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91.
Pina Romaniello 《Journal of fluorine chemistry》2004,125(2):145-149
The effect of fluorine atoms on the second-order optical nonlinear response of 4-nitro-4′-methoxy-trans-stilbene and polyene derivatives containing up to three double bonds (n=1, 2, 3) has been investigated within a semiempirical context (PM3 Hamiltonian). Experimental data reported in literature indicate a βvec(SHG) value of 34, 47 and 76 (×10−30 esu) for n=1, 2, 3, respectively, at 0.65 eV in CHCl3 solutions. Our calculations show that fluorinating the nitrophenyl group the βvec(SHG) is doubled. Further increase in the second-order nonlinear response can be obtained fluorinating the CC bond linkers between the aromatic moieties.Besides, the effect of different donor-acceptor pairs has been studied and the results interpreted in the two-state model context.Some results concerning the third-harmonic generation (THG), γ (THG), are presented, and a possible interpretation proposed. 相似文献
92.
R. A. Manzhos B. I. Podlovchenko Yu. M. Maksimov 《Russian Journal of Electrochemistry》2006,42(6):658-664
Transients of the open-circuit potential, which are observed when formic acid is interacting wit adsorbed oxygen (Oads) preliminarily accumulated on polycrystalline “smooth” platinum (pcPt), are measure in an aqueous solution of sulfuric acid. It is shown that, as with platinized platinum (Pt/Pt), at large coverage by adsorbed oxygen (θO = 1?0.8), adsorbed oxygen interacts directly with molecules of formic acid from solution. In the region of medium coverages (θO = 0.8?0.2), on the other hand, a mechanism of “conjugated reactions” is realized. It is established that, in the case of pcPt, the direct interaction of Oads with molecules of HCOOH from solution proceeds slower by nearly three times and the interaction via the mechanism of “conjugated reactions,” faster by about three times, as compared with Pt/Pt. 相似文献
93.
Digrazia Philip M. Blackburn James W. Bienkowski Paul R. Hilton Barry Reed Gregory D. King J. M. Henry Sayler Gary S. 《Applied biochemistry and biotechnology》1990,(1):237-252
An experimental and mathematical method is developed for the microbial systems analysis of polyaromatic hydrocarbon (PAH)-degrading
mixed cultures in PAH-contaminated “town gas” soil systems. Frequency response is the primary experimental and data analysis
tool used to probe the structure of these complicated systems. The objective is to provide a fundamental protocol for evaluating
the performance of specific mixed microbial cultures on specific soil systems by elucidating the salient system variables
and their interactions. Two well-described reactor systems, a constant volume stirred tank reactor (CSTR) and a plug flow
differential volume reactor, are used in order to remove performance effects that are related to reactor type as opposed to
system structure. These two reactor systems are well-defined systems that can be described mathematically and represent the
two extremes of one potentially important system variable, macroscopic mass transfer. The experimental and mathematical structure
of the protocol is described, experimental data is presented, and data analysis is demonstrated for the stripping, sorption,
and biodegradation of napththalene. 相似文献
94.
In the present work, corrosion resistance of surface-coated galvanized steel was quantitatively determined by an analysis
of the alternating current (AC) impedance spectra measured on the salt-spray-tested specimen. To evaluate the corrosion resistance
of the surface-coated galvanized steel, AC impedance spectroscopy was performed on the salt-spray-tested specimen previously
exposed to salt-sprayed corrosive environment. From the analysis of the impedance spectra, the area fraction transient of
white rust θ
2(t) was theoretically derived from the equivalent circuit equation by using two fitting parameters. The values of the two fitting
parameters were determined by fitting the empirical transient equations to the area fraction of the resin coating layer and
to the total resistance obtained from the impedance spectra measured, respectively. From the analyses of θ
2(t) for four kinds of surface-coated galvanized steels with various resin coating layers, it is indicated that as the values
of the two fitting parameters decrease in the order of CP, GI, OD and OM (commercial trade names) specimens, the corrosion
resistance increases in that order as well. Furthermore, from the quantitative comparison of the two fitting parameters with
the polarization resistance of the upper resin coating layer R
p determined from the potentiodynamic polarization curve, it is suggested that the two fitting parameters decrease in value
as well with increasing R
p. 相似文献
95.
The possibility of simultaneous application of an electron capture (ECD) and a flame ionization detector (FID) connected to a glass capillary column for analyzing polynuclear aromatic hydrocarbons (PNA) has been investigated. The ECD/FID ratio is determined for 46 PNA compounds. The ratios vary from 0.02 to 117 with relative standard deviations better than 20 percent determined from 10 replicate analyses. The results suggest that the method may be used for obtaining additional evidence in identifying PNA in environmental samples. Impurities and transformation products in the standard were identified by computerized glass capillary gas chromatography/mass spectrometry. Quinones and diones are responsible for the high EC-response determined in some trace components in the standard. An application of the method is shown for PNA from particulates in urban atmospheres. 相似文献
96.
