Experimental investigation of incremental reactivity of di-tert-butyl peroxide

Large quantities of di-tert-butyl peroxide (DTBP) have been emitted into the troposphere due to human activities. Its role in the atmospheric photochemical reaction has not been understood. This study presents the results of the photochemical reactions of DTBP and NOx, which have been simulated in a self-made smog chamber under the temperature of (29±1)℃. Both the wall decays of ozone and NO2 could be neglected, compared to the results in simulative experiments. The effective intensity of UV light used in the experiments was 1.28×10-3 s-1, which was expressed by the rate constant of NO2 photolysis in purified air. The reaction mechanism was proposed according to our results and reports of other researchers. The maximum values of incremental reactivity (IR) in the three simulative ex- periments were 9.53×10-2, 5.23×10-2 and 3.78×10-2, respectively. The incremental reactivity decreased with the increase of initial concentrations of DTBP. The IR value of DTBP obtained in this study was comparable to that of acetylene reported in our previous research.     

Rate constants for the reaction of ozone with <Emphasis Type="Italic">n</Emphasis>-butyl, <Emphasis Type="Italic">s</Emphasis>-butyl and <Emphasis Type="Italic">t</Emphasis>-butyl methyl sulfides

The rate constants for the ozone reactions with n-butyl methyl sulfide （n-BMS, CHaCH2CH2CH2SCH3）, sec-butyl methyl sulfide （s-BMS, CH3CH2（CH3）CHSCHa） and tert-butyl methyl sulfide （t-BMS, （CH3）3CSCH3） were measured using our smog chamber under supposedly pseudo-first-order conditions at 30002 K and 760 Torr. The experimental determined rate constants for n-butyl, s-butyl and t-butyl methyl sulfide are （1.23 ± 0.06）×10-19, （5.08 ± 0.19）×10-20 and （2.26 ± 0.14）×10-20 cm3 molecule-1· s-1, respectively. The reactivity-structure relationship of the reactions was discussed and used to illustrate the mechanism of the ozone reaction with thioethers. The results enrich the kinetics data of atmospheric chemistry.     

Smog chamber studies of ozone formation potentials for isopentane

The incremental reactivity and ozone formation potential of isopentane have been studied with chamber experiments and computer simulations. The chemical mechanism used in the computer simulations is an isopentane sub-mechanism from the Master Chemical Mechanism （MCM）. The results from the chamber experiments suggest that the MCM can well simulate i-C5H12-NOx chamber experiments. The heterogeneous reaction of NO2 and water is an important source for OH radicals in the chamber experiments. The photolysis of HONO is responsible for the initiation of isopentane in photochemical reactions. The reaction rate constant for NO2 → HONO was determined to be 3.9×10-4―5.9×10-3 min-1 by conducting 3 sets of CO-NOx-air irradiations. 5 sets of isopentane-NOx irradiations under different conditions were performed in our chamber. Compared with the experiment with a low relative humidity （RH）, an increase in RH can increase the reaction rate of NO2 with H2O, so that the peak ozone occurs earlier. When isopentane is predominant over NOx, the peak ozone concentration is largely dependent on NOx concentrations.     

Formate and acetate as recorded in a mid－latitude glacier in west China

Formic (HCOOH) and acetic (CH3COOH) acids are the chief carboxylic compounds in the troposphere[1]. Although weak acids, they contribute significantly to the free acidity, ionic balance of precipitation and the chemical reactions in the atmosphere, especially in the remote areas[2—4]. General sources for formate and acetate have been identified in the past 3 decades although a satisfactory source attribution is lacking to explain atmospheric observations[5]. Possible sources include veget…     

Trend, seasonal and diurnal variations of atmospheric CO2 in Beijing

The concentration of atmospheric CO₂ in Beijing increased rapidly at a mean growth rate of 3.7% · a⁻¹ from 1993 to 1995. After displaying a peak of (409.7±25.9) μmol · mol⁻¹ in 1995, it decreased slowly. Both the almost stable anthropogenic CO₂ source and increasing biotic CO₂ sink contribute to the drop of CO₂ concentration from 1995 to 2000. The seasonal variation of CO₂ concentration exhibits a clear cycle with a maximum in winter, averaging (426.8±20.6) μmol · mol⁻¹, and a minimum in summer, averaging (369.1±6.1) μmol·mol⁻¹. The seasonal variation of CO₂ concentration is mainly controlled by phenology. The mean diurnal variation of atmospheric CO₂ concentration for a year in Beijing is highly clear: daily maximum CO₂ concentration usually occurs at night, but daily minimum CO₂ concentration does in the daytime, with a mean diurnal difference more than 34.7 μmol·mol⁻¹. It has been revealed that the interannual variations of atmospheric CO₂ concentration in winter and autumn regulated the interannual trend of atmospheric CO₂, whereas the interannual variation of CO₂ concentration in summer affected the general tendency of atmospheric CO₂ in a less degree.     

