排序方式: 共有26条查询结果,搜索用时 15 毫秒
1.
Gerard de Leeuw John S. Field Raymond J. Haines Beth McCulloch Elsie Meintjies Christiaan Monberg Gillian M. Olivier Praveen Ramdial Clifford N. Sampson Beate Sigwarth Nick D. Steen Kandasamy G. Moodley 《Journal of organometallic chemistry》1984,275(1):99-111
Reaction of [Fe2(CO)9] with a half molar amount of R2PYPR2 (Y = CH2, R = Ph, Me, OMe or OPri; Y = N(Et), R = OPh, OMe or OCH2; Y = N(Me), R = OPri or OEt) leads to the ready formation of a product which on irradiation with ultraviolet light rapidly decarbonylates to the heptacarbonyl derivative [Fe2(μ-CO)(CO)6{μ-R2PYPR2}]. Treatment of the latter with a slight excess of the appropriate ligand results, under photochemical conditions, in the formation of the dinuclear pentacarbonyl complex [Fe2(μ-CO)(C))4{μ-R2PYPR2}2] but under thermal conditions in the formation of the mononuclear species [Fe(CO)3{R2PYPR2}]. Reaction of [Ru3(CO)12] with an equimolar amount of (RO)2PN(R′)P(OR)2 (R′ = Me, R = Pri or Et; R′ = Et, R = Ph or Me) under either thermal or photochemical conditions produces [Ru3(CO)10{μ-(RO)2PN(OR)2}] which reacts further with excess (RO)2PN(R′)P(OR)2 on irradiation with ultraviolet light to afford the dinuclear compound [Ru2(μ-CO)(CO4{μ-(RO)2PN(R′)P(OR)2}2]. The molecular structure of [Ru2(μ-CO)(CO)4{μ-(MeO)2PN(Et)P(OMe)2}2], which has been determined by X-ray crystallography, is described. 相似文献
2.
Fluorescence methodologies have been utilized to examine micropolarity, intramolecular motion, and singlet quenching in the intraparticle void volume of zeolites X, Y, and ultrastable Y (USY) interfaced with bathing polar solvents. Micropolarity was assessed from the 3-to-1 band ratio (III/I) of the fluorescence spectrum of pyrene (PY) and from lambda(max) of the fluorescence spectrum of 1-pyrenecarboxaldehyde (1-PCA). In zeolites bathed in anhydrous solvents, both PY and 1-PCA reported increased micropolarity according to the trend USY < bulk solvent < NaX approximately NaY. For example, in NaY (USY), III/I ranged from 0.44 (0.98) in acetonitrile to 0.52 (1.34) in n-hexanol, compared to 0.60, 1.06, and 1.62 in bulk acetonitrile (ACN), n-hexanol, and n-hexane, respectively. The polarity studies reveal that the ionic nature of NaX and NaY and the hydrophobic nature of USY strongly influence the microenvironment of the arene despite the presence of desorbing polar solvents. Constraints on intramolecular motion were examined in polar-solvated NaX through measurements of the fluorescence lifetime of trans-stilbene. Lifetimes ranged from 113 ps in NaX-ACN to 671 ps in NaX-tert-butyl alcohol. The latter value is close to that observed in bulk glycerol. Diffusion-controlled quenching of PY fluorescence by O2 and a series of nitrocompounds dissolved in solvents bathing the zeolite was examined by a time-resolved approach. For all of the quenchers and solvents studied, quenching was more efficient in USY compared to NaX and NaY. Interestingly, the rate of O2 quenching in USY-MeOH was only 12 times lower than that in bulk MeOH. In contrast, in NaY-MeOH and NaX-MeOH the rate of O2 quenching was too low to be measured. The rate constants in these systems were therefore taken as the rate constant for diffusion-controlled quenching of trapped electrons measured previously. These values were 600 times and 10(5) times lower than the rate of fluorescence quenching in USY-MeOH, respectively. The O2 quenching studies show that dispersive interactions of polar solvents with the cavity walls dominate in USY because of the hydrophobic nature of the USY surface. In NaX and NaY, stronger ion-dipole and hydrogen bonding interactions dominate and lead to more restricted access and lowered quenching efficiency. Perrin (or static) quenching of pyrene fluorescence was also examined to infer the concentration of nitromethane (NM) in the void volume of NaX and NaY bathed in MeOH, ACN, or H2O. The results indicate that access of NM to the interior of NaY is more inhibited in ACN compared to MeOH, presumably because of the higher dipole moment of ACN and its resulting stronger association with the zeolite surface. At similar levels of static quenching equated to a similar NM concentration in the zeolite, dynamic quenching by NM varied by no more than a factor of 2 in all systems compared. This implies that the rate of NM diffusion in solvated zeolite interiors is similar regardless of zeolite or solvent properties. In contrast to O2 diffusion in zeolites, NM exhibits a high dipole moment and can therefore migrate through polar-solvated zeolite apertures by adsorbing to the zeolite. Overall, the results of this study show a close relationship between the behavior of probes and quenchers in the confines of polar-solvated zeolite interiors and the chemical properties of the zeolite. Differences between weakly and strongly interacting surfaces are revealed clearly in the results. 相似文献
3.
