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.     

Atmospheric chemistry of N-methyl perfluorobutane sulfonamidoethanol, C4F9SO2N(CH3)CH2CH2OH: kinetics and mechanism of reaction with OH

Relative rate methods were used to measure the gas-phase reaction of N-methyl perfluorobutane sulfonamidoethanol (NMeFBSE) with OH radicals, giving k(OH + NMeFBSE) = (5.8 +/- 0.8) x 10(-12) cm3 molecule(-1) s(-1) in 750 Torr of air diluent at 296 K. The atmospheric lifetime of NMeFBSE is determined by reaction with OH radicals and is approximately 2 days. Degradation products were identified by in situ FTIR spectroscopy and offline GC-MS and LC-MS/MS analysis. The primary carbonyl product C4F9SO2N(CH3)CH2CHO, N-methyl perfluorobutane sulfonamide (C4F9SO2NH(CH3)), perfluorobutanoic acid (C3F7C(O)OH), perfluoropropanoic acid (C2F5C(O)OH), trifluoroacetic acid (CF3C(O)OH), carbonyl fluoride (COF2), and perfluorobutane sulfonic acid (C4F9SO3H) were identified as products. A mechanism involving the addition of OH to the sulfone double bond was proposed to explain the production of perfluorobutane sulfonic acid and perfluorinated carboxylic acids in yields of 1 and 10%, respectively. The gas-phase N-dealkylation product, N-methyl perfluorobutane sulfonamide (NMeFBSA), has an atmospheric lifetime (>20 days) which is much longer than that of the parent compound, NMeFBSE. Accordingly,the production of NMeFBSA exposes a mechanism by which NMeFBSE may contribute to the burden of perfluorinated contamination in remote locations despite its relatively short atmospheric lifetime. Using the atmospheric fate of NMeFBSE as a guide, it appears that anthropogenic production of N-methyl perfluorooctane sulfonamidoethanol (NMeFOSE) contributes to the ubiquity of perfluoroalkyl sulfonate and carboxylate compounds in the environment.     

First direct detection of HONO in the reaction of methylnitrite (CH3ONO) with OH radicals

We report on the development of a new environmental simulation chamber coupled with an in situ continuous wave cavity ring-down spectrometer operating in the near IR (～1.5 μm). The first application reported in this paper dealt with the chemical mechanism of UV photolysis of methyl nitrite (CH(3)ONO) in air. HONO has been detected for the first time and shown to be formed in the OH + CH(3)ONO reaction. A dense spectrum of cis-HONO absorption lines has been observed near 1.5 μm, in agreement with a previous study (Guilmot et al.). CH(2)O has been measured as primary product with good sensitivity and time resolution. In contrast to Zhao et al., we did not detect any NO(2) absorption features in this wavelength range. Calibration experiments provided very low NO(2) absorption cross sections in this region (～10(-25) cm(2)), leading to conclude that NO(2) cannot be observed in this wavelength range in the presence of equal amounts of CH(2)O.     

ZnSn（OH）6/Zn2SnO4复合粉体的制备及其光催化性能的研究

以Zn(NO3)2·6H2O和SnCl·5H42O为原料,NaOH为沉淀剂,采用水热法制备了ZnSn(OH)6/Zn2SnO4复合材料,样品的组成和带隙能分别采用X射线粉末衍射(XRD)和紫外-可见漫反射能谱(DRS)进行了表征;探讨了水热反应温度和p H对产物成分的影响,得出ZnSn(OH)6/Zn2SnO4复合材料的最佳制备条件:水热反应温度180℃,p H=10;并以亚甲基蓝为降解对象,研究了ZnSn(OH)6/Zn2SnO4复合材料的光催化性能,结果表明,在15 W紫外灯(λ=365 nm)下照射150 min后,亚甲基蓝的降解脱色率可达99.2%.     

