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Facile Ar-CF3 bond formation at Pd. Strikingly different outcomes of reductive elimination from [(Ph3P)2Pd(CF3)Ph] and [(Xantphos)Pd(CF3)Ph].

Facile and highly selective perfluoroalkyl-aryl reductive elimination from a metal center (Pd) has been demonstrated for the first time. At temperatures as low as 50-80 degrees C, [(Xantphos)Pd(Ph)CF3] undergoes remarkably clean decomposition to produce CF3Ph in high yield and selectivity. In contrast, analogous trifluoromethylpalladium aryls stabilized by rigid cis-chelating ligands such as dppe are completely unreactive at temperatures up to 130-140 degrees C. Decomposition of [(Ph3P)2Pd(Ph)CF3] in the presence of PhI in benzene at 60 degrees C does not produce PhCF3 but rather leads to [(Ph3P)2Pd(Ph)I] and [Ph4P]+[(Ph3P)Pd(CF3)3]- in a 2:1 ratio with high selectivity.

Crystallography, X-Ray↗

Organosulfur-functionalized Au, Pd, and Au-Pd nanoparticles on 1D silicon nanowire substrates: preparation and XAFS studies.

A hybrid preparative method was developed to prepare organosulfur-functionalized Au nanoparticles (NPs) on silicon nanowires (SiNWs) by reacting HAuCl(4) with SiNW in the presence of thiol. A number of organosulfur molecules-dodecanethiol, hexanethiol, 1,6-hexanedithiol, and tiopronin-were used to functionalize the Au surface. Size-selected NPs ranging from 1.6 to 7.5 nm were obtained by varying the S/Au ratio and the concentration of HAuCl(4). This method was further extended to the preparation Pd and Pd-Au bimetallic NPs on SiNWs. The morphology of the metal nanostructures was examined by transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The local structure and bonding of the SiNW-supported metal nanostructures were studied using X-ray absorption fine structures (XAFS) [including both X-ray near-edge structures (XANES) and extended X-ray absorption fine structures (EXAFS)] at the Au L(3)-, Pd K-, S K-, and Si K-edges. It was also found that the annealing of the thiol-capped Au NPs up to 500 degrees C transforms the surface of the thiol-capped NPs to gold sulfide, as identified using Au L(3)- and S K-edge XANES. We also illustrate that this preparative approach can be used to form size-controllable Au NPs on carbon nanotubes.

Journal Article↗

Precipitation of (PdxAg1-x)3 In in Ag-25% Pd-In alloys and the partial phase diagram of ternary Ag-Pd-In alloys.

A study was carried out to determine the partial phase diagram for the system Ag-25 wt % Pd-y wt% In with y </= 8 by X-ray powder diffraction and differential thermal analysis. The liquidus and solidus temperatures decreased with increasing indium content up to 8 wt % In for a given 25 wt % Pd. The solvus curve of gamma phase identified as (PdxAg1-x)3 In was determined by the parametric method and the temperature dependence of In-solubility in Ag-25 wt % Pd was very strong above 900 degrees C.

Journal Article↗

In vitro and in vivo activities of clinafloxacin, CI-990 (PD 131112), and PD 138312 versus enterococci.

Certain new fluoroquinolones have high activity against enterococci. Against Enterococcus faecalis (n = 18), MICs at which 90% of the isolates were inhibited were as follows (in micrograms per milliliter): clinafloxacin, 0.125; CI-990, 0.5; and PD 138312, 0.25 (compared with 1 microgram/ml for ciprofloxacin and 2 micrograms/ml for ofloxacin). Strains producing beta-lactamase or that were vancomycin resistant or resistant to high-level gentamicin were not quinolone cross-resistant. The drugs were bactericidal and were unaffected by 50% human serum. Oral efficacies (in milligrams per kilogram of body weight for 50% protective doses) in lethal mouse infections with quinolone-susceptible strains were 4.3 to 24 for clinafloxacin, 7.2 to 39 for CI-990, 7.2 to 76 for PD 138312, and 41 to > 100 for ciprofloxacin; when the drugs were given subcutaneously, the order was similar and values ranged from 1.1 to 12.5. Clinafloxacin, CI-990, and PD 138312 may have therapeutic potential in systemic enterococcal infections in humans.

