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81.
Razak J. Al-Essa Richard J. Puddephatt Charles F.H. Tipper Peter J. Thompson 《Journal of organometallic chemistry》1978,157(2):C40-C42
The platinacyclobutane complexes PtCl2L2(C3H5Me)], L pyridine, CD3CN, or tetrahydrofuran, exist as mixtures of isomers containing PH2 or P groups in rapid equilibrium. Decomposition occurs in some cases to give [PtCl2L(CH3CH2CHCH2)]. Stereospecific skeletal isomerisation also occurs in metallocyclobutanes containing the groups PH2 PHR, when R aryl further decomposition gives ν-allylplatinum complexes. 相似文献
82.
J. Popplewell A. Al-Qenaie S. W. Charles R. Moskowitz K. Raj 《Colloid and polymer science》1982,260(3):333-338
The thermal conductivity of a number of ferrofluids consisting of colloidally dispersed Fe3O4 particles in diester, hydrocarbon, water and fluorcarbon carriers have been measured at 38°C. The variation in thermal conductivity with particle concentration is well described by Tareef's equation (1940). This has enabled the ratio of the physical to magnetic size to be determined and compared with estimates of the ratio obtained from electron micrographs and magnetic measurements.The fit between theory and experiment is particularly good for hydrocarbon carrier fluids giving the ratio of solid to magnetic radiusR
i/R
m=1.24±0.03 compared with the value obtained from magnetic data and electron micrographs of 1.19±0.07. The corresponding value from the fluids with a diester carrier ranges between 1.1<R
d/R
m<1.3 which is again consistent with microscopy and magnetic data.The application of a magnetic field of 0.1 T had no noticeable effect on the thermal conductivities of ferrofluids. 相似文献
83.
Abdolhassen Talebian Alem Ghiorghis Charles F. Hammer Evelyn A. Murril Frank Pallas 《Journal of heterocyclic chemistry》1992,29(4):979-984
The syntheses and spectroscopic properties (ir, 1H nmr, 13C nmr, uv and ms) of pure samples of 2-chloro-4,6-bis(dimethylamino)-s-triazine 1 , 4,6-dichloro-2-dimethylamino-s-triazine 2 , 4,6-bis(dimethylamino)-s-triazin-2(lH)-one 3 , 4-chloro-6-dimethylamino-s-triazin-2(1H)-one 4 , 6-dimethylamino-s-triazine-2,4(1H,3H)-dione 5 , and 2,4,6-tris(dimethylamino)-s-triazine (altretamine, HMM) are reported. Evidence for enol-keto equilibria are also presented for 3 , in which the enol form exhibits as an H-bonded dimer structure similar to the dimer of organic carboxylic acids. 相似文献
84.
DNA-nanotube artificial ion channels 总被引:4,自引:0,他引:4
Harrell CC Kohli P Siwy Z Martin CR 《Journal of the American Chemical Society》2004,126(48):15646-15647
There is considerable interest in developing chemical devices that mimic the function of biological ion channels. We recently described such a device, which consisted of a single conically shaped gold nanotube embedded within a polymeric membrane. This device mimicked one of the key functions of voltage-gated ion channels: the ability to strongly rectify the ionic current flowing through it. The data obtained were interpreted using a simple electrostatic model. While the details are still being debated, it is clear that ion-current-rectification in biological ion channels is more complicated and involves physical movement of an ionically charged portion of the channel in response to a change in the transmembrane potential. We report here artificial ion channels that rectify the ion current flowing through them via this "electromechanical" mechanism. These artificial channels are also based on conical gold nanotubes, but with the critical electromechanical response provided by single-stranded DNA molecules attached to the nanotube walls. 相似文献
85.
Electron attachment to polar molecules and their non-covalent complexes can lead to different kinds of anions which differ from their excess electron localization. Spectroscopic methods for studying anion structures are reviewed. In many cases, the neutral and anion structures are identical and can be deduced from the electron attachment properties. Examples are given for complexes containing polar solvents or building blocks of biomolecules (nucleobases, amino acid residues...). 相似文献
86.
The copper-catalyzed pyrolysis of 1-diazo-3-(pyrrol-1-yl)-2-propanone (1a) and 1-diazo-4-(pyrrol-1-yl)-2-butanone (1b) in benzene solution gave 1 H-pyrrolizin-2-(3H)-one (4a) and 5,6-dihydroindolizin-7 (8H)-one (4b) , respectively, in quantitative yield. Similar pyrolysis of 1-diazo-4-(3-methylindol-1-yl)-2-butanone (9) was less efficient giving 1-methylbenzo[b]-5,6-dihydroindroindolizin-7 (8H)-one (10) and 4-(3-methylindol-1-yl)-but-l-en-3-one (11) in 7% and 24% yield, respectively. 相似文献
87.
