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1.
The reactions taking place in the mixed solution of biphenyl and nitrous acid after it was exposed to UV irradiation were studied in this research work. The transient species were identified with the nanosec- ond transient spectroscopic technique, and the final products were ascertained by GC-MS analysis. It was shown that the OH radical, generated by the direct photolysis of nitrous acid, would attack biphe- nyl molecule to form Bp-OH adduct with a rate constant of 9.5×109 L·mol?1·s?1. The Bp-OH adduct could either react with H or be oxidized by nitrous acid to form nitrosobiphenol. The reactions between biphenyl and nitrous acid under UV irradiation in atmospheric aqueous phase were therefore sug- gested to be one promising source of nitrocompounds in the environment.  相似文献   

2.
A novel photocatalytic material (Pt,Cd0.8Zn0.2S)/HLaNb2O7 was fabricated by successive intercalation and exchange reactions. The (Pt,Cd0.8Zn0.2S)/HLaNb2O7 possessed a gallery height less than 0.5 nm and showed a broad absorption with wavelength over 370-500 nm. Using (Pt,Cd0.8Zn0.2S)/HLaNb2O7 as catalyst, the photocatalytic H2 evolution was more than 160 cm3·h-1·g-1 in the presence of Na2S as a sacrificial agent under irradiation with wavelength more than 290 nm from a 100-W mercury lamp. Furthermore, the catalyst showed photocatalytic activity even under visible light irradiation.  相似文献   

3.
Nanogold particles of 10 nm were used to label goat anti-human IgG (GIgG) to obtain nanogold-labeled GIgG (AuGIgG). In a citrate-HCI buffer solution of pH 2.27, AuGIgG showed a strong catalytic effect on the reaction between HAuCl4 and NH2OH to form big gold particles that exhibited a resonance scattering (RS) peak at 796 nm. Under the chosen conditions, AuGIgG combined with IgG to form immunocomplex AuGIgG-IgG that can be removed by centrifuging at 16000 r/min. AuGIgG in the centrifuging solution also showed catalytic effect on the reaction. On those grounds, an immunonanogold catalytic RS assay for IgG was designed. With addition of IgG, the amount of AuGIgG in the centrifuging solution decreased; the RS intensity at 796 nm (I 796 nm) decreased linearly. The decreased intensity ΔI 796 nm was linear with respect to the IgG concentration in the range of 0.08–16.0 ng · mL−1 with a detection limit of 0.02 ng · mL−1. This assay was applied to analysis of IgG in sera with satisfactory sensitivity, selectivity and rapidity. Supported by the National Natural Science Foundation of China (Grant No. 20667001), Natural Science Foundation of Guangxi Province (Grant No. 0728213), and the Foundation of New Century Ten-Hundred-Thousand Talents of Guangxi Province  相似文献   

4.
UV/H2O2/micro-aeration is a newly developed process based on UV/H2O2. Halogenated pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) photochemical degradation in aqueous solution was studied under various solution conditions. The UV intensity, initial 2,4-D concentrations and solution temperature varied from 183.6 to 1048.7 μW·cm−2, from 59.2 to 300.0 μg·L−1 and from 15 to 30°C, respectively. The concentration of hydrogen peroxide (H2O2) and pH ranged from 0 to 50 mg·L−1 and 5 to 9, and different water quality solutions (tap water, distilled water and deionized water) were examined in this study. With initial concentration of about 100 μg·L−1, more than 95.6% of 2,4-D can be removed in 90 min at intensity of UV radiation of 843.9 μW·cm−2, H2O2 dosage of 20 mg·L−1, pH 7 and room temperature. The removal efficiency of 2,4-D by UV/H2O2/micro-aeration process is better than UV/H2O2 process. The photodecomposition of 2,4-D in aqueous solution follows pseudo-first-order kinetics. 2,4-D is greatly affected by UV irradation intensity, H2O2 dosage, initial 2,4-D concentration and water quality solutions, but it appears to be slightly influenced by pH and temperature. There is a linear relationship between rate constant k and UV intensity and initial H2O2 concentration, which indicates that higher removal capacity can be achieved by the improvement of these factors. Finally, a preliminary cost analysis reveals that UV/H2O2/micro-aeration process is more cost-effective than the UV/H2O2 process in the removal of 2,4-D from drinking water.  相似文献   