Fluxes of carbon dioxide and methane from swamp and impact factors in Sanjiang Plain,China

Incomplete decomposition of organic matter results in the accumulation of the carbon and other nutriments in wetlands. The wetland ecosystem gains a large amount of carbon from atmosphere CO2 by photosynthesis, and it loses much of which back into the atmosphere as CO2 and CH4 emission through the decomposition and respiration. Climate change, such as global warming and reduction of precipitation could drive the wetlands from carbon sink to source[1,2]. Wetland plays an important role in car…     

Synthesis of a novel triple-site diphosphinoamine （PNP） ligand and its applications in ethylene tetramerization

A novel triple-site diphosphinoamine （PNP） ligand was synthesized and characterized. In combination with Cr（Ⅲ） and methylaluminoxane （MAO）, it generated active catalytic systems for ethylene tetramerization toward 1-octene with high catalytic activity and long lifetime. The effects of reaction temperature, molar ratio of AI/Cr and molar ratio of ligand/Cr on catalytic activity and selectivity to 1-octene were studied with reaction kinetics of the catalytic system for ethylene tetramerization described. At the AI/Cr molar ratio of 100, the catalytic activity is up to 2.29×10^6 g· mol^-1 （Cr）· h^-1 and the selectivity to 1-octene is 49.65 wt%.     

Kinetic studies of the decomposition reaction of adducts of dinuclear Fe(Ⅱ)/O2

Kinetic studies of the decomposition reaction of dinuclear Fe(Ⅱ) adducts [Fe₂(N-Et-HPTB){O₂P(OPh)₂}](Cl- O₄)₂ (1) and [Fe₂(N-Et-HPTB) {O₂P(Ph)₂}] (ClO₄)₂ (2) with O₂ have been carried out at low temperature using UV-vis spectra. The decomposition reaction of Fe(Ⅱ)/O₂ adducts was first-order in the experimental conditions, and the activation parameters were obtained. ?H^¹ = 85.62 kJ·mol^-1, ?S¹ = 19.43 J·mol^-1·K^-1 for compound (1) and ?H^¹ = 97.97 kJ·mol^-1, ?S^¹ = 55.68 J·mol^-1·K^-1 for compound (2). These results are similar to those of dioxygen adducts of other metals complexes and natural enzymes such as methane mono- oxygenase (MMOH).     

The contribution of root respiration to soil CO2 efflux in Puccinellia tenuiflora dominated community in a semi-arid meadow steppe

Rising atmospheric CO2 and temperature are altering ecosystem carbon cycling. Grasslands play an important role in regional climate change and global carbon cycle. Below-ground processes play a key role in the grassland carbon cycle because they regulate …     

Studies on reduced extent method for inhibited thermokinetics of enzyme-catalyzed reaction

The thermokinetic reduced extent equations of reversible inhibitions for Michaiels-Menten enzymatic reaction were deduced, and then the criteria for distinguishing inhibition type was given and the methods for calculating kinetic parameters,K _M,K _i andv _m were suggested. This theory was applied to inverstigate the inhibited thermokinetics of laccase-catalyzed oxidation ofo-dihydroxybenzene bym-dihydroxybenzene. The experimental results show the inhibition belongs to reversible competitive type,K _M=6.224×10⁻³ mol·L⁻¹,K _i=2.363×10⁻² mol·L⁻¹. Xiong Ya: born Sep. 1961, Ph. D. graduate student. Curent research interest is in biothermochemistry research Supported by the National Natural Science Foundation of China     

Observation of small-scale processes over shelf break in the East China Sea

The turbulent dissipation along with temperature and salinity was measured on board R/V Dong Fang Hong 2 over the shelf break of the East China Sea from March 7 to 9, 2004. Applying the Turner angle, it is found that the ＇diffusive＇ double diffusion, salt-fingering, and stable stratification coexist in the upper water column of about 50 m. Below that depth, there exists weak salt-fingering. The turbulent dissipation rates are enhanced along the ray paths of M2 internal tides emanating from the shelf break with values ranging from 1.0×10^-9 W·kg^-1 to 1.2×10^-6 W·kg^-1. The corresponding diapycnal mixing rates are from 1×10^-6 m^2· s^-1 to 1×10^-2 m^2· s^-1. The spatially averaged mixing rate over the whole observation section is 2.3×10^-3 m^2· s^-1, which is much larger than 1×10^-5 m^2·s^-1 of the background diapycnal mixing rate in the open ocean.     

