首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
Hyperquenching of liquid water with cooling rates of 106–107 K s−1 yields glassy water. Upon γ-irradiation at 77 K, the only paramagnetic species accumulating in hyperquenched glassy water are the hydroxyl and hydroperoxyl radicals. There are no hydrogen atoms or electrons seen by the ESR technique. For irradiation doses up to about 70 kGy, the relative contributions of hydroxyl and hydroperoxyl radicals to the total amount of paramagnetic species remain virtually constant. The total amount of paramagnetic species, n, is sublinear in dose, d, well approximated by n=8.55×1016d0.8 for n in spin g−1 and d in kGy.  相似文献   

2.
Differential Scanning Calorimetry measurements on irradiated Cl3[Ru(NH3)5NO]H2O reveal the existence of two light-induced long-lived metastable states SI, SII. Irradiation with light in the spectral range 400–500 nm leads to the excitation of SI. For the first time we report experimental evidence for the state SII in this compound, which can be excited by transferring SI into SII with irradiation of light in the spectral range 1000–1200 nm. The excitation and transfer of the metastable states is described and the exponential decays are evaluated according to Arrhenius' law yielding activation energies of EA(SI)=0.73(3) eV, EA(SII)=0.66(3) eV and frequency factors of Z(SI)=1 × 1012 s−1, Z(SII) = 5 × 1012 s−1.  相似文献   

3.
Two flow injection analyses (FIA) methods for the determination of diffusion coefficients in a straight single tube FIA system were developed. Based on the analytical solution of the convection-diffusion equation, linear relationships of the logarithmic values of the dispersion coefficient (D) and the half-peak width (W1/2) with the diffusion coefficient (Dm) were obtained. Experiments were designed to verify these methods. For example, for potassium hexacyanoferrate (III) a Dm value of 0.72 × 105 cm2 s−1 was found versus a literature value of 0.76 × 105 cm2 s−1 (error, 5%). For potassium hexacyanoferrate (II) a Dm value of 0.67 × 105 cm2 s−1 was obtained versus a literature value of 0.63 × 105 cm2 s−1 (error, 6%). The diffusion coefficients of some important biomedical compounds, such as dopamine, epinephrine, norepinephrine and ascorbic acid, were then determined. The values of 105 Dm/cm2 s−1 are 0.60 ± 0.03, 0.44 ± 0.02, 0.60 ± 0.01 and 0.68 ± 0.06, respectively.  相似文献   

4.
Excitation of solutions of Fe(bipy)2(CN)2 by a 266-nm laser pulse produces a hydrated electron and the oxidized complex, Fe(bipy)2 (CN)2+, in the primary photochemical step, in homogeneous aqueous solution as well as in aqueous solutions containing cetyltrimethylammonium bromide (CTAB) or sodium dodecyl sulfate (SDS) micelles. In all cases nascent hydrated electrons react with ground state Fe(bipy)2(CN)2 to form Fe(bipy)2(CN)2, and comparison of the decay constants in the three media (H2O: k = 2.8 × 1010 M−1 s−1; CTAB: k = 2.9 × 1010 M−1 s−1; SDS: k = 5.5 × 109 M−1 s−1), shows that the reaction is essentially unaffected by CTAB micelles but is much slower in SDS solution. Similar micellar effects were found for the back reaction between eaq and Fe(bpy)2(CN)2+. Rate constants for the scavenging of the photogenerated hydrated electrons by methyl viologen (MV2+) cations and NO3 anions were measured in the three systems, and the results indicate that for scavenging by MV2+ the rate constants are decreased in the micelle systems (k in H2O, 8.4 × 1010; CTAB, 3.5 × 1010 and SDS, 1.58 × 1010 M−1 s−1), whereas for NO3 the CTAB micelle decreases while the SDS micelle enhances the scavenging compared to water solution (k in H2O, 8.3 × 109; CTAB, 7 × 108; and SDS, 2.05 × 1010 M−1 s−1). For the comproportionation reaction between Fe(bipy)2(CN)2+ and Fe(bipy)2(CN)2 both micelles reduce the rate (k in H2O, 3.3 × 1010; CTAB, 2.3 × 1010; and SDS, 1.05 × 1010 M−1s−1), but while the reaction of Fe(bipy)2(CN)2+ with MV+ is increased in CTAB compared to water, it is slowed in SDS (k in H2O, 2.4 × 1010; CTAB, 8.9 × 1010; and SDS, 1.8 × 1010 M−1s−1). All effects observed in these microheterogeneous systems can be uniformly interpreted in terms of Coulombic interactions between the actual reactants and the charged surface of the micelles.  相似文献   

