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1.
Cory J. Hill Baohua Yang Rui Q. Yang 《Physica E: Low-dimensional Systems and Nanostructures》2004,20(3-4):486
Mid-IR type-II interband cascade lasers were demonstrated in pulsed mode at temperatures up to 325 K and in continuous mode up to 200 K. At 80 K, the threshold current density was 8.9 A/cm2 and a continuous wave output power of 140 mW/facet was obtained. 相似文献
2.
Ross W. Mair David G. Cory Sharon Peled Ching-Hua Tseng Samuel Patz Ronald L. Walsworth 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1998,135(2):478-486
Pulsed-field-gradient NMR techniques are demonstrated for measurements of time-dependent gas diffusion. The standard PGSE technique and variants, applied to a free gas mixture of thermally polarized xenon and O2, are found to provide a reproducible measure of the xenon diffusion coefficient (5.71 × 10−6m2s−1for 1 atm of pure xenon), in excellent agreement with previous, non-NMR measurements. The utility of pulsed-field-gradient NMR techniques is demonstrated by the first measurement of time-dependent (i.e., restricted) gas diffusion inside a porous medium (a random pack of glass beads), with results that agree well with theory. Two modified NMR pulse sequences derived from the PGSE technique (named the Pulsed Gradient Echo, or PGE, and the Pulsed Gradient Multiple Spin Echo, or PGMSE) are also applied to measurements of time dependent diffusion of laser polarized xenon gas, with results in good agreement with previous measurements on thermally polarized gas. The PGMSE technique is found to be superior to the PGE method, and to standard PGSE techniques and variants, for efficiently measuring laser polarized noble gas diffusion over a wide range of diffusion times. 相似文献
3.
Mair RW Rosen MS Wang R Cory DG Walsworth RL 《Magnetic resonance in chemistry : MRC》2002,40(13):S29-S39
We report initial NMR studies of (i) xenon gas diffusion in model heterogeneous porous media and (ii) continuous flow laser-polarized xenon gas. Both areas utilize the pulsed gradient spin-echo (PGSE) techniques in the gas phase, with the aim of obtaining more sophisticated information than just translational self-diffusion coefficients--a brief overview of this area is provided in the Introduction. The heterogeneous or multiple-length scale model porous media consisted of random packs of mixed glass beads of two different sizes. We focus on observing the approach of the time-dependent gas diffusion coefficient, D(t) (an indicator of mean squared displacement), to the long-time asymptote, with the aim of understanding the long-length scale structural information that may be derived from a heterogeneous porous system. We find that D(t) of imbibed xenon gas at short diffusion times is similar for the mixed bead pack and a pack of the smaller sized beads alone, hence reflecting the pore surface area to volume ratio of the smaller bead sample. The approach of D(t) to the long-time limit follows that of a pack of the larger sized beads alone, although the limiting D(t) for the mixed bead pack is lower, reflecting the lower porosity of the sample compared to that of a pack of mono-sized glass beads. The Pade approximation is used to interpolate D(t) data between the short- and long-time limits. Initial studies of continuous flow laser-polarized xenon gas demonstrate velocity-sensitive imaging of much higher flows than can generally be obtained with liquids (20-200 mm s-1). Gas velocity imaging is, however, found to be limited to a resolution of about 1 mm s-1 owing to the high diffusivity of gases compared with liquids. We also present the first gas-phase NMR scattering, or diffusive-diffraction, data, namely flow-enhanced structural features in the echo attenuation data from laser-polarized xenon flowing through a 2 mm glass bead pack. 相似文献
4.
van de Riet JM Murphy CJ Pearce JN Potter RA Burns BG 《Journal of AOAC International》2005,88(3):744-749
A liquid chromatography/tandem mass spectrometry (LC/MS/MS) method was developed for determining the residues of malachite green (MG) and leucomalachite green (LMG) in a number of aquatic species. MG and its metabolite were extracted from homogenized tissues with a perchloric acid-acetonitrile solution; the extract was centrifuged; and an aliquot was taken, concentrated, and passed through a chemically bonded octadecyl C18 solid-phase extraction column. The compounds of interest were eluted with acetonitrile, and the eluate was evaporated to dryness. The residue was dissolved in acetonitrile and diluted with water in preparation for analysis by LC/MS/MS. MG and its metabolite were determined by reversed-phase LC using a Luna C18 column with an ammonium hydroxide-formic acid buffer in acetonitrile gradient and MS/MS detection using multiple reaction monitoring. Calibration curves were linear for all analyses between 5 and 500 pg injected for both analytes, with recoveries ranging from 81% for LMG to 98% for MG in salmon spiked at the 1 ng/g level. Detection limits of 0.1 ng/g for both MG and LMG were easily obtainable using the recommended method. The operational errors, interferences, and recoveries for spiked samples compared favorably with those obtained by established methodology. The recommended method is simple, rapid, and specific for monitoring residues of MG and LMG in a number of aquatic species. 相似文献
5.