Studies on the inclusion complex reaction and fluorescent analytical application of β-cyclodextrin with hymecromone

The inclusion complex reaction condition and the mechanism of β-cyclodextrin with hymecromone have been studied by fluorescent spectrum. The fluorescent intensity and the stability of the system can be qreatly increased in qiven condition, and the formation constant of the inclusion complex reaction has been determined too. The system can be applied to the determination of trace amounts of hymecromone, the maximum fluorescent intensity is obtained with excitation and emission wavelength at 362 nm and 452 nm, respectively. The linear range for hymecromone is 8.0×10⁻⁹ mol·L⁻¹ to 1.0×10⁻⁵ mol·L⁻¹. The detection limit is 1.8×10⁻⁹ mol·L⁻¹. A simple, rapid and highly sensitive fluorimetric method is proposed for the determination of hymecromone. The results obtained are in agreement with those given by an official method. Foundation item: Supported by the National Natural Science Foundation of China (G1999046703) Biography: Luo Zhao-fu(1947-), female, Associate professor.     

Synthesis of meso-tetra-(2-chloro-4-sulfophenyl) prophyrin and spectrophotometric determination of trace amounts of cadmium

Synthesis of a new high sensitive water soluble chromogenic reagent meso-tetra-(2-chloro-4-sulfophenyl) prophyrin and the conditions for the reaction of this reagent with cadmium (I) were studied. The apparent molar absorption coefficient at 434 nm is 5.20×10⁵ L·mol⁻¹·cm⁻¹. The method has been applied to the determination of 5.0×10⁻⁹ (content by weight) Cadmium (I) in honey. Supported by the National Natural Science Foundatyion of China Xiao Ling: born in Oct. 1962, Ph.D gradute student     

Export and remineralization of POM in the Southern Ocean and the South China Sea estimated from 210Po/210Pb disequilibria

Disequilibria between ^210Po and ^210Pb in the upper water and their potential applications as a proxy of particle export and remineralization were examined in the Southern Ocean （station IV3） and the South China Sea （NS44）. ^210po was deficit in surface waters but excessive relative to ^210Pb in subsurface waters. Good positive correlation between ^210Po and particulate organic carbon （POC） indicated deficits and excess of ^210Po resulted from particulate organic matter （POM） export and remJneralization respectively, which was also supported by the decreased δ^13C and increased δ^15N downwards as a result of particle remineralization. On the basis of ^210Po/^210Pb box-model, POC export flux out of the surface waters were 1.2 mmol C. m^-2. d^-1 and 2.3 mmol C. m^-2. d^-1 for station NS44 and IV3, respectively. In the subsurface waters, remineralization fluxes of ^210Po were 0.062 Bq. m^-2.d^-1 and 0.566 Bq.m^-2.d^-1 for station NS44 and IV3 along with the recycle efficiency of 52±26% and 119±52%, respectively. Remineralized fluxes of POM derived from ^210Po and exported POC were 0.6 mmol C.m^-2.d^-1 and 2.7 mmol C. m^-2. d^-1 for NS44 and IV3. This study suggested that ^210Po was a powerful tracer of particle export and remineralization.     

Synthesis and surface activity of biquaternary ammonium salt gemini surfactants with ester bond

The synthesis and surface activity of gemini surfactants with ester bond as spacer are described. Their critical micelle concentrations （CMC） are much lower than that of conventional surfactants, i.e., 1.62×10^-5, 1.38×10^-5, 1.28×10^-5 mol·L^-1 for gemini Ⅰ, Ⅱ and Ⅲ respectively. Surface tension at the CMC of gemini Ⅰ, Ⅱ and Ⅲ were 36.4, 38.5, 41.2 mN · m^-1. The physico-chemical properties such as Krafft points, foaming abilities and emulsifying power were also investigated. It is found that the title compounds have low Krafft points and show good solubility in water. The gemini surfactants synthesized also exhibit good foaming properties and excellent emulsifying power toward toluene. The foaming abilities and emulsifying power increase with the increase in carbon number of hydrophobic chain, and this might be caused by the sheer viscosity of different gemini surfactant solution.     

