Temperature effects on the removal of potential HFC replacements, CF3CH2CH2OH and CF3(CH2)2CH2OH, initiated by OH radicals

The gas-phase kinetic coefficients of OH radicals with two primary fluorinated alcohols, CF(3)CH(2)CH(2)OH (k(1)) and CF(3)(CH(2))(2)CH(2)OH (k(2)), potential replacements of hydrofluorocarbons (HFCs), are reported here as a function of temperature (T = 263-358 K) for the first time. k(1) and k(2) (together referred as k(i)) were measured under pseudo-first-order conditions with respect to the initial OH concentration using the pulsed laser photolysis/laser induced fluorescence technique. The observed temperature dependence of k(i) (in cm(3) molecule(-1) s(-1)) is described by the following Arrhenius expressions: k(1)(T) = (2.82 ± 1.28) × 10(-12) exp{-(302 ± 139)/T} cm(3) molecule(-1) s(-1) and k(2)(T) = (1.20 ± 0.73) × 10(-11) exp{-(425 ± 188)/T} cm(3) molecule(-1) s(-1).The uncertainties in the Arrhenius parameters are at a 95% confidence level (± 2σ). Uncertainties in k(i)(T) include both statistical and systematic errors. Activation energies were (2.5 ± 1.2) kJ/mol and (3.6 ± 1.6) kJ/mol for the OH-reaction with CF(3)CH(2)CH(2)OH and CF(3)(CH(2))(2)CH(2)OH, respectively. The global lifetime (τ) at 275 K for CF(3)CH(2)CH(2)OH and CF(3)(CH(2))(2)CH(2)OH due to the OH-reaction was estimated to be ca. 2 weeks and 5 days, respectively. The reported Arrhenius parameters can be used in 3D models that take into account the geographical region and season of emissions for estimating a matrix of instantaneous lifetimes. As a consequence of the substitution of the -CH(3) group by a -CH(2)OH group in HFCs, such as CF(3)CH(2)CH(3) and CF(3)(CH(2))(2)CH(3), the tropospheric lifetime with respect to the OH reaction is significantly shorter and, since their radiative forcing is similar, global warming potentials of CF(3)CH(2)CH(2)OH and CF(3)(CH(2))(2)CH(2)OH are negligible. Therefore, CF(3)CH(2)CH(2)OH and CF(3)(CH(2))(2)CH(2)OH seem to be suitable alternatives to HFCs.     

Kinetics and mechanisms of heterogeneous reaction of gaseous hydrogen peroxide on mineral oxide particles

Recent studies have shown that heterogeneous reactions of hydrogen peroxide (H(2)O(2)) on aerosol surfaces may play an important role in tropospheric chemistry. The data concerning the kinetics and mechanisms of these reactions, however, are quite scarce so far. Here, we investigated, for the first time, the heterogeneous reactions of gaseous H(2)O(2) on SiO(2) and α-Al(2)O(3) particles, two major components of mineral dust aerosol, using transmission-Fourier Transform Infrared (T-FTIR) spectroscopy, and high-performance liquid chromatography (HPLC). It is found that H(2)O(2) molecularly adsorbs on SiO(2), and a small amount of molecularly adsorbed H(2)O(2) decomposes due to its thermal instability. For α-Al(2)O(3), catalytic decomposition of H(2)O(2) evidently occurs, but there is also a small amount of H(2)O(2) molecularly adsorbed on the particle surface. The BET uptake coefficients of H(2)O(2) on both particles appear to be independent of gaseous H(2)O(2) concentration (1.27-13.8 ppmv) and particle sample mass (2.8-6.5 mg for SiO(2) and 8.6-18.9 mg for α-Al(2)O(3)), but are strongly dependent on relative humidity with the values ranging from (1.55 ± 0.14) × 10(-8) and (1.21 ± 0.04) × 10(-7) at 2% RH to (0.61 ± 0.06) × 10(-8) and (0.76 ± 0.09) × 10(-7) at 76% RH for SiO(2) and α-Al(2)O(3), respectively. On the basis of the experimental results and literature data, the potential mechanisms for heterogeneous decomposition of H(2)O(2) were proposed, and the atmospheric implications of these reactions were discussed. It is found that heterogeneous reaction of H(2)O(2) on both mineral oxides plays a significant role in processing mineral aerosols, although its role as a sink for ambient H(2)O(2) is probably limited.     

