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991.
M. R. Corson B. Kolk G. Hoy G. O. Zimmerman A. M. van der Kraan P. C. M. Gubbens 《Hyperfine Interactions》1978,4(1-2):411-414
A3He-4He dilution refrigerator was constructed to perform Mössbauer measurements well below 4.2K. Results are reported here on the pseudobinary Laves-Phase system Y (Fe1-x Cox)2 for x=0.978. We found that at low temperatures, the Fe ions undergo a disordered magnetic phase transition, with a Curie temperature of approximately 4K and a saturation field of 96K0e. The easy axis of magnetization appears to be the [111] direction. This study is an extension to very low temperatures of previous work on the system with 0X0.978.Supported by the NSF Grant No. DMR 73-07665 AO 3 相似文献
992.
The ligand substitution reactions of trans-[CoIII(en)2(Me)H2O]2+, a simple model for coenzyme B12, were studied for cyanide and imidazole as entering nucleophiles. It was found that these nucleophiles displace the coordinated water molecule trans to the methyl group and form the six-coordinate complex trans-[Co(en)2(Me)L]. The complex-formation constants for cyanide and imidazole were found to be (8.3 +/- 0.7) x 10(4) and 24.5 +/- 2.2 M-1 at 10 and 12 degrees C, respectively. The second-order rate constants for the substitution of water were found to be (3.3 +/- 0.1) x 10(3) and 198 +/- 13 M-1 s-1 at 25 degrees C for cyanide and imidazole, respectively. From temperature and pressure dependence studies, the activation parameters delta H++, delta S++, and delta V++ for the reaction of trans-[CoIII(en)2(Me)H2O]2+ with cyanide were found to be 50 +/- 4 kJ mol-1, 0 +/- 16 J K-1 mol-1, and +7.0 +/- 0.6 cm3 mol-1, respectively, compared to 53 +/- 2 kJ mol-1, -22 +/- 7 J K-1 mol-1, and +4.7 +/- 0.1 cm3 mol-1 for the reaction with imidazole. On the basis of reported activation volumes, these reactions follow a dissociative mechanism in which the entering nucleophile could be weakly bound in the transition state. 相似文献
993.
W Engels M A Kamps P J Lemmens G J van der Vusse R S Reneman 《Journal of chromatography. A》1988,427(2):209-218
A highly sensitive and specific assay for the quantitation of prostaglandins (PGs) such as PGE1, PGE2, PGF1 alpha, PGF2 alpha, 6-keto-PGF1 alpha, and including thromboxane B2, is described. The method involves the addition of PGF1 alpha and PGE1 as the internal standards, extraction from whole blood and purification by silica gel column chromatography. Following conversion into the methoximes, purification by reversed-phase chromatography and esterification with panacyl bromide, samples are analysed by high-performance liquid chromatography with fluorimetric detection. The lower limit of detection of the eicosanoids 6-keto-PGF1 alpha, thromboxane B2 and PGF2 alpha in blood is ca. 50 pg/ml and that of PGE2 is 100 pg/ml. Assay linearity is demonstrated over a range from 60 pg to 60 ng of eicosanoid injected. The method allows simultaneous assessment of prostaglandins and thromboxane extracted from complex biological fluids at picogram levels. 相似文献
994.
Alex B. Scholten Jan W. de Haan Hans-Gerd Janssen Leo J. M. van de Ven Carel A. Cramers 《Journal of separation science》1997,20(1):17-23
Retention gape deactivated with Silicone OV-1701-OH show good chromatographic performance and remarkable stability against water induced stationary phase degradrdation. In an attempt to better understand the findamentals off the deactivation process using silanol terminated polysiloxanes, a fumed silica was deactivated with Silicon OV-1701-OH. In contrast to fused silic capillaries, fumed silica (Aerosil A-200) can be studied by 29Si cross-polarization magic-angle-spinning (CPMAS) NMR, thus serving as a model substrate for fused silica. Retention data from inverse gas chromatography at infinite dilurion and 29Si CP MAS NMR data of five Aerosil phases, differing in residual silanol surface concentration, are correlated with the aim of validating this approach for stationary phase characterization. A comparatively detailed model of the deactivating polymer layer that explains the observed absorption activities is deduced. Surface silanols are shown to play a key role in the polymer layer, the structure of which is of primary importance for the absorption behavior after deactivation. Contrary to common belief, the absolute silanol surface concentration after deativation is only of secondary importance for the overall absorption activity. High silanol surface concentrations enhance degradation of the polysiloxane chains into small cyclic fragments as well as subsequent absorption and immobolization to the silica substrate surface. The mobility of linear polysiloxane chains in the kHz regime (as determined bby NMR cross-polarization dynamics) appears to determine the extent which the residual silanols are accessible for analytes. It is therefore anticipated that there is an optimum silanol surface concentration of fused silica surfaces to be deactivated with silanol terminated polysiloxanes; it should be lazrge enough to adsord polymer fragments, but not large to avoid excessive residual silanol activity. 相似文献
995.