5.
A new fluorescent sensor (1) for Pb2+ containing a 1,4-dicyano-2,5-bis(styryl)benzene fluorophore and 2-(N,N′-bis(carboxylmethyl))amino-1-carboxylmethoxylbenzene as receptor has been synthesized. The sensor selectively responds to Pb2+ in the aqueous environment, and brings about similar and significant changes in one- and two-photon excited emission spectra: λ max red-shift from 460 (519) to 590 nm. The selective response is pH-independent in a large physiological pH range, and two-photon action cross section (ϕδ) is 51 GM (1 GM = 1×10−50 cm4·s·photon−1·molecule−1) at 740 nm. Supported by the National Natural Science Foundation of China (Grant Nos. 20705621 & 20706008), the National Basic Research Project of China (Grant No. 2009CB724706), the Ministry of Education of China, Changjiang Scholars Innovative Research Team in University (Grant No. IRT0711) and Cultivation Fund of the Key Scientific and Technical Innovation Project (Grant No. 707016)  相似文献   

6.
5-HT1A receptor is associated with a variety of pathophysiology of neuropsychiatric disorders. Accordingly, we have synthesized a new 5-HT1A receptor ligand (HYNIC-MPP4) and labeled it with 99mTc using N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) as coligand. 99mTc-HEDTA/HYNIC-MPP4 was prepared under pH 6 at room temperature. Biodistribution of 99mTc-HEDTA/HYNIC-MPP4 in normal mice showed that this complex had moderate brain uptake (0.60% ID·g−1 at 2 min p.i.) and good retention. The hippocampus had the highest radioactivity uptake at 2 min p.i. (1.84% ID⋆g−1). The ratio of Hipp/CB was 3.1 at 2 min p.i. and increased to 4.4 at 60 min p.i. After blocking with 8-hydroxy-2-(dipropylamino) tetralin, the uptake of hippocampus was decreased significantly from 1.84% ID·g−1 to 0.53% ID·g−1 at 2 min p.i., while the cerebellum had no significant decrease. This 99mTc complex could be a potent agent for 5-HT1A receptor imaging. Supported by the National Natural Science Foundation of China (Grant No. 20401004) and the Analysis and Test fund of Beijing Normal University  相似文献   

7.
The heat capacity and the enthalpy increments of strontium metaniobate SrNb2O6 were measured by the relaxation method (2-276 K), micro DSC calorimetry (260-320 K) and drop calorimetry (723-1472 K). Temperature dependence of the molar heat capacity in the form C pm=(200.47±5.51)+(0.02937±0.0760)T-(3.4728±0.3115)·106/T 2 J K−1 mol−1 (298-1500 K) was derived by the least-squares method from the experimental data. Furthermore, the standard molar entropy at 298.15 K S m0 (298.15 K)=173.88±0.39 J K−1 mol−1 was evaluated from the low temperature heat capacity measurements. The standard enthalpy of formation Δf H 0 (298.15 K)=-2826.78 kJ mol−1 was derived from total energies obtained by full potential LAPW electronic structure calculations within density functional theory.  相似文献   

8.
Solubility product (Lu(OH)3(s)⇆Lu3++3OH) and first hydrolysis (Lu3++H2O⇆Lu(OH)2++H+) constants were determined for an initial lutetium concentration range from 3.72·10−5 mol·dm−3 to 2.09·10−3 mol·dm−3. Measurements were made in 2 mol·dm−3 NaClO4 ionic strength, under CO2-free conditions and temperature was controlled at 303 K. Solubility diagrams (pLuaq vs. pC H) were determined by means of a radiochemical method using 177Lu. The pC H for the beginning of precipitation and solubility product constant were determined from these diagrams and both the first hydrolysis and solubility product constants were calculated by fitting the diagrams to the solubility equation. The pC H values of precipitation increases inversely to [Lu3+]initial and the values for the first hydrolysis and solubility product constants were log10 β* Lu,H = −7.92±0.07 and log10 K*sp,Lu(OH)3 = −23.37±0.14. Individual solubility values for pC H range between the beginning of precipitation and 8.5 were S Lu3+ = 3.5·10−7 mol·dm−3, S Lu(OH)2+ = 6.2·10−7 mol·dm−3, and then total solubility was 9.7·10−7 mol·dm−3.  相似文献   