Influence of high hydrostatic pressure on the proteolysis of beta-lactoglobulin A by trypsin

This work describes the effect of the hydrolysis time and pressure (0.1-400 MPa) on the proteolysis of beta-lactoglobulin A (beta-lg A) with trypsin, either conducting hydrolysis of beta-lg under pressure or hydrolysing beta-lg that was previously pressure treated. Pressurisation, before or during enzyme treatments, enhanced tryptic hydrolysis of beta-lg. Trypsin degraded pressure-modified beta-lg and pressure-induced beta-lg aggregates, favouring proteolysis to the intermediate degradation products: (Val(15)-Arg(40)), (Val(41)-Lys(69))S-S(Leu(149)-Ile(162)) and (Val(41)-Lys(70))S-S(Leu(149)-Ile(162)). These were further cleaved at the later stages of proteolysis to yield: (Val(15)-Tyr(20)), (Ser(21)-Arg(40)), (Val(41)-Tyr(60)), (Trp(61)-Lys(69))S-S(Leu(149)-Ile(162)) and (Trp(61)-Lys(70))S-S(Leu(149)-Ile(162)). Particularly, in the tryptic hydrolysates of pre-pressurized beta-lg, two other fragments linked by disulphide bonds: (Lys(101)-Arg(124))S-S(Leu(149)-Ile(162)) and (Tyr(102)-Arg(124))S-S(Leu(149)-Ile(162)), were found. These corresponded to rearrangement products induced by SH/SS exchange between the free thiol group of Cys(121) and Cys(160), that normally forms the disulphide bond Cys(66)-Cys(160). In the light of these results, structural modifications of beta-lg under high pressure are discussed.     

Chemical reduction of U(VI) by Fe(II) at the solid-water interface using natural and synthetic Fe(III) oxides

Abiotic reduction of 0.1 mM U(VI) by Fe(II) in the presence of synthetic iron oxides (biogenic magnetite, goethite, and hematite) and natural Fe(III) oxide-containing solids was investigated in pH 6.8 artificial groundwater containing 10 mM NaHCO3. In most experiments, more than 95% of added U(VI) was sorbed to solids. U(VI) was rapidly and extensively (> or = 80%) reduced in the presence of synthetic Fe(III) oxides and highly Fe(II) oxide-enriched (18-35 wt % Fe) Atlantic coastal plain sediments. In contrast, long-term (20-60 d) U(VI) reduction was less than 30% in suspensions of six other natural solids with relatively low Fe(III) oxide content (1-5 wt % Fe). Fe(II) sorption site density was severalfold lower on these natural solids (0.2-1.1 Fe(II) nm(-2)) compared tothe synthetic Fe(lII) oxides (1.6-3.2 Fe(II) nm(-2)), which may explain the poor U(VI) reduction in the natural solid-containing systems. Addition of the reduced form of the electron shuttling compound anthrahydroquinone-2,6-disulfonate (AH2DS; final concentration 2.5 mM) to the natural solid suspensions enhanced the rate and extent of U(VI) reduction, suggesting that AH2DS reduced U(VI) at surface sites where reaction of U(VI) with sorbed Fe(II) was limited. This study demonstrates that abiotic, Fe(II)-driven U(VI) reduction is likely to be less efficient in natural soils and sediments than would be inferred from studies with synthetic Fe(III) oxides.     

Biodegradation of RDX and MNX with Rhodococcus sp. strain DN22: new insights into the degradation pathway

Previously we demonstrated that Rhodococcus sp. strain DN22 can degrade RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) aerobically via initial denitration. The present study describes the role of oxygen and water in the key denitration step leading to RDX decomposition using (18)O(2) and H(2)(18)O labeling experiments. We also investigated degradation of MNX (hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine) with DN22 under similar conditions. DN22 degraded RDX and MNX giving NO(2)(-), NO(3)(-), NDAB (4-nitro-diazabutanal), NH(3), N(2)O, and HCHO with NO(2)(-)/NO(3)(-) molar ratio reaching 17 and ca. 2, respectively. In the presence of (18)O(2), DN22 degraded RDX and produced NO(2)(-) with m/z at 46 Da that subsequently oxidized to NO(3)(-) containing one (18)O atom, but in the presence of H(2)(18)O we detected NO(3)(-) without (18)O. A control containing NO(2)(-), DN22, and (18)O(2) gave NO(3)(-) with one (18)O, confirming biotic oxidation of NO(2)(-) to NO(3)(-). Treatment of MNX with DN22 and (18)O(2) produced NO(3)(-) with two mass ions, one (66 Da) incorporating two (18)O atoms and another (64 Da) incorporating only one (18)O atom and we attributed their formation to bio-oxidation of the initially formed NO and NO(2)(-), respectively. In the presence of H(2)(18)O we detected NO(2)(-) with two different masses, one representing NO(2)(-) (46 Da) and another representing NO(2)(-) (48 Da) with the inclusion of one (18)O atom suggesting auto-oxidation of NO to NO(2)(-). Results indicated that denitration of either RDX or MNX and denitrosation of MNX by DN22 did not involve direct participation of either oxygen or water, but both played major roles in subsequent secondary chemical and biochemical reactions of NO and NO(2)(-).     