5.
Stark widths of 34 spectral lines of Pb I have been measured in a Laser-Induced-Plasma (LIP). The optical emission spectroscopy from a LIP generated by a 10 640 Å radiation, with an irradiance of 1.4 × 1010 W cm− 2 on a Sn–Pb target in an atmosphere of argon was analyzed between 1900 and 7000 Å. The Local Thermodynamic Equilibrium (LTE) conditions and plasma homogeneity have been checked. The 34 spectral lines measured in this paper correspond to the transitions n(n = 7, 8)s→6p2, n(n = 6, 7)d→6p2. The population levels distribution and the corresponding temperatures were obtained using Boltzmann plots. The plasma electron densities were determined using well-known Stark broadening parameters of spectral lines. Special attention was dedicated to the possible self-absorption of the different transitions. Stark broadening parameters of the spectral lines were measured at 2.5 µs after each laser light pulse, where the electron temperature was close to 11 200 K and the electron density to 1016 cm− 3. The experimental results obtained have been compared with the experimental values given by other authors.  相似文献   

6.
Tarazi L  George A  Patonay G  Strekowski L 《Talanta》1998,46(6):1413-1424
The spectral features of the near-infrared (NIR) dye TG-170 in different solutions and its complexation with several metal ions were investigated. The absorbance maxima of the dye are at λ=819, 805, and 791 nm in dimethyl sulfoxide (DMSO), methanol, and a buffer of pH 5.9, respectively. These values match the output of a commercially available laser diode (780 nm), thus making use of such a source practical for excitation. The emission wavelengths of the dye are at λem =822, 812, and 803 nm in DMSO, methanol, and the buffer, respectively. The molar absorptivity and fluorescence quantum yield increase accordingly. The addition of either an Al(III) ion or Be(II) ion resulted in fluorescence quenching of the dye. The Stern–Volmer quenching constant, KSV, was calculated from the Stern–Volmer plot to be KSV=3.11×105 M−1 for the Al(III) ion and KSV=1.17×106 M−1 for the Be(II) ion. The molar ratio of the metal to the dye was established to be 1:1 for both metal ions. The stability constant, KS, of the metal–dye complex was calculated to be 4.37×104 M−1 for the Al–dye complex and 1.94×106 M−1 for the Be–dye complex.  相似文献   

7.
Antigen I/II can be found on streptococcal cell surfaces and is involved in their interaction with salivary proteins. In this paper, we determine the adsorption enthalpies of salivary proteins to Streptococcus mutans LT11 and S. mutans IB03987 with and without antigen I/II, respectively, using isothermal titration calorimetry. In addition, protein adsorption to the cell surfaces was determined spectrophotometrically. S. mutans LT11 with antigen I/II, yielded a much higher, exothermic adsorption enthalpy at pH 6.8 (ranging from −2073 × 10−9 to −31707 × 10−9 μJ per bacterium) when mixed with saliva than did S. mutans IB03987 (−165 × 10−9 to −1107 × 10−9 μJ per bacterium) at all bacterial concentrations studied (5 × 109, 5 × 108, and 5 × 107 ml−1), largest effects per bacterium being observed for the lowest concentration. However, the enthalpy of salivary protein adsorption to S. mutans LT11 became smaller at pH 5.8. Adsorption isotherms for the S. mutans LT11 showed considerable protein adsorption at pH 6.8 (1.2–2.1 mg/m2), that decreased only slightly at pH 5.8 (1.1–1.6 mg/m2), with the largest amount adsorbed at the lowest bacterial concentration. This suggests that the protein(s) in the saliva with the strongest affinity for antigen I/II is (are) readily depleted from saliva. In conclusion, antigen I/II surface proteins on S. mutans play a determinant role in adsorption of salivary proteins through the creation of enthalpically favorable adsorption sites.  相似文献   

