the publication of the work entitled "Dermatan sulfate in tunicate phylogeny: Order-specific sulfation pattern and the effect of [→4IdoA(2-Sulfate)β-1→3GalNAc(4-Sulfate)β-1→] motifs in dermatan sulfate on heparin cofactor II activity", by Kozlowski et al., BMC Biochemistry 2011, 12:29, we found that the legends to Figures 2 to 5 contain serious mistakes that compromise the comprehension of the work. This correction article contains the correct text of the legends to Figures 2 to 5.