Animals↗

Development of Ag-Pd-Au-Cu alloy for multiple dental applications. Part 1. Effects of Pd and Cu contents, and addition of Ga or Sn on physical properties and bond with ultra-low fusing ceramic.

Ag-Pd-Au-Cu quaternary alloys consisting of 30-50% Ag, 20-40% Pd, 10-20% Cu and 20% Au (mother alloys) were prepared. Then 5% Sn or 5% Ga was added to the mother alloy compositions, and another two alloy systems (Sn-added alloys and Ga-added alloys) were also prepared. The bond between the prepared alloys and an ultra-low fusing ceramic as well as their physical properties such as the solidus point, liquidus point and the coefficient of thermal expansion were evaluated. The solidus point and liquidus point of the prepared alloys ranged from 802 degrees C to 1142 degrees C and from 931 degrees C to 1223 degrees C, respectively. The coefficient of thermal expansion ranged from 14.6 to 17.1 x 10(-6)/degrees C for the Sn- and Ga-added alloys. In most cases, the Pd and Cu contents significantly influenced the solidus point, liquidus point and coefficient of thermal expansion. All Sn- and Ga-added alloys showed high area fractions of retained ceramic (92.1-100%), while the mother alloy showed relatively low area fractions (82.3%) with a high standard deviation (20.5%). Based on the evaluated properties, six Sn-added alloys and four Ga-added alloys among the prepared alloys were suitable for the application of the tested ultra-low fusing ceramic.

Analysis of Variance↗

Sulfuration resistance of five experimental Ag-Pd-Au-Cu alloys with low Pd content of 10 or 12%.

Commercial Ag-based alloy (46Ag-20Pd-12Au-20Cu alloy) is widely used in Japan as a casting alloy. As opposed to the commercial composition, we prepared five experimental Ag-based alloys with reduced Pd content of 10 or 12%, increased Au content of 20 to 30%, and reduced Cu content of 12 to 20%. We then evaluated their sulfuration resistance by analyzing cast specimen surfaces dipped in 0.1% Na2S solution with SEM/EPMA, TF-XRD, and XPS. It became evident that all alloys were susceptible to sulfuration in the segregated Ag-rich Pd-poor phases. The degree and speed of sulfuration, however, differed among the six alloys examined. In particular, one experimental alloy (46Ag-10Pd-30Au-12Cu) possessed a sulfuration resistance equal or superior to that of commercial Ag-based alloy, while the other four experimental alloys were inferior in sulfuration resistance. Based on the results of this study, we concluded that our newly developed 46Ag-10Pd-30Au-12Cu alloy could be employed as a new sulfuration-resistant Ag-based casting alloy--which is especially useful if the price of Pd is skyrocketing again.

Corrosion↗

Novel antitumor agents CI-920, PD 113,270 and PD 113,271. I. Taxonomy, fermentation and biological properties.

CI-920 (PD 110,161) and two analogues (PD 113,270 and PD 113,271) are novel antitumor compounds produced by a new actinomycete characterized as Streptomyces pulveraceus subsp. fostreus ATCC 31906. The antitumor compounds are predominantly produced during the stationary (idiophase) growth phase of the organism. CI-920 is active versus the murine P388 lymphocytic and L1210 lymphoid leukemia with T/C values of 246 and 207, respectively. This compound has no significant antimicrobial activity.

Alkenes↗

PD 124,895 and PD 124,966, two new antitumor antibiotics.

The isolation and characterization of the title antibiotics, which are produced by the same Streptomyces sp., is described. The potent antitumor agent, PD 124,895, is an analog of hydroxyelactocin (PD 114,721). PD 124,966 is a new member of the depsipeptide family of antibiotics.