8.
Structures of AgAF6 (A=Sb, Ta) have been determined by X-ray single crystal studies at ambient temperatures. AgSbF6 crystallizes in space group Ia with a=979.85(4) pm, V=9.4076(12)×108 pm3, z=8, and AgTaF6 crystallizes in space group P42/mcm with a=499.49(4) pm, c=960.51(8) pm, V=2.3964(6)×108 pm3, z=2. Only the crystal system and cell parameters were obtained for the isomorphic AgNbF6; primitive tetragonal, a=497.80(10) pm, b=960.40(10) pm, V=2.3799(12)×108 pm3, z=2. The results of the Raman spectroscopy of AgAF6 support the obtained structures. The structures are discussed by comparing with that of AgPF6 and AgAsF6 which have recently been determined in a series of our study.  相似文献   

9.
Marczenko Z  Balcerzak M  Kuś S 《Talanta》1980,27(12):1087-1089
The optimum conditions for preparation of stable solutions of ruthenate and osmate, after alkaline fusion of ruthenium(IV) compounds, ruthenium metal and osmium metal in a silver crucible, have been determined. The molar absorptivities of ruthenate and osmate are 1.74 × 103 1. mole−1.cm−1 at 465 nm (Ru) and 2.75 × 103 1.mole−1.cm−1 at 340 nm (Os) in 2M sodium hydroxide. A differential spectrophotometric method has been developed for determination of ruthenium in ruthenium dioxide, lead ruthenite and bismuth pyroruthenate. Simultaneous spectrophotometric determination is proposed for ruthenium and osmium. The other platinum metals interfere seriously only when present in> 1:1 w/w ratio to Ru.  相似文献   

10.
The photoionization of methyl iodide beam seeded in argon and helium is studied by time-of-flight mass spectrometry using a 25 ns, 532 nm Nd-YAG laser with intensities in the range of 2 × 1010–2 × 1011 W/cm2. Multiply charged ions of Iq+ (q = 2–3) and C2+ with tens of eV kinetic energies have been observed when laser interacts with the middle part of the pulsed molecular beam, whose peak profiles are independent on the laser polarization directions. Strong evidences show that these ions are coming from the Coulomb explosion of multiply charged CH3I clusters, and laser induced inverse bremsstrahlung absorption of caged electrons plays a key role in the formation of multiply charged ions.  相似文献   

11.
Palladium, silver and palladium–silver catalysts supported on silica were prepared by coimpregnation of support with solution of AgNO3 and Pd(NO3)2. The catalysts were characterized by X-ray powder diffraction (XRD), temperature programmed reduction (TPR), time of flight ion mass spectrometry (ToF-SIMS), chemisorption of carbon monoxide and were tested in the reaction of selective oxidation of glucose to gluconic acid.

XRD and TPR studies have shown that an interaction between Pd and Ag on the surface of silica after oxidation at 500 °C and reduction at 260 °C leads to the formation of solid solutions.

ToF-SIMS images of the surface of 5% Ag/SiO2 catalyst after oxidation at 500 °C and reduction at 260 °C show that Ag atoms supported on silica are not distributed homogenously but tend to form regions of enhanced Ag concentration. Positive ions images of the surface of 5% Pd/SiO2 catalyst also display regions of enhanced concentration of Pd atoms, but they are more homogenously distributed on silica.