Atmospheric chemistry of HFE-7500 [n-C3F7CF(OC2H5)CF(CF3)2]: reaction with OH radicals and Cl atoms and atmospheric fate of n-C3F7CF(OCHO*)CF(CF3)2 and n-C3F7CF(OCH2CH2O*)CF(CF3)2 radicals

Relative rate techniques were used to measure k(OH + HFE-7500) = (2.6+/-0.6) x 10(-14), k(Cl + HFE-7500) = (2.3+/-0.7) x 10(-12), k[Cl + n-C3F7CF(OC(O)H)CF(CF3)2] = (9.7+/-1.4) x 10(-15), and k[Cl + n-C3F7CF(OC(O)CH3)CF(CF3)2] < 6 x 10(-17) cm3 molecule(-1) s(-1) at 295 K [HFE-7500 = n-C3F7-CF(OC2H5)CF(CF3)2]. From the value of k(OH + HFE-7500) an estimate of 2.2 years for the atmospheric lifetime of HFE-7500 is obtained. Two competing loss mechanisms for n-C3F7-CF(OCHO.CH3)CF(CF3)2 radicals were identified in 700 Torr of N2/O2 diluent at 295 K; reaction with O2 and decomposition via C-C bond scission with kO2/k(decomp) = 0.013+/-0.006 Torr(-1). The Cl atom initiated oxidation of HFE-7500 in N2/O2 diluent gives n-C3F7CF(OC(O)CH3)CF(CF3)2 as the major product and n-C3F7CF(OC(O)H)CF(CF3)2 as a minor product. The atmospheric oxidation of HFE-7500 gives n-C3F7-CF(OC(O)CH3)CF(CF3)2 and n-C3F7CF(OC(O)H)CF(CF3)2 as oxidation products. The results are discussed with respect to the atmospheric chemistry and environmental impact of HFE-7500.     

快速测定磷酸(氢)钙中磷含量

通过加入硝酸镧作沉淀释放剂,使H2PO4-中的H+游离出来。用标准氢氧化钠溶液直接滴定游离出来的H+（pH调节和滴定过程都由自动电位滴定仪来完成）,根据所消耗的氢氧化钠溶液体积,求出样品中磷的含量。本方法操作简单、快速、重现性好,省略硅钼柠酮沉淀标准方法中许多繁琐的步骤,而测定结果与标准方法测定结果无显著性差异。本方法适合于pH=4.2时水溶性的磷酸盐中磷含量的测定。采用本方法测定磷酸（氢）钙中磷含量,结果令人满意。     

Roles of Li+ and Zr4+ cations in the catalytic performances of Co(1-x)M(x)Cr(2)O(4) (M = Li, Zr; x = 0-0.2) for methane combustion

Co(1-x)M(x)Cr(2)O(4) (M = Li, Zr; x = 0-0.2) catalysts were prepared via the citric acid method and investigated for catalytic combustion of methane. Substitution at tetrahedral (A) sites with monovalent (Li) or tetravalent (Zr) metal ions led to a decrease or increase of the catalytic activity, respectively. The Co(0.95)Zr(0.05)Cr(2)O(4) catalyst proved to be the most active and its catalytic activity reached 90% of methane conversion at 448 °C, which dropped by 66 °C compared with that of the undoped CoCr(2)O(4) catalyst. XRD and Raman results indicated that lithium or zirconium substitution could modify the spinel structure and electronic properties. For lithium-doped catalysts, oxygen deficiency and a strong surface enrichment in lithium and chromium were detected. Zirconium substitution enhanced the reducibility of zirconium-doped catalysts and decreased the strength constant of both the Co-O band and the Cr-O band, which may contribute to the catalytic activity toward methane combustion. In addition, the prevalent catalytic combustion activity of the zirconium-substituted catalysts could be explained by their higher concentration of suprafacial, weakly chemisorbed oxygen.     

Enhanced photocatalytic degradation of dye pollutants under visible irradiation on Al(III)-modified TiO2: structure, interaction, and interfacial electron transfer

Aluminum(III)-modified TiO2 was prepared by sol-gel process via a sudden gelating method. The structure of the modified material and the local environment of aluminum were investigated using X-ray diffraction, HRTEM, XPS, 27Al MAS NMR, and xi-potential measurements. The effect of the aluminum modification on interaction between the dye and photocatalyst, the interfacial electron transfer process, and thereby the degradation of dye pollutants under visible irradiation were also examined by FTIR spectra and UV-vis diffuse reflectance spectra. It was found that, rather than incorporating into the crystal lattice of TiO2, the aluminum forms an overlayer of Al2O3 on the surface of TiO2, interfaced with Ti-O-Al bonds. It is interesting that the carboxylate-containing dyes such as Rhodamine B (RhB) adsorb preferentially on the Al2O3, rather than the Ti(IV) sites on the surface of TiO2. The photodegradation rate observed for RhB is nearly 5-fold faster than that obtained in the pristine TiO2 system. The photodegradation of dyes on the aluminum(III)-modified photocatalyst is of great dependence on the structure and anchoring group of the dyes. Structure with carboxylate as anchoring group and amino group as electron donor is favorable for degradation. The mechanistic details are discussed on the basis of experimental results.     