In depth, comparative studies on the catalytic dehydrocoupling of the amine-borane adduct Me(2)NH.BH(3) (to form [Me(2)N-BH(2)](2)) and the phosphine-borane adduct Ph(2)PH.BH(3) (to form Ph(2)PH-BH(2)-PPh(2)-BH(3)) with a variety of Rh (pre)catalysts such as [[Rh(1,5-cod)(micro-Cl)](2)], Rh/Al(2)O(3), Rh(colloid)/[Oct(4)N]Cl, and [Rh(1,5-cod)(2)]OTf have been performed in order to determine whether the dehydrocoupling proceeds by a homogeneous or heterogeneous mechanism. The results obtained suggest that the catalytic dehydrocoupling of Me(2)NH.BH(3) is heterogeneous in nature involving Rh(0) colloids, while that of Ph(2)PH.BH(3) proceeds by a homogeneous mechanism even when starting with Rh(0) precursors such as Rh/Al(2)O(3). The catalytic dehydrocoupling reactions are thought to proceed by different mechanisms due to a combination of factors such as (i) the greater reducing strength of amine-borane adducts, (ii) the increased ease of dissociation of phosphine-borane adducts, and (iii) phosphine ligation and/or poisoning of active catalytic sites on metal colloids. 相似文献
6.
(trans) 1-Chloro-2-iodoethylene (3), (trans) 1-bromo-2-iodoethylene (4), (trans) 1,2-diiodoethylene (5) and (cis and trans) 1,2-dibromoethylene (11) were reacted under Suzuki, Sonogashira and Negishi cross-coupling conditions using Pd catalysis to obtain mono coupled products. Only olefin template 3 provided the desired coupling products reliably under all reaction conditions. Compound 5 did not provide cross coupled products under any of the reaction conditions used. The Negishi reaction was the only one that worked for templates 4 and 11. Studies indicate that oxidative addition of the most reactive carbon-halogen bond to Pd(0) is followed by elimination of the second halide, when the second halide is a bromide or an iodide. This happens to a much lesser degree when the second halogen is a chloride. 相似文献
7.
Cory Momany Marvin L. Hackert Jyotsna Sharma Narinder S. Poonia 《Journal of inclusion phenomena and macrocyclic chemistry》1987,5(3):343-354
Sodium salicylate (NaSal where Sal=2-hydroxybenzoate), when mixed with dibenzo-24-crown-8 (DB24C8) yields a bimetallic complex [NaSal]2DB24C8 in most polar organic media, while potassium salicylate (KSal) under similar conditions shows a tendency to yield 11 or 21 complexes depending upon medium or synthesis. However, the presence of both NaSal and KSal together results in a unique mixed cation complex of composition NaKSal2DB24C8. This product melts sharply (190-92°C) without decomposition, displays IR spectral characteristics comparable to those of [Na(Sal)]2DB24C8, and is stable in aqueous media as shown by the detectable cation effect on the UV absorption bands of Sal and DB24C8. Single crystal X-ray analysis of NaK(Sal)2DB24C8 reveals that the system represents a co-crystallization complex of individual (KSal)2DB24C8 and (NaSal)2DB24C8 molecules. The crystals are monoclinic,P21/c,a=19.976(2) Å,b=9.031(1) Å,c=25.541(5) Å,=122.065(9)°, Å3,T=298 K,Z=2+2, CuK =1.5418 Å, and 2 (2.5°–100°). FinalR factor for the 3012 observed reflections (F>3) is 0.092. Both the Na2- and K2-molecules possess crystallographic centers of symmetry with one metal and its associated anion on each side of the crown ring. However, the conformations of the crowns are very different in the two molecules, with the K2-crown being nearly planar and the Na2-crown being quite puckered. Four oxygen atoms from the DB24C8 (KO, 2.680–2.908 Å) and three carboxyl oxygen atoms (KO, 2.472–2.708 Å) from separate salicylate ions coordinate with each potassium. Three oxygens from the crown (NaO, 2.536–2.65 Å) and three carboxyl oxygens (NaO, 2.31–2.563 Å) coordinate with each sodium. The salicylate ions lie on opposite sides and nearly perpendicular (77.2°, Na2-molecule; 82.7° K2-molecule) to each crown but coordinate to both of the metal ions within a molecule. The K+K+ and Na+Na+ distances in the respective molecules are 3.95 and 3.34 Å.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82044 (18 pages). 相似文献
8.