Atomistic-scale simulations of the initial chemical events in the thermal initiation of triacetonetriperoxide 总被引:1,自引:0,他引:1
van Duin AC Zeiri Y Dubnikova F Kosloff R Goddard WA 《Journal of the American Chemical Society》2005,127(31):11053-11062
To study the initial chemical events related to the detonation of triacetonetriperoxide (TATP), we have performed a series of molecular dynamics (MD) simulations. In these simulations we used the ReaxFF reactive force field, which we have extended to reproduce the quantum mechanics (QM)-derived relative energies of the reactants, products, intermediates, and transition states related to the TATP unimolecular decomposition. We find excellent agreement between the QM-predicted reaction products and those observed from 100 independent ReaxFF unimolecular MD cookoff simulations. Furthermore, the primary reaction products and average initiation temperature observed in these 100 independent unimolecular cookoff simulations match closely with those observed from a TATP condensed-phase cookoff simulation, indicating that unimolecular decomposition dominates the thermal initiation of the TATP condensed phase. Our simulations demonstrate that thermal initiation of condensed-phase TATP is entropy-driven (rather than enthalpy-driven), since the initial reaction (which mainly leads to the formation of acetone, O(2), and several unstable C(3)H(6)O(2) isomers) is almost energy-neutral. The O(2) generated in the initiation steps is subsequently utilized in exothermic secondary reactions, leading finally to formation of water and a wide range of small hydrocarbons, acids, aldehydes, ketones, ethers, and alcohols. 相似文献
996.
A critical review of applications for the period 2000-2003, taken from the Web of Knowledge database, of the techniques high performance liquid chromatography-electrospray ionisation-mass spectrometry (HPLC-ESI-MS) and capillary electrophoresis-electrospray ionisation-mass spectrometry (CE-ESI-MS) to the detection and determination of small molecules of significance in clinical and forensic science is presented. The molecules of mass less than 500 Da are chosen according to selected structural classes in which they give ESI signals primarily as [M+H](+) ions although other ions such as [M-H](-), [M+Na](+) and [M+NH(4)](+) are also reported. The structural classes are drugs with amine-containing side chains, drugs with N-containing saturated ring structures, 1,4-benzodiazepines, carbohydrates, benzimidazoles, other heterocycles, sulphonylureas, anthracyclines, sulphonamides, penicillins, cephalosporins, tetracyclines, nitrocatechols, steroids, flavonoids, oxazaphosphorines, cannabinols, and miscellaneous molecules. Details are given on the fragmentations, where available, that these ionic species exhibit in-source and in ion-trap, triple quadrupole and time-of-flight mass spectrometers. The review then gives a critical evaluation of these recent HPLC-ESI-MS and CE-ESI-MS analytical methods for the detection and determination of small molecules of clinical and forensic significance. Analytical information on, for example, sample concentration techniques, HPLC and CE separation conditions, recoveries from biological media and limits of detection (LODs) are provided. 相似文献
997.
A new class of monocrystalline diamond paste-based electrodes is proposed for the determination of chromium(III) at trace levels in vitamins. Three types of monocrystalline diamond—natural diamond 1 (natural diamond), synthetic diamond 50 (synthetic-1), and synthetic diamond 1 (synthetic-2)—were used for electrode construction. The linear concentration ranges are between 10–10 and 10–8; 10–9 and 10–7, and 10–10 to 10–8 mol L–1, with limits of detection of 10–12, 10–12, and 10–11 mol L–1, when natural diamond, synthetic-1, and synthetic-2, respectively, are used as electrode materials. For electrodes based on natural diamond and synthetic-1 it was found that Cr(III) yields a peak at about +0.275±0.015 V (vs. Ag/AgCl) within a predetermined positive potential range situated between +0.4 and +0.2 V, while for the electrode based on synthetic-2 the peaks are found at +0.300±0.015 V (vs. Ag/AgCl). The proposed method is reliable for the determination of chromium(III) at trace levels in two vitamin tablets (RSD<0.2%). 相似文献
998.
An SCF MO calculation followed by extensive configuration interaction between all singly-excited singlet states has been performed for the excimer of naphthalene in a perfect and in some distorted sandwich structures. With these results an assignment is given for the bonds in the absorption spectrum of the excimer of 1-methyl naphthalene. It is further shown that the similarity between the optical properties of the 1-methyl naphthalene excimer and those of 1,1′-binaphthyl in fluid solution, is also reflected by the calculations. 相似文献
999.