Quantum Monte Carlo estimates of the spectrum of rotationally invariant states of noble gas clusters suggest interdimensional degeneracy in N-1 and N+1 spatial dimensions. We derive this property by mapping the Schrodinger eigenvalue problem onto an eigenvalue equation in which D appears as a continuous variable. We discuss implications for quantum Monte Carlo and dimensional scaling methods. 相似文献
4.
We investigate the constraints imposed by current data on correlated mixtures of adiabatic and nonadiabatic primordial perturbations. We discover subtle flat directions in parameter space that tolerate large (approximately 60%) fractions of nonadiabatic fluctuations. In particular, larger values of the baryon density and a spectral tilt are allowed. The cancellations in the degenerate directions are explored and the role of priors is elucidated. 相似文献
5.
Conversion electron Mössbauer spectroscopy (CEMS) measurements have been made on Fe-silcide samples formed using the method of concentration controlled phase selection. To prepare the samples a 10 nm layer of Fe30M70 (M=Cr, Ni) was evaporated onto Si(100) surfaces, followed by evaporation of a 60 nm Fe layer. Diffusion of the Fe into the Si substrate and the formation of different Fe–Si phases was achieved by subjecting the evaporated samples to a series of heating stages, which consisted of (a) a 10 min anneal at 800°C plus etch of the residual surface layer, (b) a further 3 hr anneal at 800°C, (c) a 60 mJ excimer laser anneal to an energy density of 0.8 J/cm2, and (d) a final 3 hr anneal at 800°C. CEMS measurements were used to track the Fe-silicide phases formed. The CEMS spectra consisted of doublets which, based on established hyperfine parameters, could be assigned to - or -FeSi2 or cubic FeSi. The spectra showed that -FeSi2 had formed already at the first annealing stage. Excimer laser annealing resulted in the formation of a phase with hyperfine parameters consistent with those of -FeSi2. A further 3 hr anneal at 800°C resulted in complete reversal to the semiconducting -FeSi2 phase. 相似文献
6.
Ramakanth Pagadala Suresh MaddilaVashen Moodley Werner E. van ZylSreekantha B. Jonnalagadda 《Tetrahedron letters》2014
Au/MgO proved to be a highly efficient and reusable catalyst for multicomponent coupling reactions at 70 °C. The synthesized multisubstituted pyridines were obtained in high yields and in short reaction times. With facile work-up, the novel catalyst can be readily recovered after the reaction and reused without any loss of its catalytic activity. 相似文献
7.
Metal-sulphur phase-based semiconductor materials are often investigated in the field of nanotechnology. Herein, we describe the synthetic route to obtain Mo2S3 nanocrystals from MoS2 via a laser-furnace technique. These nanocrystals have been tested for cytotoxicity against the monocytic leukemic THP-1 cell line. The synthetic process caused a phase change from MoS2 to Mo2S3 at a temperature of 1100 °C and a pressure of 400 Torr. Powder X-ray diffraction analysis confirmed the crystallinity and structure and X-ray photoelectron spectroscopy confirmed the chemical composition and oxidation states of the Mo2S3 nanocrystals. The morphology of the Mo2S3 has been observed by using field emission scanning electron microscopy and high-resolution transmission electron microscopy. The in vitro cytotoxicity evaluation of the Mo2S3 nanocrystals was determined in the THP-1 cell line. The cytotoxic potential of the Mo2S3 against THP-1 cells was assessed by the WST-1 assay and intracellular caspase activities. The caspase activities were significantly elevated indicating the initiation of both the intrinsic and extrinsic apoptotic pathways when compared to untreated cells. Field emission scanning electron microscopy revealed that the Mo2S3 NCs compromised the cell membrane integrity resulting in a loss of THP-1 cell viability and apoptosis. Thus, Mo2S3 is an aqueous nanocrystal which shows promising cytotoxicity effect against THP-1 with good photoluminescent properties. 相似文献
8.