Macroscopic studies of the effects of selenate and selenite on cobalt sorption to gamma-Al2O3

Metal ion sorption can be significantly impacted by the presence of other solutes or complexing species. In this research, macroscopic sorption studies were conducted to evaluate the effect of strongly sorbing Se(IV) and weakly sorbing Se(VI) oxyanions on cobalt(II) sorption to gamma-Al2O3. Se(IV) was found to significantly alter Co(ll) sorption as a function of Co(II) surface coverage, while Se(VI) was found to have no effect on Co(II) sorption. Under low Co(II) surface loadings (<0.1 micromol/m2), Se(IV) increased Co(II) sorption as a function of the Se(IV) coverage. At low Se(IV) surface coverages, no change in Co(II) sorption was detectable, while at high Se(IV) loadings Co(II) sorption was significantly increased. The increase in Co(ll) sorption in the bisorbate systems can be explained by either an electrostatic enhancement mechanism or byternary complex formation. Se(IV) decreased Co(II) sorption at high Co(ll) surface loadings (>0.5 micromol/m2) where coprecipitation of Co(II) and A(III) in the form of layered double hydroxides (LDH) is expected to be the dominant sorption mechanism for the single-sorbate case. The extent of the Co(ll) sorption reduction in Co(III)/Se(IV) bisorbate systems compared to the corresponding single-sorbate systems increased with increasing Co(II) surface coverage. The rate of Co(II) desorption was reduced in the presence of Se(IV) compared to the single-sorbate case, indicating a direct interaction between Co(II) and Se(IV). A reaction between Co(II) and Se(IV) is further supported by an increase in Se(IV) sorption in the same bisorbate samples where Co(II) sorption is decreased. Thus, the macroscopic data indicates Se(IV) may be altering the mechanism of Co(II) sorption, potentially forming a ternary surface complex or different surface precipitate.     

Carbon isotopic fractionation of CFCs during abiotic and biotic degradation

Carbon stable isotope ((13)C) fractionation in chlorofluorocarbon (CFC) compounds arising from abiotic (chemical) degradation using zero-valent iron (ZVI) and biotic (landfill gas attenuation) processes is investigated. Batch tests (at 25 °C) for CFC-113 and CFC-11 using ZVI show quantitative degradation of CFC-113 to HCFC-123a and CFC-1113 following pseudo-first-order kinetics corresponding to a half-life (τ(1/2)) of 20.5 h, and a ZVI surface-area normalized rate constant (k(SA)) of -(9.8 ± 0.5) × 10(-5) L m(-2) h(-1). CFC-11 degraded to trace HCFC-21 and HCFC-31 following pseudo-first-order kinetics corresponding to τ(1/2) = 17.3 h and k(SA) = -(1.2 ± 0.5) × 10(-4) L m(-2) h(-1). Significant kinetic isotope effects of ε(‰) = -5.0 ± 0.3 (CFC-113) and -17.8 ± 4.8 (CFC-11) were observed. Compound-specific carbon isotope analyses also have been used here to characterize source signatures of CFC gases (HCFC-22, CFC-12, HFC-134a, HCFC-142b, CFC-114, CFC-11, CFC-113) for urban (UAA), rural/remote (RAA), and landfill (LAA) ambient air samples, as well as in situ surface flux chamber (FLUX; NO FLUX) and landfill gas (LFG) samples at the Dargan Road site, Northern Ireland. The latter values reflect biotic degradation and isotopic fractionation in LFG production, and local atmospheric impact of landfill emissions through the cover. Isotopic fractionations of Δ(13)C ～ -13‰ (HCFC-22), Δ(13)C ～ -35‰ (CFC-12) and Δ(13)C ～ -15‰ (CFC-11) were observed for LFG in comparison to characteristic solvent source signatures, with the magnitude of the isotopic effect for CFC-11 apparently similar to the kinetic isotope effect for (abiotic) ZVI degradation.     