Heterogeneous photocatalytic reduction of chromium(VI) over TiO2 particles in the presence of oxalate: involvement of Cr(V) species

Cr(VI) photocatalytic reduction experiments over TiO2 particles under near UV irradiation in the presence of excess oxalate were performed at acid pH (2 and 3) and under air and N2 bubbling. Initial photonic efficiencies for Cr(VI) reduction are nearly the same under aerobic and anaerobic conditions, but show a significant increase at the lowest pH. At pH 2, the addition of oxalate facilitates Cr(VI) reduction, hindering the electron-shuttle mechanism taking place in pure water. The oxalate synergistic effect at pH 2 is lower than that previously found for EDTA and negligible at pH 3. Chromium(V) oxalate concentration profiles were obtained by EPR spectroscopy in the presence of excess oxalate at pH 1.5. Coordinated Cr(V) complexes [Cr(V)(O)(Ox)2]-, [Cr(V)(OH2)(Ox)2]-, and [Cr(V)(O)(OH)2(Ox)]- were identified, on the basis of the comparison of their corresponding g values with recent literature data. The kinetic analysis of the temporal evolution of the paramagnetic Cr(V) species indicates also an effective photocatalytic degradation of chromium(V) oxalate complexes. This new evidence reinforces previous findings regarding sequential one-electron-transfer processes in Cr(VI) photocatalytic reduction, suggesting that this route may represent a general behavior for the Cr(VI) reduction over UV-irradiated TiO2 particles.     

Kinetics of ascorbic acid degradation and colour change in ground cashew apples treated at high temperatures (100–180 °C)

Ascorbic acid (AA) degradation and colour changes, measured by the lightness index (L*), were determined in cashew apples (at low dissolved O₂ concentrations) heated at high temperature (100–180 °C) in a hermetically sealed cell. A nonisothermal method was developed to estimate thermal degradation kinetics. The results showed that reaction kinetics during heat treatments were well represented by first‐order reactions. The temperature dependence of the kinetic constants was described by an Arrhenius type equation. The activation energy (E_a) for AA degradation and lightness index were 94 ± 3 and 98 ± 3 kJ mol^?1, respectively. The reaction rate constant at 140 °C for AA degradation (64 × 10^?5 ± 3 × 10^?5 s^?1) was twice that for the lightness index change (33 × 10^?5 ± 2 × 10^?5 s^?1). Results allow generating temperature profiles of heat processes that would help preserve the AA of cashew apples as well as control the colour formation during high‐temperature processes.     

Enhanced-Oxidation and Highly Sensitive Detection of Tartrazine in Foodstuffs via New Platform Based on Poly(5-Sulfosalicylic Acid)/Cu(OH)<Subscript>2</Subscript> Nanoparticles

Poly(5-sulfosalicylic acid) (PSSA)/Cu(OH)₂ nanoparticle–graphite (Gr) nanocomposite-modified glassy carbon electrode (PSSA/Cu(OH)₂–Gr/GCE) was utilized for sensitive determination of tartrazine using squarewave voltammetry (SWV). The structure of the nanocomposite was investigated by transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM(. PSSA/Cu(OH)₂–Gr/GCE exhibited an enhancement in anodic peak current, electron transfer kinetics, effective surface area, and reactive sites and indicated good electrocatalytic activity toward the oxidation of tartrazine. The as-proposed modified electrode achieved a satisfactory dynamic range between the anodic peak current and the concentration of tartrazine at two concentration ranges of 0.01–0.6 and 0.6–10 μmol/L, and the detection limit was obtained to be 8 nmol/L (S/N = 3). The resulting sensor was successfully used to determine tartrazine in real samples such as candy, softdrink, orange juice powder, banana-flavored jelly powder, and candy-coated chocolate.     