Brousmiche DW Xu M Lukeman M Wan P 《Journal of the American Chemical Society》2003,125(42):12961-12970
Evidence is presented for the photochemical generation of novel biphenyl quinone methide (BQM)-type intermediates on photolysis of hydroxybiphenyl alkenes 7 and 8 and hydroxybiphenyl alcohols 9 and 10. Mechanistic investigations utilizing product, fluorescence, and nanosecond laser flash photolysis (LFP) studies indicate two distinct pathways for the formation of these BQMs depending upon the functional groups of the progenitor. Formal excited-state intramolecular proton transfer (ESIPT) between the phenol and the alkene led to BQMs upon irradiation of the hydroxybiphenyl alkenes 7 and 8, while excited-state proton transfer (ESPT) to solvent followed by dehydroxylation was responsible for BQM formation from the hydroxybiphenyl alcohols 9 and 10. Photolysis of 7 and 8 in aqueous CH(3)CN gave photohydration products via attack of water on the respective BQMs, while photolysis of the analogous methyl ethers (of the phenolic moiety) gave only carbocation intermediates. Hydroxybiphenyl alcohols 9 and 10 yielded the corresponding photomethanolysis products in aqueous methanol, through attack of CH(3)OH on the respective BQMs. Although no evidence was found for BQM formation in LFP studies of 8 and 10, due to its suspected short lifetime, the respective diaryl carbocation (lambda(max) 420 nm, tau = 8.5 micros) has been observed upon irradiation of 8 in 2,2,2-trifluoroethanol. A BQM (lambda(max) 580 nm) was observed for 9 but not for 10, the latter having more complex chemistry on laser excitation, resulting in a transient that appears to mask any BQM absorption. Significant quenching of fluorescence from the hydroxybiphenyl alkenes at low water content implies that H(2)O is directly involved in reaction from the singlet excited state. The decrease in fluorescence intensity of 8 was found to depend on [H(2)O](3); however, the distance required for ESIPT in these systems is too large to be bridged by a water trimer. The nonlinear quenching has been attributed to deprotonation of the phenol by two water molecules, with concerted protonation at the alkene by another molecule of water. Fluorescence quenching of the hydroxybiphenyl alcohols required much higher water content, implying a different mechanism of reaction, consistent with the proposal of ESPT (to solvent water) followed by dehydroxylation. 相似文献
1000.
Dixon FM Masar MS Doan PE Farrell JR Arnold FP Mirkin CA Incarvito CD Zakharov LN Rheingold AL 《Inorganic chemistry》2003,42(10):3245-3255
The ligand 1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene, 3, was used to synthesize a mononuclear Rh(II) complex [(eta(1):eta(6):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh][PF(6)](2), 6+, in a two-legged piano-stool geometry. The structural and electronic properties of this novel complex including a single-crystal EPR analysis are reported. The complex can be cleanly interconverted with its Rh(I) form, allowing for a comparison of the structural properties and reactivity of both oxidation states. The Rh(I) form 6 reacts with CO, tert-butyl isocyanide, and acetonitrile to form a series of 15-membered mononuclear cyclophanes [(eta(1):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CO)(3)][PF(6)] (8), [(eta(1):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CNC(CH(3))(3))(2)][PF(6)] (10), and [(eta(1):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CO)(CH(3)CN)][PF(6)] (11). The Rh(II) complex 6+ reacts with the same small molecules, but over shorter periods of time, to form the same Rh(I) products. In addition, a model two-legged piano-stool complex [(eta(1):eta(6):eta(1)-1,4-bis[3-(diphenylphosphino)propoxy]-2,3,5,6-tetramethylbenzene)Rh][B(C(6)F(5))(4)], 5, has been synthesized and characterized for comparison purposes. The solid-state structures of complexes 5, 6, 6+, and 11 are reported. Structure data for 5: triclinic; P(-)1; a = 10.1587(7) A; b = 11.5228(8) A; c = 17.2381(12) A; alpha = 96.4379(13) degrees; beta = 91.1870(12) degrees; gamma = 106.1470(13) degrees; Z = 2. 6: triclinic; P(-)1; a = 11.1934(5) A; b = 12.4807(6) A; c = 16.1771(7) A; alpha = 81.935(7) degrees; beta = 89.943(1) degrees; gamma = 78.292(1) degrees; Z = 2. 6+: monoclinic; P2(1)/n; a = 11.9371(18) A; b = 32.401(5) A; c = 12.782(2) A; beta = 102.890(3) degrees; Z = 4. 11: triclinic; P(-)1; a = 13.5476(7) A; b = 13.8306(7) A; c = 14.9948(8) A; alpha = 74.551(1) degrees; beta = 73.895(1) degrees; gamma = 66.046(1) degrees; Z = 2. 相似文献