9.
Methane (CH4) and nitrous oxide (N2O) saturation concentration and gas-water interface emission flux in surface water of the Yangtze Delta plain river net were investigated in summer at representative sites including the upper reaches of the Huangpu River and the rivers in the Chongming Island. The results show that the CH4 concentration in river water ranged from 0.30±0.03 to 6.66±0.14 μmol.L-1, and N2O concentration ranged from 13.8±2.33 to 435±116 nmol.L-1. River surface water had a very high satura- tio...  相似文献   

10.
Data obtained for the kinetics of oxidation of diethyl sulfide (Et2S) by hydrogen peroxide in aqueous solution catalyzed by boric acid indicate that monoperoxoborates B(O2H)(OH) 3 and diperoxoborates B(O2H)2(OH) 2 are the active species. The rates of the reactions of Et2S with B(O2H)(OH) 3 and B(O2H)2(OH) 2 are 2.5 and 100 times greater than with H2O2. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 1, pp. 38–42, January–February, 2007.  相似文献   

11.
An indium tin oxide (ITO) electrode modified with monolayer clay/[Ru(phen)2(dC18bpy)]2+ (phen=1,10-phenanthroline, dC18bpy = 4,4′-dioctadecyl-2,2′ bipyridyl) hybrid film has been fabricated by the Langmuir-Blodgett (LB) method. Atomic force microscopy revealed that the single-layered hybrid film of clay/[Ru(phen)2(dC18bpy)]2+ (denoted as Clay-Ru) was closely packed at a surface pressure of 25 mN·m−1 and had a thickness of 3.4±0.5 nm. Cyclic voltammograms showed that the redox current of Ru(II) complex decreased when incorporated into the clay film, suggesting that the clay layer acts as a barrier against electron transfer. When applied to oxidizing the mononucleotide of guanosine 5′-monophosphate (GMP), a large catalytic oxidative current was achieved on the Clay-Ru(II) modified ITO electrode at the external potential above 900 mV (vs. Ag|AgCl|KCl) and, more significantly, this response was further enhanced by light irradiation (λ>360 nm), in which the photocurrent is increased about 11 times in comparison with that of a bare ITO. Mechanism of the photoelectrocatalytic effect was proposed in terms of the reduction of the photoelectrochemically generated Ru(III) complex in the Clay-Ru film by GMP. Supported by the National Natural Science Foundation of China (Grant Nos. 20471043 and 20843007), Zhejiang Provincial Natural Science Foundation (Grant Nos. Y404118 and Y408177), the “151” Distinguished Person Foundation of Zheji-ang Province of China, Zhejiang Technology Project Foundation (Grant No. 2007C21134) and Wenzhou Technology Project Foundation (Grant No. N2004B040)  相似文献   

12.
The rate constants of the reactions of the chlorine atom with C3F7I (k 1) and CF3I (k 2) have been measured using the resonance fluorescence of chlorine atoms in a flow reactor at 295 K: k 1 = (5.2 ± 0.3) × 10−12 cm3 molecule−1 s−1 and k 2 = (7.4 ± 0.6) × 10−13 cm3 molecule−1 s−1. No iodine atoms have been detected in the reaction products.  相似文献   

13.
N,N-dimethyl-3-oxa-glutaramic acid was purified and characterized by 1H-NMR, Fourier transform infrared spectroscopy (FT-IR) and elemental analysis. The thermal decomposition of the title compound was studied by means of thermogravimetry differential thermogravimetry (TG-DTG) and FT-IR. The kinetic parameters of its second-stage decomposition reaction were calculated and the decomposition mechanism was discussed. The kinetic model function in a differential form, apparent activation energy and pre-exponential constant of the reaction are 3/2 [(1−α)1/3−1]−1, 203.75 kJ·mol−1 and 1017.95s−1, respectively. The values of ΔS , ΔH and ΔG of the reaction are 94.28 J·mol−1·K−1, 203.75 kJ·mol−1 and 155.75 kJ·mol−1, respectively. Supported by the National Natural Science Foundation of China (Grant No. 20106009)  相似文献   