Using laser flash photolysis/transient absorption technique for the study of two photon photodissociation of carbon disulfide in acetonitrile solution at 266 nm, the transient UV-Vis absorption spectrum of Rydberg state CS2 (6sσg) within 240-370 nm and subsequent dissociation product CS (α^3П) with the maximum absorption at 260 nm were directly observed. The lifetime of CS (α^3П) in the nitrogen and oxygen saturated solution is also studied in our experiment. 相似文献
97.
用真空蒸发沉积的方法制备了纳米稀土(La、Nd、Sm)粒子 BaO介质薄膜.研究表明薄膜的光电发射光谱响应阈值受纳米稀土粒子形状和大小的影响,球形纳米稀土(Sm)粒子 BaO介质薄膜的光谱响应阈值波长为720 nm,条状纳米稀土(La和Nd)粒子 BaO介质薄膜阈值波长分别为650 nm和660 nm.研究得到纳米稀土粒子 介质薄膜等效界面位垒高度在1.7~2.0 eV之间.由于纳米稀土粒子与BaO介质各自逸出功不同,当构成薄膜后使得纳米粒子周围的空间电荷分布发生变化,纳米粒子周围的能带发生弯曲. 相似文献
98.
In this work, the mechanochemical synthesis of a moderately agglomerated tin oxide (SnO2) powders and the subsequent preparation of semiconductor gas sensors as prototypes, were studied. Tin (II) chloride (SnCl2) powder was milled with calcium hydroxide (Ca(OH)2) and potassium carbonate, (K2CO3) powder, respectively, in a ball mill at room temperature and in an air atmosphere. Heat treatment of milled mixtures at 400 °C resulted in the formation of a tetragonal phase, confirmed by X-ray diffraction (XRD). During milling in the presence of water, a high number of hydroxide (OH) groups are formed at the surface. When SnCl2 was milled with K2CO3, no water was produced and the Fourier-transform infrared spectrum (FT-IR) of the powder has no surface hydroxyl deformations. On exposure to hydrogen sulfide (H2S) gas, the particles, prepared from anhydrous powder, have higher sensitivity than these, prepared from hydrated powder. The SnO2 thick film, prepared from anhydrous powder may be successfully applied to a H2S gas sensor. 相似文献
99.
A supported liquid and a poly(vinyl chloride) (PVC)-based membrane selective for dodecylsulfate (DS−) ion are described. The active element is a membrane containing a dissolved ion association complex of DS− with cetylpyridinium (CP+) cation. The supported liquid membrane electrode (acetophenone as solvent) showed a Nernstian response towards the DS− anion over the concentration range of sodium dodecylsulfate (SDS) from 8.3×10−3 to 1.0×10−6 mol dm−3 at 25 °C. The proposed electrode also showed a super-Nernstian potential response (108±2 mV decade−1) at low concentrations (1.0×10−9 to 1.0×10−6 mol dm−3). Moreover, this electrode showed good selectivity and precision (R.S.D.?2.0%), and was usable within the pH range 4.0-6.8. The proposed electrode revealed a lower limit of detection of 6.3×10−7 mol dm−3 and improved selectivity in comparison with the some previously reported DS− ion selective electrodes. The isothermal temperature coefficient of this electrode amounted to −0.001 V °C−1. The liquid membrane electrode may find application in the direct determination of SDS by the standard addition method at pH 5.0, and in the physicochemical studies of surfactant solutions. 相似文献
100.
Investigation of the Interactions of β‐Peptides with DNA Duplexes by Circular Dichroism Spectroscopy
Kenji Namoto James Gardiner Thierry Kimmerlin Dieter Seebach 《Helvetica chimica acta》2006,89(12):3087-3103
The interaction of β‐peptides with the DNA duplexes of dA20dT20 and a GCN4‐binding CRE sequence was examined. To gauge the factors that govern these interactions, two β‐pentadecapeptides, 1 and 2 , a β‐dodecapeptide, 3 , three β‐decapeptides, 4 – 6 , three β‐heptapeptides, 7 – 9 , and β‐octaarginine 10 were designed and synthesized. The β‐peptides were conceived to adopt a β‐peptide 314 helix, in which the side chains at position i and i + 3 are aligned vertically along one side of the helix. The side chains of Lys, Asn, and Arg were positioned such that potential H‐bonding sites were created for a helical conformation to interact with the base pairs of DNA. CD Analysis showed that β‐peptides 1, 2 , and 10 interacted with dA20dT20. In addition, β‐peptides 1 and 2 showed significant interaction with a DNA‐duplex 20mer containing the ATF/CREB recognition sequence for the regulatory protein GCN4. It is impossible, at this stage of the investigation, to make a safe proposal about the actual nature of the interaction of the structures(s) of the complexes, the formation of which is suggested by the CD spectra reported herein. 相似文献