Binding of mercury(II) to aquatic humic substances: influence of pH and source of humic substances

Conditional distribution coefficients (K(DOM')) for Hg(II) binding to seven dissolved organic matter (DOM) isolates were measured at environmentally relevant ratios of Hg(II) to DOM. The results show that K(DOM') values for different types of samples (humic acids, fulvic acids, hydrophobic acids) isolated from diverse aquatic environments were all within 1 order of magnitude (10(22.5 +/-1.0)-10(23.5 +/- 1.0)) L kg(-1)), suggesting similar Hg(ll) binding environments, presumably involving thiol groups, for the different isolates. K(DOM') values decreased at low pHs (4) compared to values at pH 7, indicating proton competition for the strong Hg(II) binding sites. Chemical modeling of Hg(II)-DOM binding at different pH values was consistent with bidentate binding of Hg(II) by one thiol group (pK(a) = 10.3) and one other group (pK(a) = 6.3) in the DOM, which is in agreement with recent results on the structure of Hg(II)-DOM bonds obtained by extended X-ray absorption fine structure spectroscopy (EXAFS).     

第一过渡金属对槲皮素的化学改性及抗氧化活性

通过对槲皮素的化学改性,合成了槲皮素的第一过渡系生命元素的配合物,并对槲皮素配合物的溶解性、总抗氧化能力、清除O2·自由基和DPPH·自由基的活性进行了比较研究.研究结果表明,槲皮素配合物的在水中的溶解性优于槲皮素;槲皮素配合物的总抗氧化能力强弱为:槲皮素＜槲皮素铁(Ⅱ)＜槲皮素铬(Ⅱ)＜槲皮素镍(Ⅱ)＜槲皮素钴(Ⅱ)＜槲皮素锰(Ⅱ)＜槲皮素铜(Ⅱ)＜槲皮素锌(Ⅱ);清除O2自由基的能力为:槲皮素＜槲皮素铁(Ⅱ)＜槲皮素铬(Ⅱ)＜槲皮素镍(Ⅱ)＜槲皮素锰(Ⅱ)＜槲皮素铜(Ⅱ)＜槲皮素钴(Ⅱ)＜槲皮素锌(Ⅱ);清除DPPH·自由基的能力为:槲皮素＜槲皮素铁(Ⅱ)＜槲皮素镍(Ⅱ)＜槲皮素铬(Ⅱ)＜槲皮素铜(Ⅱ)＜槲皮素钴(Ⅱ)＜槲皮素锰(Ⅱ)＜槲皮素锌(Ⅱ).槲皮素经化学改性的产物比槲皮素有更好的生物活性.     

同时蒸馏萃取/GC-MS分析干黄酱的挥发性成分

通过同时蒸馏萃取的方法提取干黄酱的挥发性成分,经过气质联机分析,共分析出73种物质,鉴定出3-甲基丁醛(13·36%)、亚油酸乙酯(10·49%)、2-甲基丁醛(7·00%)、(反,反)-9,12-十八碳二烯酸(6·97%)、油酸乙酯(5·97%)、十六酸(5·05%)、苯乙醛(4·28%)、糠醛(3·51%)、1-(1H-吡咯基-2-)-乙酮(3·01%)、糠醇(1·96%)、3-甲基-1-丁醇(1·32%)、5-羟甲基糠醛(0·97%)、3-甲硫基丙醛(0·84%)、2-甲氧基-4-乙烯基苯酚(0·82%)、2,5-二甲基-4-羟基-3(2H)-呋喃酮(0·27%)、3,4-二甲氧基苯酚(0·26%)等33种物质,总相对百分含量为76·84%。经过调配实验,确认了对干黄酱特征香气起主要作用的香料。     

The effects of modified atmosphere gas composition on microbiological criteria, color and oxidation values of minced beef meat

