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1.
In an extension of studies of flameless atomizers for atomic-absorption spectrometry, an electrically heated tungsten-rhenium alloy wire loop was examined. Reduction of metallic salts to ground-state metal atoms was accomplished with the high temperature produced by the loop. Lead and nickel were investigated. Experimental parameters such as wavelength, slit width, atomization temperature and sheathing gas flow rate were optimized. Absolute detection limits of 6.6·10?10 and 1.2·10?10, and absolute sensitivities of 7·10?10 and 8·10?11 g of lead, were established for unenclosed and enclosed cells, respectively. The interferences of twenty cations and sixteen anions were studied; foreign cations generally enhanced the lead absorption by retarding its vaporization, allowing the slow detection system to respond more efficiently. Nickel was investigated as a representative less volatile metal; an absolute detection limit of 1.6·10?9 and an absolute sensitivity of 9·10?10 g of nickel were established. 相似文献
2.
Khademhosseini A Yeh J Eng G Karp J Kaji H Borenstein J Farokhzad OC Langer R 《Lab on a chip》2005,5(12):1380-1386
We present a soft lithographic method to fabricate multiphenotype cell arrays by capturing cells within an array of reversibly sealed microfluidic channels. The technique uses reversible sealing of elastomeric polydimethylsiloxane (PDMS) molds on surfaces to sequentially deliver various fluids or cells onto specific locations on a substrate. Microwells on the substrate were used to capture and immobilize cells within low shear stress regions inside channels. By using an array of channels it was possible to deposit multiple cell types, such as hepatocytes, fibroblasts, and embryonic stem cells, on the substrates. Upon formation of the cell arrays on the substrate, the PDMS mold could be removed, generating a multiphenotype array of cells. In addition, the orthogonal alignment and subsequent attachment of a secondary array of channels on the patterned substrates could be used to deliver fluids to the patterned cells. The ability to position many cell types on particular regions within a two dimensional substrate could potentially lead to improved high-throughput methods applicable to drug screening and tissue engineering. 相似文献
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4.
The sodium/liquid ammonia cleavage of the dimethoxybenzenes and related substances, reported in large part by Birch in 1947, has been re-examined with use of improved techniques. Remarkable patterns of reactivity (e.g., ortho > meta > para) that he described are confirmed and extended. They are agreeably rationalized by means of a simple, approximate adaptation from MO theory. 相似文献
5.
The electrochemical and spectroelectrochemical properties of niobium(V) and the Nb(3)O(2)(SO(4))(6)(H(2)O)(3)(5-) cluster in sulfuric acid and methanesulfonic acid were investigated using cyclic voltammetry, constant potential electrolysis, and spectroelectrochemistry. These chemical systems were suitable to probe the formation of "Nb(3)O(2)" core trinuclear clusters. In 9 M H(2)SO(4) the cluster Nb(3)O(2)(SO(4))(6)(H(2)O)(3)(5-) exhibited a reversible 1-electron reduction peak at E(pc) = -1.30 V vs Hg/Hg(2)SO(4) electrode, as well as a 4-electron irreversible oxidation peak at E(pa) = -0.45 V. Controlled potential reduction at E = -1.40 V produced the green Nb(3.33+) cluster anion Nb(3)O(2)(SO(4))(6)(H(2)O)(3)(6-). In 12 M H(2)SO(4) Nb(V) displayed two reduction peaks at E(pc) = -1.15 V and E(pc) = -1.30 V. It was determined that the first process involves a quasi-reversible 2-electron reduction. After reduction of Nb(V) to Nb(III) the following chemical step involves formation of [Nb(III)](2) dimer, which further reacts with Nb(V) to produce the Nb(3)O(2)(SO(4))(6(H(2)O)(3)(5-) cluster (ECC process). The second reduction peak at E(pc) = -1.30 V corresponds to further 2-electron reduction of Nb(III) to Nb(I). The electrogenerated Nb(I) species also chemically reacts with starting material Nb(V) to produce additional [Nb(III)](2). In 5 M H(2)SO(4), the rate of the second chemical step in the ECC process is relatively slower and reduction of Nb(V) at E = -1.45 V/-1.2 V produces a mixture of Nb(3)O(2)(SO(4))(6)(H(2)O)(3)(5-) and [Nb(III)](2) dimer. [Nb(III)](2) can be selectively oxidized by two 2-electron steps at E = -0.65 V to Nb(V). However, if the oxidation is performed at E = -0.86 V, the product is Nb(3)O(2)(SO(4))(6)(H(2)O)(3)(5-). A double potential pulse electrolysis waveform was developed to direct the reduction of Nb(V) toward selective formation of the Nb(3)O(2)(SO(4))(6)(H(2)O)(3)(5-) cluster. Proper application of dc-voltage pulses alternating between E(1) = -1.45 V and E(2) = -0.86 V yields only the target trinuclear cluster. Analogous double potential pulse electrolysis of Nb(V) in methanesulfonic acid generates the "Nb(3)O(2)" core cluster Nb(3)O(2)(CH(3)SO(3))(6)(H(2)O)(3)(+). 相似文献
6.