ToF-SIMS peak intensity ratio 108Pd+/107Ag+ for bimetallic 5% Pd–5% Ag/SiO2 catalysts has a lower value than that obtained for physical mixture 5% Pd/SiO2–5% Ag/SiO2 which indicates that the surface of bimetallic catalyst is enriched with silver atoms.  相似文献   


12.
Saran L  Cavalheiro E  Neves EA 《Talanta》1995,42(12):2027-2032
The highly neutralized ethylenediaminetetraacetate (EDTA) titrant (95–99% as Y4− anion) precipitates with Ag+ cations to form the Ag4Y species, in aqueous medium, which is well characterized from conductometric titration, thermal analysis and potentiometric titration of the silver content of the solid. The precipitate dissolves in excess Y4− to form a complex, AgY3−. Equilibrium studies at 25°C and ionic strength 0.50 M (NaNO3) have shown from solubility and potentiometric measurements that the formation constant (95% confidence level) β1 = (1.93 ± 0.07) × 105 M−1 and the solubility products are KS0 = [Ag +]4[Y4−] = (9.0 ± 0.4) × 10−18 M5 and KS1 = [Ag +]3[AgY3−] = (1.74 ± 0.08) × 10−12 M4. The presence of Na+, rather than ionic strength, markedly affects the equilibrium; the data at ionic strength 0.10 M are: β1 = (1.19 ± 0.03) × 106 M−1, KS0 = (1.6 ± 0.4) × 10−19 M5 and KS1 = (1.9 ± 0.5) × 10−13 M4; at ionic strength tending to zero; β1 = (1.82 ± 0.05) × 107 M−1, KS0 = (2.6 ± 0.8) × 10−22 M5 and KS1 = (5 ± 1) × 10−15 M4. The intrinsic solubility is 2.03 mM silver (I) in 0.50 M NaNO3. Well-defined potentiometric titration curves can be taken in the range 1–2 mM with the Ag indicator electrode. Thermal analysis revealed from differential scanning calorimetry a sharp exothermic peak at 142°C; thermal gravimetry/differential thermal gravimetry has shown mass loss due to silver formation and a brown residue, a water-soluble polymeric acid (decomposition range 135–157°C), tending to pure silver at 600°C, consistent with the original Ag4Y salt.  相似文献   

13.
In this article we report a femtosecond time-resolved transient absorption study of a neutral organic mixed-valence (MV) compound with the aim to gain insight into its charge-transfer dynamics upon optical excitation. The back-electron transfer was investigated in five different solvents, toluene, dibutyl ether, methyl-tert-butyl ether (MTBE), benzonitrile and n-hexane. In the pump step, the molecule was excited at 760 nm and 850 nm into the intervalence charge-transfer band. The resulting transients can be described by two time constant. We assign one time constant to the rearrangement of solvent molecules in the charge-transfer state and the second time constant to back-electron transfer to the electronic ground state. Back-electron transfer rates range from 1.5 × 1012 s−1 in benzonitrile through 8.3 × 1011 s−1 in MTBE, around 1.6 × 1011 s−1 in dibutylether and toluene and to 3.8 × 109 s−1 in n-hexane.  相似文献   

14.
Flow injection visible diffuse reflectance quantitative analysis of nickel   总被引:1,自引:0,他引:1  
Flow injection (FI) methodology, using diffuse reflectance in the visible region of the spectrum, for the analysis of nickel, precipitated in the form of dimethylglyoximate, is presented. A reflectance cell, constructed in polytetrafluoroethylene, using a LED (light emitting diode) as light source and a LDR (light dependent resistor) as detector, is described. The analytical signal (S) correlates with nickel concentration (C) between 1.6 × 10−4 and 6.6 × 10−4 mol L−1. This correlation is described by the equation S = −1.108 + 3.314 × 104C − 2.081 × 107C2 (r = 0.9996). The experimentally observed limit of detection is about 1.3 × 10−4 mol L−1, as in lower concentrations the formation of precipitate is not observed. The experimental quantitation limit is about 1.6 × 10−4 mol L−1. The mean R.S.D. (relative standard deviation) is about 2.7%. Samples containing nickel were analyzed and the results obtained in this method were compared with those of other methods using the statistical Student's t-test.  相似文献   