This paper reports the effects of modified atmosphere gas compositions with different concentrations of CO(2)/O(2)/N(2) on color properties (L*, a* and b* values), oxidation stability (TBARS value) and microbiological properties of minced beef meat stored at +4 °C. Sampling was carried out on the 1st, 3rd, 5th, 7th, 9th, 11th and 14th day of storage. The gas mixtures used were as follows: (i) %30O(2) + %70CO(2) (MAP1), (ii) %50O(2) + %50CO(2) (MAP2), (iii) %70O(2) + %30CO(2) (MAP3), (iv) %50O(2) + %30CO(2) + %20N(2) (MAP4), and (v) %30O(2) + %30CO(2) + %40N(2) (MAP5). Control samples (AP) were packaged under atmospheric air. Pseudomonas, lactic acid bacteria, Brochothrix thermosphacta, and Enterobacteriaceae members were monitored. Among these five modified atmosphere gas compositions, the best preservation for minced beef meat was in MAP4 gas combination maintaining acceptable color together with oxidation stability and acceptable microbial loads until the end of storage period of fourteen days.     

Kinetics and mechanistic aspects of As(III) oxidation by aqueous chlorine, chloramines, and ozone: relevance to drinking water treatment

Kinetics and mechanisms of As(III) oxidation by free available chlorine (FAC-the sum of HOCl and OCl-), ozone (O3), and monochloramine (NH2Cl) were investigated in buffered reagent solutions. Each reaction was found to be first order in oxidant and in As(III), with 1:1 stoichiometry. FAC-As(III) and O3-As(III) reactions were extremely fast, with pH-dependent, apparent second-order rate constants, k'app, of 2.6 (+/- 0.1) x 10(5) M(-1) s(-1) and 1.5 (+/- 0.1) x 10(6) M(-1) s(-1) at pH 7, whereas the NH2Cl-As(III) reaction was relatively slow (k'app = 4.3 (+/- 1.7) x 10(-1) M(-1) s(-1) at pH 7). Experiments conducted in real water samples spiked with 50 microg/L As(III) (6.7 x 10(-7) M) showed that a 0.1 mg/L Cl2 (1.4 x 10-6 M) dose as FAC was sufficient to achieve depletion of As(III) to <1 microg/L As(III) within 10 s of oxidant addition to waters containing negligible NH3 concentrations and DOC concentrations <2 mg-C/L. Even in a water containing 1 mg-N/L (7.1 x 10(-5) M) as NH3, >75% As(III) oxidation could be achieved within 10 s of dosing 1-2 mg/L Cl2 (1.4-2.8 x 10(-5) M) as FAC. As(III) residuals remaining in NH3-containing waters 10 s after dosing FAC were slowly oxidized (t1/2 > or = 4 h) in the presence of NH2Cl formed by the FAC-NH3 reaction. Ozonation was sufficient to yield >99% depletion of 50 microg/L As(III) within 10 s of dosing 0.25 mg/L O3 (5.2 x 10(-6) M) to real waters containing <2 mg-C/L of DOC, while 0.8 mg/L O3 (1.7 x 10(-5) M) was sufficientfor a water containing 5.4 mg-C/L of DOC. NH3 had negligible effect on the efficiency of As(III) oxidation by O3, due to the slow kinetics of the O3-NH3 reaction at circumneutral pH. Time-resolved measurements of As(III) loss during chlorination and ozonation of real waters were accurately modeled using the rate constants determined in this investigation.     

Comparison of acidic and alkaline catalysts for preparation of fatty acid methyl esters from ovine muscle with emphasis on conjugated linoleic acid