The mobilities of three aromatic sulfonates, ranging in charge from -1 to -3, were investigated by capillary electrophoresis using buffers containing 0 to 75% ethanol or 2-propanol. Absolute mobilities were determined by extrapolation of the effective mobilities to zero ionic strength according to the Pitts' equation. For all buffers studied, ions of higher charge experienced larger ionic strength effects. The resulting ionic strength-induced selectivity alterations were more dramatic when organic solvents were present in the media. Furthermore, for different organic modifier types and contents, the magnitude of the ionic strength effect was governed to a large extent by the 1/(eta epsilon 1/2) dependence in the electrophoretic effect of the Pitts' equation. Addition of ethanol or 2-propanol to the electrophoretic media resulted in changes in the absolute mobilities of the ions. These solvent-induced mobility changes are attributed to dielectric friction. As predicted by the Hubbard-Onsager model, dielectric friction increased with increasing organic content and with increasing analyte charge. As a result, dramatic changes in the relative absolute mobilities were observed, such as a reversal in migration order between sulfonates of -1 and -3 charge in 75% 2-propanol. Within the alcohols, the Hubbard-Onsager model was successful at predicting the relative mobility trends upon changing solvent. However, the relative trends observed between acetonitrile-water and alcohol-water media were not consistent with the model. This may be explained by the continuum nature of the model, whereby the different ion-solvent interactions characteristic to each solvent class are not taken into account. 相似文献
88.
X-ray mapping in electron-beam instruments. 总被引:1,自引:0,他引:1
This review traces the development of X-ray mapping from its beginning 50 years ago through current analysis procedures that can reveal otherwise obscure elemental distributions and associations. X-ray mapping or compositional imaging of elemental distributions is one of the major capabilities of electron beam microanalysis because it frees the operator from the necessity of making decisions about which image features contain elements of interest. Elements in unexpected locations, or in unexpected association with other elements, may be found easily without operator bias as to where to locate the electron probe for data collection. X-ray mapping in the SEM or EPMA may be applied to bulk specimens at a spatial resolution of about 1 microm. X-ray mapping of thin specimens in the TEM or STEM may be accomplished at a spatial resolution ranging from 2 to 100 nm, depending on specimen thickness and the microscope. Although mapping has traditionally been considered a qualitative technique, recent developments demonstrate the quantitative capabilities of X-ray mapping techniques. Moreover, the long-desired ability to collect and store an entire spectrum at every pixel is now a reality, and methods for mining these data are rapidly being developed. 相似文献
89.
Charles S. Oakes John M. Simonson Robert J. Bodnar 《Journal of solution chemistry》1995,24(9):897-916
Relative densities of CaCl
2
(aq) with 0.22ml(mol-kg–1)6.150 were measured with vibrating- tube densimeters between 25 and 250°C and near 70 and 400 bars. Apparent molar volumes V calculated from the measured density differences were represented with the Pitzer ioninteraction treatment, with appropriate expressions chosen for the temperature and pressure dependence of the virial coefficients of the model. It was found that the partial molar volume at infinite dilution V
o
, and the second and third virial coefficients B
V
and C
V
, were necessary to represent V near the estimated experimental uncertainty. The ionic-strength dependent (1)v term in the B
V
coefficient was included in the fit. The representation for V has been integrated with respect to pressure to establish the pressure dependence of excess free energies over the temperature range studied. The volumetric data indicate that the logarithm of the mean ionic activity coefficient, ln ±(CaCl
2
), increases by a maximum of 0.3 at 400 bars, 250°C, and 6 mol-kg–1 as compared with its value at saturation pressure. 相似文献
90.
Dimethylmethyl phosphonate (DMMP), dimethyl phosphite (DMPI), trimethyl phosphite (TMPI) and trimethyl phosphate (TMP) were investigated using H2O and D2O atmospheric-pressure ionization (API) tandem mass Spectrometry. All daughter ions could be explained by losses of one or a successive number of stable molecules as opposed to losses of radicals such as the hydride, methyl and methoxy species. Losses of neutral methanol and dimethyl ether and of protonated methanol and formaldehyde ions from all four organophosphorus pseudo-molecular ions were observed. The DMMP and DMPI MH+ pseudomolecular ions produced the losses of neutral C2H6 and water, respectively. Formaldehyde loss was not observed for the MH+ ions, but it was well represented in the decomposition pathways of daughter ions. The D2O reagent gas highlighted the role of the ionizing proton/ deuteron in the various daughter ions, including m/z 95, 79, 65, 49, 33, 31 and 47. The last ion was found to be isobaric in that m/z 47 and 48 both appeared with similar abundances in the D2O-API daughter ion mass spectra of TMPI and TMP. 相似文献