15.
An unexpected novel coordination mode of diazoalkanes has been verified via addition of 2-diazopropane to the metal—metal triple bond of bis[dicarbonyl(η5-pentamethylcyclopentadienyl)molybdenum] (MoMo). The dinuclear 1:1 addition product isolated in nearly quantitative yield is structurally characterized by a bent, 4-electron type η12-diazoalkane ligand, with the terminal nitrogen atom symmetrically bridging the metal-metal “single bond” (d(MoMo) 305.0(2) pm; d(Mo---N(1)) 212.0(12) and 212.6(10) pm, respectively) and the second nitrogen atom being bonded to one molybdenum atom only (d(Mo---N(2)) 213.4(13) pm).  相似文献   

16.
The collisional behaviour of Ba[6s5d(3DJ)], 1.151 eV above the 6s2(1S0) electronic ground state, in the presence of atomic strontium, has been investigated in the ‘long-time domain' (ca. 100 μs–1 ms) following the pulsed dye-laser excitation of barium vapour at elevated temperature at λ = 553.5 nm (Ba[6s6p(1P1)] ← Ba[6s2(1S0)]. Ba(3DJ) is subsequently produced from the short-lived 1P1 state (τe = 8.37 ± 0.38 ns) by a number of radiative and collisional processes. It may then be monitored in the ‘long-time domain' by atomic spectroscopic marker methods involving either collisional activation of Ba(3DJ) by Ba(1S0) and He buffer gas to yield Ba[6s6p(3PJ)] with subsequent emission from the 3P1 state (τe = 1.2 ± 0.1 μs): Ba[6s6p(3P1)] → Ba[6s2(1S0)] + hv (λ = 791.1 nm). Alternatively, emission from Ba(1P1) may be monitored at long times following the generation of this short-lived state by energy pooling following self-annihilation of Ba(3DJ) + Ba(3DJ) from Ba[6s6p(1P1)] → Ba[6s2(1S0)] + hv (λ = 553.5 nm). The generation of Ba(3DJ) in the presence of atomic strontium yields emission in the long-time domain from Sr[5s5p(3P1)] (τe = 19.6 μs): Sr[5s5p(3P1)] → Sr[5s2(1S0)]  + hv (λ = 689.3 nm). Whilst the decay profiles at short times are complex in form, at long times all these atomic profiles show first-order kinetic removal with the decay coefficients for λ = 791.1 nm, 689.3 nm and 553.5 nm emissions in the ratio 1 : 2 : 2, consistent with overall third-order activation of the form: Ba(3DJ) + Ba(3DJ) + Sr(1S0) → Sr(3PJ) + 2Ba(1S0). The mechanism is modelled in detail, including measurement of integrated emission intensities, yielding kinetic data for fundamental collisional processes. The overall rate constant for the third-order collisional activation of Sr[5s5p(3PJ])from 2Ba[6s5d(3DJ)] + Sr[5s2(1S0)] takes the upper limit of 5.8 × 10−27 cm6 atom−2 s−1 (T = 900 K). The rate constant for the two body collisional quenching of Ba[6s5d(3DJ)] by ground state atomic strontium, Sr[5s2(1S0)], is found to be (2.0 ± 0.1) × 10−12 cm3 atom−1 s−1 (T = 900 K).  相似文献   

17.
Norfloxacin, 1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid (NORH), reacts with aluminium(III) ion forming the strongly fluorescent complex [Al(HNOR)]3+, in slightly acidic medium. The complex shows maximum emission at 440 nm with excitation at 320 nm. The fluorescence intensity is enhanced upon addition of 0.5% sodium dodecylsulphate. Fluorescence properties of the Al-NOR complex were used for the direct determination of trace amounts of NOR in serum. The linear dependence of fluorescence intensity on NOR concentration, at a NOR to Al concentration ratio of 1:10, was found in the concentration range 0.001–2 μg/ml NOR with a detection limit of 0.1 ng/ml. The ability of aluminium (III) ion to form complexes with NOR was investigated by titrations in 0.1 M LiCl medium, using a glass electrode, at 298 K, in the concentration range: 2 × 10−4 ≤ [Al] ≤ 8 × 10−4; 5 × 10−4 ≤ [NOR] ≤ 9 × 10−4 mol/dm3; 2.8 ≤ pH ≤ 8.3. The experimental data were explained by the following complexes and their respective stability constants, log(β ± σ): [Al(HNOR)], (14.60 ± 0.05); [Al(NOR)], (8.83 ± 0.08); [A1(OH)3(NOR)], (−14.9 ± 0.1), as well as several pure hydrolytic complexes of A13+. The structure of the [Al(HNOR)] complex is discussed, with respect to its fluorescence properties.  相似文献   