Methanolic reagents containing acidic catalysts, HCl (0.5 M, 1 h, 80° C) or BF(3) (14%, 1 h, 80° C), or alkaline catalysts, KOH (0.2 M, 15-60 min, 50° C) or NaOCH(3) (0.5 M, 15-60 min, 50° C), were compared for use in preparation of fatty acid methyl esters for GC analysis of total lipids from freeze-dried semitendinosus muscle of lambs fed a 3.6% linoleate diet. Lipid preparations were in duplicate and included a total lipid extract, as well as direct transesterification and direct saponification of freeze-dried muscle. For the total lipid extracts, the weight% of 18:2 cis-9, trans-11 (CLA) with BF(3) (1.15) was 14.0% lower (P=0.001) than with either KOH (1.32) or NaOCH(3) (1.36); however, with HCl (1.25) CLA was intermediate (P=0.02). Concentrations of CLA (mg/g tissue) were similar (P ?0.44) within acidic or alkaline catalysts, but were 18.1% higher (P ?0.01) with KOH (2.56) and NaOCH(3) (2.52) than with HCl (2.01) or BF(3) (2.12). For direct transesterification, weight% of CLA was similar (P=0.55) with KOH (1.34) and NaOCH(3) (1.33), but each was 11.9% greater (P=0.003) than with HCl (1.18) and 19.1% greater (P=0.005) than with BF(3) (1.08). Concentrations of CLA after direct transesterification were greatest (P ?0.04) with KOH (3.31), followed by HCl (2.89, P=0.04), BF(3) (2.42, P ?0.004), and lowest (P ?0.002) with NaOCH(3) (2.21), indicating differences in efficiency of direct transesterification. Weight% of CLA in semitendinosus muscle, ranked highest to lowest, was lambs fed 3.6% linoleate (P ?0.003) > lambs fed 3.8% oleate (P ?0.01) > lambs fed a non-fat supplemented control diet (P ?0.01) when either BF(3) (saponified lipids) or KOH (direct transesterification) was used. Thus, dietary treatment effects on muscle CLA were not affected by catalyst. For the muscle of high-linoleate, high-oleate, and control lambs, CLA was 20.2, 13.9 and 0.0% higher, respectively, with KOH than BF(3), indicating that degradation of CLA by acidic catalysts decreased with lower starting amounts of CLA.     

Spectroscopic investigation of Cr(III)- and Cr(VI)-treated nanoscale zerovalent iron

The reaction of hexavalent chromium (Cr(VI)) with zerovalent iron (Fe0) during soil and groundwater remediation is an important environmental process. This study used several techniques including X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy to investigate nanometer scale Fe0 particles (nano Fe0) treated with Cr(III) and Cr(VI). X-ray diffraction and XPS analyses of oxidized nano Fe0 showed the crystalline Fe(III) phase is composed of lepidocrocite (gamma-FeOOH). Results of XPS Cr 2p data and Cr K-edge X-ray absorption near edge spectroscopy (XANES) provided evidence that Cr(VI) was entirely reduced to Cr(III) by nano Fe0 with no residual Cr(VI) after reaction. In addition, XPS and XANES results of Cr(III) precipitated as Cr(OH)3 in the presence of corroding nano Fe0 were nearly identical to the Cr(VI)-nano Fe0 reaction product. Detailed analysis of XPS O 1s line spectra revealed that both Cr(III)- and Cr(VI)-treated nano Fe0 yielded a predominantly hydroxylated Cr(OH)3 and/ or a mixed phase CrxFe(1 - x)(OH)3 product. The structure of the Cr(III)- and Cr(VI)-treated nano Fe0 determined using extended X-ray absorption fine structure spectroscopy (EXAFS) revealed octahedral Cr(III) with Cr-O interatomic distances between 1.97 and 1.98 A for both Cr(III) and Cr(VI) treatments and a pronounced Cr-Cr second interatomic shell at 3.01 A. Our results suggest that the reaction product of Cr(VI)-treated nano Fe0 is either a poorly ordered Cr(OH)3 precipitate or possibly a mixed phase CrxFe(1 - x)(OH)3 product, both of which are highly insoluble under environmental conditions.     

Density functional theory study on aqueous aluminum-fluoride complexes: exploration of the intrinsic relationship between water-exchange rate constants and structural parameters for monomer aluminum complexes

Density functional theory (DFT) calculation is carried out to investigate the structures, (19)F and (27)Al NMR chemical shifts of aqueous Al-F complexes and their water-exchange reactions. The following investigations are performed in this paper: (1) the microscopic properties of typical aqueous Al-F complexes are obtained at the level of B3LYP/6-311+G**. Al-OH(2) bond lengths increase with F(-) replacing inner-sphere H(2)O progressively, indicating labilizing effect of F(-) ligand. The Al-OH(2) distance trans to fluoride is longer than other Al-OH(2) distance, accounting for trans effect of F(-) ligand. (19)F and (27)Al NMR chemical shifts are calculated using GIAO method at the HF/6-311+G** level relative to F(H(2)O)(6)(-) and Al(H(2)O)(6)(3+) references, respectively. The results are consistent with available experimental values; (2) the dissociative (D) activated mechanism is observed by modeling water-exchange reaction for [Al(H(2)O)(6-i)F(i)]((3-i)+) (i = 1-4). The activation energy barriers are found to decrease with increasing F(-) substitution, which is in line with experimental rate constants (k(ex)). The log k(ex) of AlF(3)(H(2)O)(3)(0) and AlF(4)(H(2)O)(2)(-) are predicted by three ways. The results indicate that the correlation between log k(ex) and Al-O bond length as well as the given transmission coefficient allows experimental rate constants to be predicted, whereas the correlation between log k(ex) and activation free energy is poor; (3) the environmental significance of this work is elucidated by the extension toward three fields, that is, polyaluminum system, monomer Al-organic system and other metal ions system with high charge-to-radius ratio.     