Picosecond time-resolved Stokes and anti-Stokes resonance Raman spectra of all-trans-beta-carotene are obtained and analyzed to reveal the dynamics of excited-state (S(1)) population and decay, as well as ground-state vibrational relaxation. Time-resolved Stokes spectra show that the ground state recovers with a 12.6 ps time constant, in agreement with the observed decay of the unique S(1) Stokes bands. The anti-Stokes spectra exhibit no peaks attributable to the S(1) (2A(g) (-)) state, indicating that vibrational relaxation in S(1) must be nearly complete within 2 ps. After photoexcitation there is a large increase in anti-Stokes scattering from ground-state modes that are vibrationally excited through internal conversion. The anti-Stokes data are fit to a kinetic scheme in which the C=C mode relaxes in 0.7 ps, the C-C mode relaxes in 5.4 ps and the C-CH(3) mode relaxes in 12.1 ps. These results are consistent with a model for S(1)-S(0) internal conversion in which the C=C mode is the primary acceptor, the C-C mode is a minor acceptor, and the C-CH(3) mode is excited via intramolecular vibrational energy redistribution. 相似文献
7.
Clay A. Henry Mel Judy Barbara Dyer Martin Wagner James L. Matthews 《Photochemistry and photobiology》1995,61(4):410-413
Abstract— The phototoxicity of argon laser irradiation was studied in aqueous suspensions of Porphyromonas endodontalis (American Type Culture Collection [ATCC] 35406), Porphyromonas gingivalis (ATCC 33277), Prevotella denticola (ATCC 33184) and two strains of Prevotella intermedia (ATCC 15033 and 49046), all "black-pigmented bacteria," BPB, that accumulate cellular porphyrins. Several of these species have been implicated in the etiology of Periodontol disease. Non-black-pigmented bacteria were also studied to test the specificity of irradiation as a potential photodynamic treatment for Periodontol infections. Cell suspensions were irradiated with an argon laser at fluences of 20–200 J/cm2 . When cultured in hemin-supplemented media, ATCC 15033 was the most sensitive to irradiation. However, a second strain of the same species (ATCC 49046) was resistant. The photosensitivity of other species ranked ATCC 33277 > 35406 = 33184 = 35496. When hemin was replaced in media by hemoglobin, ATCC 33277 became resistant to irradiation. Protoporphyrin IX content in BPB cells was shown not to be a major factor determining photosensitivity. Oxygen was required during irradiation for BPB species to be affected. Non-black-pigmented bacteria were much less sensitive to irradiation than BPB. 相似文献
8.
9.
Picosecond Stokes and anti-Stokes Raman spectra are used to probe the structural dynamics and reactive energy flow in the primary cis-to-trans isomerization reaction of rhodopsin. The appearance of characteristic ethylenic, hydrogen out-of-plane (HOOP), and low-wavenumber photoproduct bands in the Raman spectra is instrument-response-limited, consistent with a subpicosecond product appearance time. Intense high and low-frequency anti-Stokes peaks demonstrate that the all-trans photoproduct is produced vibrationally hot on the ground-state surface. Specifically, the low-frequency modes at 282, 350, and 477 cm(-1) are highly vibrationally excited (T > 2000 K) immediately following isomerization, revealing that these low-frequency motions directly participate in the reactive curve-crossing process. The anti-Stokes modes are characterized by a approximately 2.5 ps temporal decay that coincides with the conversion of photorhodopsin to bathorhodopsin. This correspondence shows that the photo-to-batho transition is a ground-state cooling process and that energy storage in the primary visual photoproduct is complete on the picosecond time scale. Finally, unique Stokes vibrations at 290, 992, 1254, 1290, and 1569 cm(-1) arising from the excited state of rhodopsin are observed only at 0 ps delay. 相似文献
10.