18.
Free radical reactions of dehydrozingerone (DZ), a methoxy phenol, were studied at dfferent pHs with a variety of oxidants using nanosecond pulse radiolysis technique. Hydroxyl radical (OH) reaction with the phenolic form at pH 6 led mainly to the formation of an OH-adduct absorbing at 460 nm in addition to a minor oxidation product. On the other hand, at pH 10 with the deprotonated phenoxide ion, the only reaction observable was oxidation generating a phenoxyl radical absorbing at 360 nm. HPLC analysis indicated formation of two different products at pH 6 from addition and oxidation reactions, whereas at pH 10, only the oxidation product was detectable. Reactions of more specific secondary oxidizing radicals, N3√, Br√, Br2√ and Tl(II) with DZ gave rise to the phenoxyl radical over the entire pH range. DZ in the phenoxide ion form reacted with nitrogen dioxide and trichloromethyl peroxyl radicals with rate constants 6×108 and 8.8×108 dm3 mol−1 s−1 respectively leading to the phenoxyl radicals. The DZ phenoxyl radical reacted with trolox C (an analogue of -tocopherol) with a rate constant of 8.3×107 dm3 mol−1 s−1. One electron reduction potential of the DZ phenoxyl radical at pH 6 was determined to be +1.1 V vs NHE using N3√/N3 as the standard couple.  相似文献   

19.
Using N3 species as specific electron acceptor a defined ascorbate radical: AH↔A+H+max=360 nm, =3400 dm3 mol−1 cm−1) is observed. The attack of DMSO+ on vit.E results in a vit.E radical (k=1×109 dm3 mol−1 s−1; λmax=425 nm, =2400 dm3 mol−1 cm−1; 2k=4.7×108 dm3 mol−1 s−1). Vit.E-acetate leads to the formation of a radical cation (vit.E-ac+). β-carotene reacts also with DMSO+ forming a radical cation, β-car+ (k=1.75×108 dm3 mol−1 s−1; λmax=942 nm, =14 600 dm3 mol−1 cm−1), which probably leads to the formation of a dimer radical cation, (β-car)+2 (k=2.5×107 dm3 mol−1 s−1).

Using E.coli bacteria (AB1157) as a model system in vitro it was found that all three vitamins are rather efficient radiation protecting agents. They can also increase the activity of cytostatica, e.g., mitomycin C (MMC), by electron transfer process. The mixture of vit.E-ac and β-car acts contradictory, but adding vit.C to it a strong cooperative enhancement of the MMC activity is observed once again. A relationship between the pulse radiolysis and the radiation biological data is found and discussed. A possible explanation of the previously reported trials concerning the role of vit.E and β-car on the increased occurence of lung and other types of cancer in smokers and drinkers is presented.  相似文献   


20.
To evaluate the contribution of local pulsed heating of light-absorbing microregions to biochemical activity, irradiation of Escherichia coli was carried out using femtosecond laser pulses (λ = 620 nm, τp=3 × 10−13 s, fp = 0.5 Hz, Ep = 1.1 × 10−3J cm−2, Iav = 5.5 × 10−4 W cm−2, Ip = 109 W cm−2) and continuous wave (CW) laser radiation (λ = 632.8 nm, I = 1.3 W cm−2). The irradiation dose required to produce a similar biological effect (a 160%–190% increase in the clonogenic activity of the irradiated cells compared with the non-irradiated controls) is a factor of about 103 lower for pulsed radiation than for CW radiation (3.3 × 10−1 and 7.8 × 102 J cm−2 respectively). The minimum size of the microregions transiently heated on irradiation with femtosecond laser pulses is estimated to be about 10 Å, which corresponds to the size of the chromophores of hypothetical primary photoacceptors—respiratory chain components.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号