Philiswa N. Nomngongo J. Catherine Ngila Joseph N. Kamau Titus A.M. Msagati Ljiljana Marjanovic Brenda Moodley 《Analytica chimica acta》2013
Chelex-100, Dowex 50W-x8 and Dowex MAC-3 exchange resins were investigated for separation and pre-concentration of trace amounts of Cd, Cr, Cu, Fe, Mn, Pb, Ti and Zn in alcohols with respect to retention and desorption characteristics. Dowex 50W-x8 was found to be the best sorbent with percentages recoveries >95%. In addition, Chelex-100 appeared to be suitable for the pre-concentration of Cu, Fe and Zn, whereas Dowex MAC-3 was selective for Cu and Fe. Therefore, Dowex 50W-x8 was used for further investigations. The relative standard deviations <4% (n = 20), limits of detection and quantification were 0.1–1.2 μg L−1 and 0.3–1.5 μg L−1, respectively. The SPE method was validated against a certified reference material and the results were in agreement with certified values. The accuracy of the optimized method was verified by the recovery test in the spiked alcohol samples. The accuracy and spike recovery test for different metal ions were in the range 98–102% and 95–105%, respectively. The optimized method was applied to the separation and pre-concentration of metal ions in different commercial alcohol samples. 相似文献
9.
The Amatungula fruit, from Carissa macrocarpa, is commonly consumed by the local people of KwaZulu-Natal (KZN), South Africa. Levels of elements in the fruit were determined to assess if they conform to recommended dietary allowances (RDAs) and to assess for potential toxicities. Soils and fruit samples from nine sites in eastern KZN were investigated. Concentrations of elements in the fruit were found to be in the order of Ca > Mg > Fe > Mn ≈ Cu ≈ Pb > Se > Cr > Ni > Zn. For the elements in focus, except for Pb, all of the elements found in the fruit contribute significantly towards the RDAs. Lipid profiling was also done to determine the fruits potential as a source of essential fatty acids. The fruit was rich in monounsaturated and essential fatty acids with the linoleic acid to α-linolenic acid ratio conforming to the recommended range for cardiac health. Concentrations of elements in soil had no significant effect on plant concentrations, but competition between elements in soil influenced their availability. Total soil concentrations of most metals studied have significantly correlated Pb availability, indicating the impact of these metals on Pb availability. The Amatungula fruit showed tendency to accumulate Pb, with Pb levels in fruit at all sites being toxic to human health. Site location had a major effect on plant concentrations however uptake and distribution was primarily dependent on the plants inherent controls, as evidenced by the accumulation and exclusion of elements, to meet its physiological requirements. 相似文献
10.
Sreejarani?K.?Pillai Letlhogonolo?Matlhoko Chris?Arendse Suprakas?Sinha?Ray Mathew?Moodley 《Applied Physics A: Materials Science & Processing》2009,94(3):585-591
Multi-walled carbon nanotubes (MWCNTs) were synthesized a by chemical vapour deposition method. The effect of calcination
at temperatures ranging from 300 to 550°C in exposing the metal nanoparticles within the nanotube bundles was studied. The
degree of degradation of the structural integrity of the MWCNTs during the thermal process was studied by Raman spectroscopy,
X-ray diffraction analysis, field-emission scanning electron microscopy, and transmission electron microscopy. The thermal
behaviour of the as-prepared and calcined samples was investigated by thermogravimetric analysis. Calcination in air, at 400°C
for 1 h, was found to be an efficient and simple method to extract metallic impurities from the amorphous carbon shells with
minimal damage to the tube walls and lengths. The nanotubes were observed to be damaged at temperatures higher than 450°C. 相似文献