Animals↗

Erythrocyte G-6-PD and 6-PGD genetic polymorphisms in South African Negroes, with a note on G-6-PD and the malaria hypothesis.

Sample of 981 and 998 South African Negroes belonging to seven different ethnic groups were screened for G-6-PD and 6-PGD phenotypes, respectively. The results are discussed in terms of the interethnic variability and the possible adaptive values of these genetic polymorphisms. Particular attention is paid to the geographic co-distribution and interrelationship of G-6-PD deficiency and the occurrence of malaria in South Africa.

Black People↗

Separation of pd(GC)12 from pd(AT)12 by free solution capillary electrophoresis.

The two synthetic self complementary oligonucleotides pd(AT)12 and pd(GC)12 were separated by free solution capillary electrophoresis (CZE) using simple borate buffers. The effects of pH (7.5-9) and the concentration of the buffer (0.03-0.35 M) were investigated. Higher pH values and buffer concentrations led to better resolution and longer migration times, the pH having a more pronounced effect on the separation than the concentration of the buffer. It is proposed that the conformation and effective length of the oligonucleotides may have a role in their separation in free solution capillary electrophoresis.

Boric Acids↗

Theoretical and experimental determination of dosimetric characteristics for brachyseed Pd-103, model Pd-1, source.

Dosimetric characteristics of the BrachySeed Pd-103, Model Pd-1 source have been determined using both theoretical and experimental methods. Dose rate constant, radial dose function, and anisotropy functions of the source have been obtained following the TG-43 recommendations. Derivation of the dose rate constant was based on recent NIST WAFAC calibration performed in accordance with their 1999 Standard. Measurements were performed in Solid Water using LiF TLD chips. Theoretical simulation calculations were performed in both Solid Water and water phantom materials using MCNP4C2 Monte Carlo code using DLC-200 interaction data. The results of the Monte Carlo simulation indicated a dose rate constant of 0.65 cGyh(-1)U(-1) and 0.61 cGyh (-1)U(-1) in water and Solid Water, respectively. The measured dose rate constant in Solid Water was found to be 0.63+/-7% cGyh (-1)U(-1), which is within the experimental uncertainty of the Monte-Carlo simulated results. The anisotropy functions of the source were calculated in both water and in Solid Water at the radial distances of 1 to 7 cm. Measurements were made in Solid Water at distances of 2, 3, 5, and 7 cm. The Monte-Carlo calculated anisotropy constant of the new source was found to be 0.98 in water. The tabulated data and 5th order polynomial fit coefficients for the radial dose function along with the dose rate constant and anisotropy functions are provided to support clinical use of this source.

Anisotropy↗

van der Waals Radii of Pt(II) and Pd(II) in Molecular Mechanics Models and an Analysis of Their Relevance to the Description of Axial M.H(-C), M.H(-N), M.S, and M.M (M = Pd(II) or Pt(II)) Interactions.

Parameters have been developed for the molecular mechanics modeling of nonbonded interactions involving Pt(II) and Pd(II). The value obtained for the van der Waals radius-about 1.7 Å-accords well with the value proposed by Bondi (J. Chem. Phys. 1964, 68, 441-451). This model has been used to investigate close M.H(-C), M.H(-N), M.H(-O), M.S, and M.M (M = Pd(II) or Pt(II)) contacts that have previously been described as weak or agostic bonds. It is argued that the M.H(-C) interactions are best described as van der Waals interactions that are in the repulsive region but the results are in accord with the description of M.H(-N) and M.H(-O) contacts as weak hydrogen bonds. M.S and M.M separations in systems without pi-acceptor ligands were accurately reproduced by using the same van der Waals parameters.

Journal Article↗

Pd-Ti and Pd-Co-Au electrocatalysts as a replacement for platinum for oxygen reduction in proton exchange membrane fuel cells.