14.
Pulse radiolysis has been used to investigate the reaction of hydroxyl radical (·OH) and oxide radical anion (O·−) with 2-aminopurine (2AP), a fluorescent analogue of adenine, in aqueous medium. The second-order rate constant for the reaction of ·OH with 2AP was determined to be 3 × 109 dm3 mol−1s−1 and for the reaction of O·− it was 7.1 × 108 dm3 mol−1s−1. The transient absorption spectrum obtained in the reaction of ·OH at pH 7 has absorption maxima at 370 and 470 nm. The spectrum undergoes a time-dependent transformation at higher time-scale. The intermediate species was found to react with N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD). The yield of TMPD·+ was calculated in terms of G(TMPD·+) to be 3.3 × 10−7 mol J−1 at pH 7. The ·OH reactions were also carried out at pH 10 and the transient absorption spectra have λ max at 400 and 480 nm. The transient spectra obtained in the reaction of O·− at pH ≈14 have maxima at 400 and 480 nm. The transient intermediate species at pH 7 are assigned to the formation of 2AP-4-OH· (54%), 2AP-5-OH· (7%) and 2AP-8-OH· (39%) based on the spectral evidence and TMPD·+ build-up. Both 2AP-4-OH· and 2AP-5-OH· undergo OH elimination to form a radical cation. At higher pH (pH 10), the dehydration reaction of these OH-adducts leads to a N-centered radical (2AP-N(9)·, 71%). Formation of 2AP-8-OH· (29%) is also proposed at this pH. In the reaction of O·− with 2AP, it is proposed that a similar nitrogen centered 2AP-N(9)· radical is formed by an electron-transfer reaction at N(9).  相似文献   

15.
Radical-ion salts bis(biphenyl)chromium(i) 1,4-di(2-cyanoisopropyl)-1,4-dihydrofulleride [(Ph2)2Cr][1,4-(CMe2CN)2C60]−· and bis(biphenyl)chromium(i) 1-(2-cyanoisopropyl)-1,2-dihydrofulleride [(Ph2)2Cr][1,2-(CMe2CN)(H)C60]−·, the salt bis(biphenyl)chromium(i) (2-cyanoisopropyl)fulleride [(Ph2)2Cr][(CMe2CN)C60], and neutral 1-(2-cyanoisopropyl)-1,2-dihydrofullerene 1,2-(CMe2CN)(H)C60 have been synthesized for the first time. The compounds [(Ph2)2Cr][1,4-(CMe2CN)2C60]−· and [(Ph2)2Cr][1,2-(CMe2CN)(H)C60]−· decompose in THF to form [(Ph2)2Cr][(CMe2CN)C60], whose protonation affords 1,2-(CMe2CN)(H)C60. 1,4-Di(2-cyanoisopropyl)-1,4-dihydrofullerene 1,4-(CMe2CN)2C60 and 1,2-(CMe2CN)(H)C60 are stable in vacuo up to 513 K. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1935–1939, September, 2008.  相似文献   

16.
The reactions of e aq, H-atoms, OH radicals and some one electron oxidants and reductants were studied with dithio-oxamide (DTO) in aqueous solutions using pulse radiolysis technique. The transient species formed by the reaction of e aq with DTO at pH 6.8 has an absorption band with λ max at 380 nm and is reducing in nature. H-atom reaction with DTO at pH 6.8 also produced the same transient species. The semi-reduced species was found to be neutral indicating that the electron adduct gets protonated quickly. However at pH 1, the species produced by H-atom reaction had a different spectrum with λ max at 360 and 520 nm. Reaction of acetone ketyl radicals and CO2 radicals with DTO at pH 6.8 gave transient spectra which were identical to that obtained by e aq reaction. However at pH 1, the spectrum obtained by the reaction of acetone ketyl radicals with DTO was similar to that obtained by H-atom reaction at that pH. The transient species formed by OH radical reaction with DTO in the pH range 1–9.2 also has two absorption maxima at 360 and 520 nm. This spectrum was identical with the spectrum obtained by H-atom reaction at pH 1. This means that all these radicals viz. OH, H-atom and (CH3)2COH radicals react with DTO at pH 1 by H-abstraction mechanism. The transient species produced was found to be sensitive to the presence of oxygen. One-electron oxidizing radicals such as Br2 −· and SO4 −· radicals reacted with DTO at neutral pH to give the same species as produced by OH radical reaction having absorption maxima at 360 to 520 nm. At acidic pHs, only Br2 −· and Cl2 −· radicals were able to oxidize DTO to give the same species as produced by OH radical reaction. The semioxidized species is a resonance stabilized species with the electron delocalized over the-N-C-S bond. This species was found to be neutral and non-oxidizing in nature.  相似文献   