Investigation of the cross-reaction mechanism of C<Subscript>6</Subscript>H<Subscript>5</Subscript>F-HNO<Subscript>2</Subscript> aqueous solution irradiated at 355 nm by transient absorbance spectrum technique

The transient absorption spectrum technique was employed to investigate the cross-reaction mechanism of C6H5F-HNO2 aqueous solution irradiated at 355 nm. The characteristic and the kinetic parameters of transient species were also detected. Hydroxyl radical derived from the photolysis of HNO2 was added to monofluorobenzene with a second-order rate constant of （5.83±0.17）×10^9 L·mol^-1·s^-1 to form an adduct, C6H5F…OH, which was able to react with HNO2 as the main reaction pathway with a rate constant of （8.3±0.1）×10^7 L·mol^-1·s^-1. The C6F6…OH adduct can also be decayed by elimination of H2O to yield monofluorophenyl radical C6H4F-. By GC-MS technique, the final products were identified to be monofluorophenol, nitro-monofluorobenzene, nitro-monofluorophenol and para-fluorobiphenyl.     

Electrochemical determination of trace amounts of lead (II) and cadmium (II) at a calix[6]arene modified carbon paste electrode

An electrochemical method for the simultaneous determination of lead(II) and Cadmium(II) with a calix[6]arene modified carbon paste electrode (CPE) has been developed. Pb²⁺ and Cd²⁺ were accumulated at the surface of the modified electrode via formation of chemical complexes with calix[6]arene, and reduced at 1.40 V. During the following anodic potential sweep, reduced lead and cadmium were oxidized, and two well-defined striping peaks appeared at about −0.60 V and −0.84 V. Compared with a bare carbon paste electrode, the calix[6]arene modified CPE greatly improves the sensitivity of determining lead and cadmium. The stripping peak currents change linearly with the concentration of Pb²⁺ 3.0×10⁻⁸–8.0×10⁻⁶ mol·L⁻¹ and with that of Cd²⁺ 6.0×10⁻⁸–1.0×10⁻⁵ mol ·L⁻¹. The detection limits of Pb²⁺ and Cd²⁺ are found to be 8.0×10⁻⁹ mol·L⁻¹ and 2.0×10⁻⁸ mol·L⁻¹, respectively. The modified carbon paste electrode was applied to determine trace levels of lead and cadmium in water samples. Comparing with that of atomic absorption spectrometry, the results suggests that the calix[6]arene modified CPE has great potential for the practical sample analysis. Foundation item: Supported by the National Natural Science Foundation of China (60171023) Biography: JI Xiao-bo (1980-), male, Master, research direction: electroanalytical chemistry.     

Third-order optical nonlinearities for lanthanum (III) complexes with 1, 10-phenanthroline components

The nonlinear refractive indexesn ₂ for the ethanol solutions of 1, 10-phenanthroline (2.0 × 10⁻³ mol · L⁻¹), [bis(l, 10-phenanthroline) lanthanum (III)] nitrate (1.0 × 10⁻³ mol · L⁻¹), and [nitrato-fluoracil-bis (1, 10_{-phenanthroline}) lanthanum (III) ] nitrate (1.0 × 10⁻³ mol · L⁻¹) are first measured, the third-order nonlinear optical susceptibilities χ(³) and 〈γ〉 are calculated, and the mechanisms of the third-order optical nonlinearities enhanced by lanthanum (III) are discussed preliminarily.     

Density functional theory study on the insertion reaction mechanism of dibromocarbene with formaldehyde

The insertion reaction mechanism of CBr2 with CH3CH2O has been studied by using the B3LYP/6-311G(d) and CCSD(T)/6-311G(d) at single point. The geometries of reactions,transition state and products were completely optimized. All the transition state is verified by the vibrational analysis and the internal re-action coordinate (IRC) calculations. The results show that reaction (1) is the dominant reaction path,which proceeds via two steps: i) two reactants form an intermediate (IM1),which is an exothermal re-action of 8.62 kJ·mol?1 without energy barrier; ii) P1 is obtained via the TS1 and the H-shift,in which the energy barrier is 44.53 kJ·mol?1. The statistical thermodynamics and Eyring transition state theory with Wigner correction are used to study the thermodynamic and kinetic characters of this reaction in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature ranges from 200 to 1900 K at 1.0 atm,in which the reaction has a bigger spontaneity capability,equi-librium constant (K) and higher rate constant (k).     

Fluorescence Determination of Artemisinin Using Hemoglobin as Catalyst and Pyronine B as Substrate

0 IntroductionMaalnadria siusb atr ompajicosr .he aAltrthe pmrisoibnlienmi (n qtihneghtraoopsiucs,QHS,Fig.1) is a sesquiterpene endoperoxide isola-ted fromArtemisia annuaL., an ancient Chineseherbal medicine usedfor treatment of fever and ma-laria.Studies of the structure and activity relation-ship have shownthat endoperoxide groupis essentialfor anti malarial activity of QHS and absence of thismoiety lead to completely loss in activity of thedrug. Many techniques have been developed to de…