Fuel cells are appealing for a variety of energy needs, but the high materials and manufacturing costs have hampered their commercialization. The limited availability and the high cost of the currently used platinum catalysts, for example, pose a serious problem in their practical application. We report here non-platinum electrocatalyst systems, such as Pd-Co-Au and Pd-Ti, that are proposed from simple thermodynamic guidelines and selected by a rapid screening technique, which show electrochemical performance in proton exchange membrane fuel cells (PEMFC) similar to that found with commercial platinum catalysts. This finding opens up a new avenue to develop potentially less expensive electrocatalysts.

Alloys↗

Sequential Pd(II)-Pd(0) catalysis for the rapid synthesis of coumarins.

Electrophilic palladium-catalyzed cycloisomerization of brominated aryl propiolates produces brominated coumarins. The brominated coumarins can be diversified by reduction of the Pd(II) catalyst to Pd(0) followed by Suzuki, Sonogashira, Heck, or Hartwig-Buchwald coupling. Thus, a single loading of precatalyst can be used to conduct sequential reactions, allowing the synthesis of functionalized coumarins. Extension of this methodology toward the synthesis of coumarin libraries is discussed.

Bromine↗

Ethene adsorption, dehydrogenation and reaction with Pd(110): Pd as a carbon 'sponge'.

The interaction of ethene with the Pd(110) surface has been investigated, mainly with a view to understanding the dehydrogenation reactions of the molecule and mainly using a molecular beam reactor. Ethene adsorbs with a high probability over the temperature range 130 to 800 K with the low-coverage sticking probability dropping from 0.8 at 130 K to 0.35 at 800 K. The adsorption is of the precursor type, with a weakly held form of ethene being the intermediate between the gas phase and strong chemisorption. Dehydrogenation begins at approximately 300 K and is fast above 350 K. If adsorption is carried out at temperatures up to approximately 380 K, adsorption saturates after about 0.25 monolayer have adsorbed, but above approximately 450 K, adsorption continues at a high rate with continuous hydrogen evolution and C deposition onto the surface. It appears that, in the intermediate temperature range, the carbonaceous species formed is located in the top layer and thus interferes with adsorption, whereas the C goes subsurface above 450 K, the adsorption is almost unaffected, and the C signal is significantly attenuated in XPS. However, the deposited carbon can easily be removed again by reaction with oxygen, thus implying that the carbon remains in the selvedge, that is, in the immediate subsurface region probably consisting of a few atomic layers. No well-ordered structures are identified in either LEED or STM, though some evidence of a c(2 x 2) structure can be seen. The Pd surface, at least above 450 K, appears to act as a "sponge" for carbon atoms, and this effect is also seen for the adsorption of other hydrocarbons such as acetaldehyde and acetic acid.

Journal Article↗

Synthesis and structural characterization of the first unsymmetrical diarylpalladium complex trans-Pd(C6F5)(2,4,6-C6F3H2)(PEt3)2, derived from transmetallation between 2,4,6-trifluorophenylboronic acid and trans-Pd(C6F5)I(PEt3)2.

The reactions of 2,4,6-trifluorophenylboronic acid with aryl(iodo)palladium(ii) complexes, trans-Pd(C(6)F(5))I(PR(3))(2)(PR(3)= PEt(3), PMe(2)Ph, PMePh(2)) in the presence of Ag(2)O afforded trans-Pd(C(6)F(5))(2,4,6-C(6)F(3)H(2))(PR(3))(2) which are stabilized by fluorine atoms in the ortho positions.

Journal Article↗

Pd-Dissolution through a mild and effective one-step reaction and its application for Pd-recovery from spent catalytic converters.

We describe here an innovative method for Pd-dissolution using the reagent N,N'-dimethylperhydrodiazepine-2,3-dithione diiodine adduct which, being safe and powerful, is appealing for practical applications: remarkably almost quantitative Pd-recovery from model spent three-way catalysts has been obtained, showing that the effectiveness of the method is maintained when palladium is contained in a complex system such as a car catalyst, a ceramic material which has undergone severe thermal stress.

Journal Article↗