17.
A new tripodal rhodamine B derivative 2 was designed and synthesized by tripodal trialdehyde and rhodamine B hydrazide for the first time. This derivative could be used as a fluorescent chemosensor for the selective and sensitive determination of copper(II) in Tris-HCl buffer and ethanol aqueous mixed media. Under the optimum conditions described herein, fluorescence enhancement at 557/577 nm was linearly related to the concentration of copper(II) in the range of 0.10 to 10.00×10−5 mol·L−1, with a correlation coefficient of R 2=0.9964 (n=15) and a detection limit of 1.129×10−7 mol·L−1 (the relative standard deviation for five repeated measurements at 4.00×10−5 mol·L−1 Cu(II) was 2.2%). The absorbance measurements at 557 nm were linearly related to the concentration of Cu(II) in the range of 0.50 to 25.00×10−5 mol·L−1, with a correlation coefficient of R 2=0.9948 (n=13) and a detection limit of 3.338×10−7mol·L−1. Supported by the Foundation of the Governor of Guizhou Province, China (Grant No. 200617) and the Talented Person Foundation of Guizhou University (Grant No. 2007039)  相似文献   

18.
Fullerenyl radicals (FR) RC60 · and chemiluminescence (CL) are generated in the presence of O2 in C60—R3Al (R = Et, Bui) solutions in toluene (T = 298 K). The FR are formed due to the addition of the R· radical, which is an intermediate of R3Al autooxidation, to C60. Mass spectroscopy and HPLC were used to identify EtnC60Hm (n, m = 1–6), EtpC60 (p = 2–6), and dimer EtC60C60Et as stable products of FR transformations. As found by ESR, the EtC60 · radical (g = 2.0037) is also generated by photolysis of solutions obtained after interaction in the (C60— R3Al)—O2 system. In the presence of dioxygen, the FR is not oxidized but yields complexes with O2, which appear as broadening of the ESR signals. Chemiluminescence arising in the (C60—R3Al)—O2 system is much brighter (I max = 1.86·108 photon s−1 mL−1) than the known background CL (I max = 6.0·106 photon s−1 mL−1) for the autooxidation of R3Al and is localized in a longer-wavelength spectral region (λmax = 617 and 664 nm). This CL is generated as a result of energy transfer from the primary emitter 3CH3CHO* to the products of FR transformation: RnC60Hm, RpC60, and EtC60C60Et. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 205–213, February, 2007.  相似文献   

19.
Homogeneous manganocolumbite (MnNb2O6) was synthesized from Nb2O5 and MnO oxides. Powder sample was orthorhombic with unit cell parameters: α = 0.5766 nm, b = 1.4439 nm, c = 0.5085 nm and V = 0.4234 nm3. Heat capacity over the temperature range of 313–1253 K was measured in an inert atmosphere with combined thermogravimetry and calorimetry using NETZSCH STA 449C Jupiter thermoanalyzer. Melting point was 1767 ± 3 K, enthalpy of melting was 144 ± 4 kJ mol−1. Experimental heat capacity of MnNb2O6 is fitted to polynomial C pm = 221.46 + 3.03 · 10−3 T + −39.79 · 105 T −2 + 40.59 · 10−6 T 2.  相似文献   

20.
The dissolution of UO2 particles in 4 mol·L−1 nitric acid medium at temperatures of 90–110°C by microwave heating and conventional heating has been investigated, respectively. It is found that the dissolution ratios of UO2 particles by microwave heating were 10%–40% higher than that by conventional heating. Kinetics research shows that the dissolution of UO2 particles in 4 mol·L−1 nitric acid is controlled by the diffusion control model for microwave heating and by the surface reaction control model for conventional heating. The diffusion control model for the dissolution of UO2 particles by microwave heating could be explained by the diffuseness on the surface of UO2 particles.  相似文献   

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