Antioxidative and anti-inflammatory protection of oleanolic acid and ursolic acid in PC12 cells

PC12 cells were used to examine the in vitro antioxidative and anti-inflammatory effects of oleanolic acid (OA) and ursolic acid (UA). PC12 cells were pretreated with OA or UA at 20 and 40 microM and followed by exposure of hydrogen peroxide (H(2)O(2)) or 1-methyl-4-phenylpyridinium ion (MPP(+)) to induce cell injury. Results showed that H(2)O(2)- or MPP(+)-treatment significantly decreased cell viability and increased lactate dehydrogenase (LDH) release (P < 0.05). The pretreatment from OA or UA significantly and concentration-dependently reduced subsequent H(2)O(2)- or MPP(+)-induced cell death and LDH release (P < 0.05). Either H(2)O(2)- or MPP(+)-treatment significantly increased malonyldialdehyde (MDA) formation, decreased glutathione (GSH) content, and diminished glutathione peroxidase (GPX), catalase, and superoxide dismutase (SOD) activities (P < 0.05). The pretreatment from OA or UA significantly retained GSH, and reversed H(2)O(2)- and MPP(+)-induced impairment in catalase and SOD activities (P < 0.05), and decreased MDA formation (P < 0.05). Either H(2)O(2)- or MPP(+)-treatment significantly elevated interleukin-6 (IL-6) and tumor necrosis factor (TNF)-alpha levels (P < 0.05). The pretreatments from OA or UA significantly attenuated subsequent H(2)O(2)- or MPP(+)-induced release of IL-6 and TNF-alpha (P < 0.05). Based on the observed antioxidative and anti-inflammatory activities from OA and UA, these 2 compounds were potent agents against neurodegenerative disorder.     

Thermal inactivation of avian influenza virus and Newcastle disease virus in a fat-free egg product

High-pathogenicity avian influenza (HPAI) virus, low-pathogenicity avian influenza (LPAI) virus, virulent Newcastle disease virus (vNDV) and low-virulent Newcastle disease virus (lNDV) can be present on the eggshell surface, and HPAI viruses and vNDV can be present in the internal contents of chicken eggs laid by infected hens. With the increase in global trade, egg products could present potential biosecurity problems and affect international trade in liquid and dried egg products. Therefore, the generation of survival curves to determine decimal reduction times (D(T)-values) and change in heat resistance of the viruses (z(D)-value) within fat-free egg product could provide valuable information for development of risk reduction strategies. Thermal inactivation studies using A/chicken/Pennsylvania/1370/83 (H5N2) HPAI virus resulted in D(55)-, D(56)-, D(56.7)-, D(57)-, D(58)-, and D(59)-values of 18.6, 8.5, 3.6, 2.5, 0.4, and 0.4 min, respectively. The z(D)-value was 4.4 °C. LPAI virus A/chicken/New York/13142/94 (H7N2) had D(55)-, D(56.7)-, D(57)-, D(58)-, D(59)-, and D(60)-values of 2.9, 1.4, 0.8, 0.7, 0.7, and 0.5 min, respectively, and a z-value of 0.4 °C. vNDV avian paramyxoviruses of serotype 1 (AMPV-1)/chicken/California/212676/2002 had D(55)-, D(56)-, D(56.7)-, D(57)-, D(58)-, and D(59)-values of 12.4, 9.3, 6.2, 5, 3.7, and 1.7 min, respectively. The z(D)-value was 4.7 °C. lNDV AMPV-1/chicken/United States/B1/1948 had D(55)-, D(57)-, D(58)-, D(59)-, D(61)-, and D(63)-values of 5.3, 2.2, 1.1, 0.55, 0.19, and 0.17 min, respectively, and a z(D)-value of 1.0 °C. Use of these data in developing egg pasteurization standards for AI and NDV-infected countries should allow safer trade in liquid egg products.     

