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61.
Co/Rh (Co:Rh = 2:2) heterobimetallic nanoparticles derived from Co(2)Rh(2)(CO)(12) react with alkynes and alpha,beta-unsaturated aldehydes such as acrolein, crotonaldehyde, and cinnamic aldehyde and release products resulting from [2 + 2 + 1]cycloaddition of alkyne, carbon monoxide, and alkene. alpha,beta-Unsaturated aldehydes act as a CO and alkene source. These reactions produce 2-substituted cyclopentenones. 相似文献
62.
A series of chemoselective polymers had been designed and synthesized to enhance the sorption properties of polymer coated chemical sensors for polynitroaromatic analytes. To evaluate the effectiveness of the chemoselective coatings, a polynitroaromatic vapor test bed was utilized to challenge polymer coated surface acoustic wave (SAW) devices with different explosive vapors. Dinitrotoluene detection limits were determined to be in the <100 parts per trillion ranges. ATR-FTIR studies were used to determine the nature of the polymer-polynitroaromatic analyte interactions, and confirm the presence of hydrogen-bonding between polymer pendant groups and the nitro functional groups of polynitroaromatic explosive materials. 相似文献
63.
King RB 《Dalton transactions (Cambridge, England : 2003)》2004,(21):3420-3424
Nickel and palladium atoms with their closed-shell d(10) electronic configurations are encapsulated in the icosahedral clusters [Ni@Ni(10)E(2)(CO)(18)](4-)(E = Sb, Bi, Sb[rightward arrow]Ni(CO)(3), CH(3)Sn and n-C(4)H(9)Sn) and the geometrically related pentagonal antiprismatic cluster Pd@Bi(10)(4+) found in Bi(14)PdBr(16). Such endohedral d(10) atoms in pentagonal antiprismatic clusters are donors of zero skeletal electrons and interact only weakly with the atoms in the surrounding polyhedron so that they may be regarded as analogous to endohedral noble gases in fullerenes such as He@C(60). On the other hand, endohedral nickel and palladium atoms in 10- and 11-vertex flattened deltahedral bare metal clusters of group 13 metals without five-fold symmetry, such as Ni@E(10)(10-) found in Na(10)NiE(10)(E = Ga, In) and Pd@Tl(11)(7-) found in A(8)Tl(11)Pd (A = Cs, Rb, K), interact significantly with the cluster atoms, particularly those at the flattened vertices of the deltahedron. The role of endohedral d(10) atoms Ni and Pd in polyhedra with five-fold symmetry as "pseudo-noble-gases" can be related to their positions at the "composite divide" of the "Metallurgists' Periodic Table" proposed by H. E. N. Stone on the basis of alloy systematics as well as the equivalence of the five d orbitals in polyhedra with five-fold symmetry. 相似文献
64.
For large-volume stacking with the electroosmotic flow pump (LVSEP) in capillary electrophoresis of anionic analytes it is required that the electroosmotic mobility (EOM) should be smaller than the magnitudes of the effective mobilities of the analytes. When a fused-silica capillary is treated with an acidic solution, the silanoate group on the silica surface is neutralized to silanol and the EOM is suppressed. Due to the slow deprotonation equilibrium of the silanol group at an intermediate pH, this reduced EOM can be retained during a number of electrophoresis runs. Using a bare fused-silica capillary preconditioned with 0.01 M HCl, successful LVSEP at pH 6.0 was achieved for weakly acidic compounds with two orders of magnitude enhancements in the concentration sensitivity. The repeatability in migration times of ten analytes stacked by LVSEP in a single day was excellent with the relative standard deviation (RSD) less than 1% (n = 6). The day-to-day repeatability was also excellent with RSD less than 3% (n = 3 x 6) when the capillary was preconditioned each day. 相似文献
65.
This paper describes the synthesis of three neutral water soluble poly(amidoamine) (PAMAM) dendrimer derivatives. The ability of the two larger dendrimers to bind small acidic hydrophobic molecules is reported. Spectroscopic data and pH behaviour suggested that the acidic hydrophobes were forming stable ion pairs with the dendrimer's internal, basic tertiary nitrogens. With respect to forming 1:1 and 2:1 substrate/dendrimer complexes, both of the larger dendrimers were equally efficient at binding. All dendrimer/substrate complexes were completely miscible with water in all proportions (i.e. infinitely water soluble). When the bound substrates are drug moieties, then the resulting complexes could be considered as potential drug delivery systems. Flow calorimetry demonstrated that the dendrimers were able to release their hydrophobic guests when in contact with a biological cell. 相似文献
66.