Zinc(II) Hydration in Aqueous Solution: A Raman Spectroscopic Investigation and An ab initio Molecular Orbital Study of Zinc(II) Water Clusters 总被引:1,自引:0,他引:1
Raman spectra of aqueous Zn(II)–perchlorate solutions were measured over broad concentration (0.50–3.54 mol-L–1) and temperature (25–120°C) ranges. The weak polarized band at 390 cm–1 and two depolarized modes at 270 and 214 cm–1 have been assigned to 1(a
1g), 2(e
g), and 5(f
2g) of the zinc–hexaaqua ion. The infrared-active mode at 365 cm–1 has been assigned to 3(f
1u). The vibrational analysis of the species [Zn(OH2)
2
+
] was done on the basis of O
h symmetry (OH2 as point mass). The polarized mode 1(a
1g)-ZnO6 has been followed over the full temperature range and band parameters (band maximum, full width at half height, and intensity) have been examined. The position of the 1(a
1g)-ZnO6 mode shifts only about 4 cm–1 to lower frequencies and broadens by about 32 cm–1 for a 95°C temperature increase. The Raman spectroscopic data suggest that the hexaaqua–Zn(II) ion is thermodynamically stable in perchlorate solution over the temperature and concentration range measured. These findings are in contrast to ZnSO4 solutions, recently measured by one of us, where sulfate replaces a water molecule of the first hydration sphere. Ab initio geometry optimizations and frequency calculations of [Zn(OH2)
2
+
] were carried out at the Hartree–Fock and second-order Møller–Plesset levels of theory, using various basis sets up to 6-31 + G*. The global minimum structure of the hexaaqua–Zn(II) species corresponds with symmetry T
h. The unscaled vibrational frequencies of the [Zn(OH2)
2
+
] are reported. The unscaled vibrational frequencies of the ZnO6, unit are lower than the experimental frequencies (ca. 15%), but scaling the frequencies reproduces the measured frequencies. The theoretical binding enthalpy for [Zn(OH2)
2
+
] was calculated and accounts for ca. 66% of the experimental single-ion hydration enthalpy for Zn(II).Ab initio geometry optimizations and frequency calculations are also reported for a [Zn(OH2)
2
18
] (Zn[6 + 12]) cluster with 6 water molecules in the first sphere and 12 in the second sphere. The global minimum corresponds with T symmetry. Calculated frequencies of the zinc [6 + 12] cluster correspond well with the observed frequencies in solution. The 1-ZnO6 (unscaled) mode occurs at 388 cm–1 almost in perfect correspondence to the experimental value. The theoretical binding enthalpy for [Zn(OH2)
2
18
] was calculated and is very close to the experimental single ion-hydration enthalpy for Zn(II). The water molecules of the first sphere form strong hydrogen bonds with water molecules in the second hydration shell because of the strong polarizing effect of the Zn(II) ion. The importance of the second hydration sphere is discussed. 相似文献
9.
Jaska CA Dorn H Lough AJ Manners I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(1):271-281
Reaction of [Pt(PEt(3))(3)] with the primary and secondary phosphine-borane adducts PhRPH x BH(3) (R=H, Ph) resulted in oxidative addition of a P-H bond at the Pt(0) center to afford the complexes trans-[PtH(PPhR x BH(3))(PEt(3))(2)] (1: R=H; 2: R=Ph). The products 1 and 2 were characterized by (1)H, (11)B, (13)C, (31)P, and (195)Pt NMR spectroscopy, and the molecular structures were verified by X-ray crystallography. In both cases, a trans arrangement of the hydride ligand with respect to the phosphidoborane ligand was observed. When 2 was treated with PhPH(2) x BH(3), a novel phosphidoborane ligand-exchange reaction occurred which yielded 1 and Ph(2)PH x BH(3). Treatment of 2 with one equivalent of depe (depe=1,2-bis(diethylphosphino)ethane) resulted in the formation of the complex cis-[PtH(PPh(2) x BH(3))(depe)] (3), in which the hydride ligand and the phosphidoborane ligand are in a cis arrangement. Treatment of 3 with PhPH(2) x BH(3) was found to result in an exchange of the phosphidoborane ligands to give the complex cis-[PtH(PPhH x BH(3))(depe)] (4) and Ph(2)PH x BH(3). Complex 4 was found to undergo further reaction in the presence of PhPH(2) x BH(3) to give meso-cis-[Pt(PPhH x BH(3))(2)(depe)] (5) and rac-cis-[Pt(PPhH x BH(3))(2)(depe)] (6). 相似文献
10.