Enhancement of activity and sulfur resistance of CeO2 supported on TiO2-SiO2 for the selective catalytic reduction of NO by NH3

A series of novel metal-oxide-supported CeO(2) catalysts were prepared via the wet impregnation method, and their NH(3)-SCR activities were investigated. The Ce/TiO(2)-SiO(2) catalyst with a Ti/Si mass ratio of 3/1 exhibited superior NH(3)-SCR activity and high N(2) selectivity in the temperature range of 250-450 °C. The characterization results revealed that the activity enhancement was correlated with the properties of the support material. Cerium was highly dispersed on the TiO(2)-SiO(2) binary metal oxide support, and the interaction of Ti and Si resulted in greater conversion of Ce(4+) to Ce(3+) on the surface of the catalyst compared to that on the single metal oxide supports. As a result of in the increased number of acid sites on Ce/TiO(2)-SiO(2) that resulted from the addition of SiO(2), the NH(3) adsorption capacity was significantly improved. All of these factors played significant roles in the high SCR activity. More importantly, Ce/TiO(2)-SiO(2) exhibited strong resistance to SO(2) and H(2)O poisoning. After the addition of SiO(2), the number of Lewis-acid sites was not decreased, but the number of Br?nsted-acid sites on the TiO(2)-SiO(2) carrier was increased. The introduction of SiO(2) further weakened the alkalinity over the surface of the Ce/TiO(2)-SiO(2) catalyst, which resulted in sulfate not easily accumulating on the surface of the Ce/TiO(2)-SiO(2) catalyst in comparison with Ce/TiO(2).     

Role for Fe(III) minerals in nitrate-dependent microbial U(IV) oxidation

Microbiological reduction of soluble U(VI) to insoluble U(IV) is a means of preventing the migration of that element in groundwater, but the presence of nitrate in U(IV)-containing sediments leads to U(IV) oxidation and remobilizaton. Nitrite or iron(III) oxyhydroxides may oxidize U(IV) under nitrate-reducing conditions, and we determined the rate and extent of U(IV) oxidation by these compounds. Fe(III) oxidized U(IV) at a greater rate than nitrite (130 and 10 microM U(IV)/day, respectively). In aquifer sediments, Fe(III) may be produced during microbial nitrate reduction by oxidation of Fe(II) with nitrite, or by enzymatic Fe(II) oxidation coupled to nitrate reduction. To determine which of these mechanisms was dominant, we isolated a nitrate-dependent acetate- and Fe(ll)-oxidizing bacterium from a U(VI)- and nitrate-contaminated aquifer. This organism oxidized U(IV) at a greater rate and to a greater extent under acetate-oxidizing (where nitrite accumulated to 50 mM)than under Fe(II)-oxidizing conditions. We showthatthe observed differences in rate and extent of U(IV) oxidation are due to mineralogical differences between Fe(III) produced by reaction of Fe(II) with nitrite (amorphous) and Fe(III) produced enzymatically (goethite or lepidocrocite). Our results suggest the mineralogy and surface area of Fe(III) minerals produced under nitrate-reducing conditions affect the rate and extent of U(IV) oxidation. These results may be useful for predicting the stability of U(IV) in aquifers.     

Atmospheric HFEs degradation in the gas phase: reactions of HFE-7100 and HFE-7200 with Cl atoms at low temperatures

Kinetic rate coefficients for the reactions of HFE-7100 (1) (C4F9OCH3) and HFE-7200 (2) (C4F9OC2H5) with Cl atoms have been measured using a discharge flow mass spectrometric technique (DFMS) at 1 Torr total pressure. The reactions have been studied under pseudo-first-order kinetic conditions in excess of HFEs over Cl atoms and the study has been extended from 333 down to 234 K to approach the tropospheric temperature profile. At room temperature the measured rate constants are k (1) = (1.43 +/- 0.28) x 10(-13) cm3molecule(-1)s(-1) and k (2) = (2.1 +/- 0.1) x 10(-12) cm3molecule(-1)s(-1). The Arrhenius expressions from our results are (units in cm3molecule(-1)s(-1)): k (1) = (2.3 +/- 1.4) x 10(-10) exp - (2254 +/- 177)/T(234-315 K) and k (2) = (3.7 +/- 0.5) x 10(-11) exp - (852 +/- 38)/T(234-333 K) (errors are sigma). The reactions proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.88 +/- 0.09 and 0.95 +/- 0.10 (errors are 2sigma) were obtained for HFE-7100 and HFE-7200 reactions, respectively.