The water gas shift reaction (CO + H2O = CO2+ H2) is catalyzed by aqueous metal carbonyl systems derived from simple mononuclear carbonyls such as Fe(CO)5 and M(CO)6 (M = Cr, Mo, and W) and bases in the 140–200 °C temperature range. The water gas shift reaction in a basic methanol-water solution containing Fe(CO)5 is first order in [Fe(CO)5], zero order in [CO], and essentially independent of base concentration and appears to involve an associative mechanism with a metallocarboxylate intermediate [(CO)4Fe-CO2H]–. The water gas shift reactions using M(CO)6 as catalyst precursors are first order in [M(CO)6], inverse first order in [CO], and first order in [HCO2
–] and appear to involve a dissociative mechanism with formatometallate intermediates [(CO)5M-OCHO]–.The Reppe hydroformylation of ethylene to produce propionaldehyde and 1-propanol in basic solutions containing Fe(CO)5 occurs at 110–140 °C. This reaction is second order in [Fe(CO)5], first order in [C2H4] up to a saturation pressure >1.5 MPa, and inhibited by [CO]. These experimental results suggest a mechanism where the rate-determining step involves a binuclear iron carbonyl intermediate. The substitution of Et3N for NaOH as the base facilitates the reduction of propionaldehyde to 1-propanol but results in a slower rate for the overall reaction.The homogeneous photocatalytic decomposition of the formate ion to H2 and CO2 in the presence of Cr(CO)6 appears to be closely related to the water gas shift reaction. The rate of H2 production from the formate ion exhibits saturation kinetics in the formate ion and is inhibited by added pyridine. The infrared spectra of the catalyst solutions indicate an LCr(CO)5 intermediate. Photolysis of the Cr(CO)6/formate system in aqueous methanol in the presence of an aldehyde RCHO (R =n-heptyl,p-tolyl, andp-anisyl) results in catalytic hydrogenation of the aldehyde to the corresponding alcohol RCH2OH by the formate ion. Detailed kinetic studies onp-tolualdehyde hydrogenation by this method indicates saturation kinetics in formate ion, autoinhibition by thep-tolualdehyde, and a threshold effect for Cr(CO)6 at concentrations >0.004 mol L–1. The presence of an aldehyde can interrupt the water gas shift catalytic cycle by interception of an HCr(CO)5
– intermediate by the aldehyde.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1533–1539, September, 1994. 相似文献
67.
A new dihydroberberine alkaloid, 7,8‐dihydro‐8‐methoxyberberine ( 1 ), along with six known compounds including two dihydroberberine alkaloids, 7,8‐dihydro‐8‐hydroxyberberine ( 2 ) and oxyberberine ( 3 ) and four protoberberine alkaloids, berberine ( 4 ), palmatine ( 5 ), jatrorrhizine ( 6 ) and columbamine ( 7 ), were isolated from the stems of Mahonia japonica. These compounds were characterized and identified by physical and spectral evidence. 相似文献
68.
69.
J. Jung H. S. Jeong H. H. Chung M. J. Lee J. H. Jin K. B. Park 《Journal of Radioanalytical and Nuclear Chemistry》2003,255(3):543-546
The radioactive concentrations of radionuclides were measured in the soil and groundwater below the 12 GeV proton beam-line tunnel at KEK. Various long-lived radionuclides, (7Be, 22Na, 46Sc, 54Mn, 60Co, 134Cs, 152Eu and 154Eu) were observed in the soil samples by -ray spectra measurements, and 3H was also detected by liquid scintillation counting. On the other hand, 3H, 22Na and 54Mn, which were leached from the soil were measured in the groundwater below the EP2 beam line. 3H and 22Na were also found in slight amounts in groundwater collected in a well dug beside the East Counter Hall. From a comparison with the radioactive concentration in soil and groundwater, the order of the leaching percentages were 3H>22Na>54Mn. This tendency was in agreement with an experimental result of the RI laboratory. 相似文献
70.
A variety of simple alkyl and aryl isocyanides have been polymerized using 0.5% NiCl2 in ethanol as a catalyst. The resulting poly(iminomethylenes) have been characterized by carbon-13 NMR spectroscopy and their polystyrene-equivalent molecular weights have been determined by gel permeation chromatography. Straight chain aliphatic isocyanides having from three to ten carbon atoms in the chain form readily solyble polymers having molecular weights (Mw) in the general range 10,000 to 30,000. Neopentyl isocyanide unlike tert-butyl isocyanide forms an insoluble polymer. A number of new soluble aryl isocyanide polymers have been obtained. However, aryl isocyanides having a single alkyl substituent (CH3, C2H5, CF3) in the ortho position give only insoluble polymers, whereas aryl isocyanides having alkyl substituents in both ortho positions (e.g., 2,6-(CH3)2C6H3NC and 2,4,6-(CH3)3C6H2NC) fail to polymerize under these conditions. The highest molecular weight soluble aryl isocyanide homopolymer is obtained from 3-CH3OC6H4NC(Mw = 26,000). The trimethylsilyl substituted isocyanide (CH3)3SiCH2CH2NC has been obtained from LiCH2NC and (CH3)SiCH2Cl and gives a brown soluble homopolymer with a molecular weight (Mw) of 19,000. 相似文献