Photocatalytic oxidation mechanism of As(III) on TiO2: unique role of As(III) as a charge recombinant species

Using TiO(2) photocatalyst, arsenite, As(III), can be rapidly oxidized to arsenate, As(V), which is less toxic and less mobile in the aquatic environment. Therefore, the TiO(2)/UV process can be employed as an efficient pretreatment method for arsenic contaminated water. Since we first reported in 2002 that the superoxide (or hydroperoxyl radical) plays the role of main oxidant of As(III) in the TiO(2)/UV process, there has been much debate over the true identity of the major photooxidant among superoxides, holes, and OH radicals. The key issue is centered on why the much stronger OH radicals cannot oxidize As(III), and it has been proposed that the unique role of As(III) as an external charge recombination center on the UV-excited TiO(2) particle is responsible for this eccentric mechanism. Although the proposed mechanism has been supported by many experimental evidences, doubts on it were not clearly removed. In this study, we provided direct and undisputed evidence to support the role of As(III) in the charge recombination dynamics using time-resolved transient absorption spectroscopy. The presence of As(III) indeed mediated the charge recombination in TiO(2). Under this condition, the role of the OH radical is suppressed because of the null cycle, and the weaker oxidant, superoxide, should prevail. The role of the superoxide has been previously doubted on the basis of the observation that the addition of excess formic acid (hole scavenger that should enhance the production of superoxides) inhibited the photocatalytic oxidation of As(III). However, this study proved that this was due to the photogeneration of reducing radicals (HCO(2)·) that recycle As(V)/As(IV) back to As(III). It was also demonstrated that the 4-chlorophenol/TiO(2) system under visible light that cannot generate neither OH radicals nor valence band holes converted As(III) to As(V) through the superoxide pathway.     

Effect of CO<Subscript>2</Subscript>/O<Subscript>2</Subscript>-containing modified atmospheres on packed deepwater pink shrimp (<Emphasis Type="Italic">Parapenaeus longirostris</Emphasis>)

The purpose of this study was to analyse the effect of two gas mixtures, containing 40% CO₂/30% O₂/30% N₂ and 45% CO₂/5% O₂/50% N₂, on the microbiological flora (total bacteria count, H₂S-producers microorganisms and enterobacteria) and some biochemical indexes (trimethylamine, total volatile basic nitrogen and biogenic amines) of chilled shrimp. Modified atmosphere packaging (MAP) on shrimps delayed the microbial growth compared to air-packed or iced stored shrimp as well as the trimethylamine and total volatile nitrogen production. However, the production of some biogenic amines seemed to be enhanced during the storage of MAP-shrimp.     

Nucleotide degradation and biogenic amine formation of wild white grouper (Epinephelus aeneus) stored in ice and at chill temperature (4 °C)

Sensory (cooked and uncooked), chemical (proximate composition, TVB-N, nucleotide degradation products and biogenic amines) and microbiological quality (TVC and total coliform) changes were investigated during storage of ungutted white grouper kept in ice and at chill temperature (4 °C). According to the sensory assessment, the shelf life of white grouper was 16 days in ice and 4 days for fish stored at chill temperature. TVB-N values increased with storage time. Amines found in white grouper stored in ice were TMA, putrescine, cadaverine, 2-phenylethylamine, dopamine, agmatine, tryptamine and serotonin. Histamine, spermine, spermidine were never detected with either storage condition. The acceptability limit in terms of microbial count was exceeded at 8 days in ice and at 4 days for fish stored at chill temperature. Total coliform count was 2.8 log₁₀ cfu/ml at 1 day and reached 10⁵ cfu/ml for both storage conditions.     

The influence of mash pre-aging on the development of the flavour-active compound, 4-hydroxy-2(or5)-ethyl-5(or2)-methyl-3(2H)-furanone (HEMF), during soy sauce fermentation

Inoculation of Zygosaccharomyces rouxii into a soy sauce mash free from lactic acid bacteria at 10⁶ cells mL⁻¹ resulted in the formation of the flavour-active compound HEMF over a number of days at 30°C. Delays in inoculation up to 14 days after production of the mash greatly increased the amount of HEMF formed and under some conditions concentrations in the commercial range were achieved without addition of any other microorganisms.     

卤水-氨法碱式氯化镁晶须的制备及影响因素的研究

在常压下用液相反应法制备了碱式氯化镁晶须,研究了氯化镁浓度、氯化镁与氨水的摩尔比、反应温度、陈化温度、陈化时间对碱式氯化镁晶须制备的影响.根据XRD和SEM测试结果,提出了制备碱式氯化镁晶须的最佳工艺条件:(1)氯化镁浓度为3mol/l;(2)氯化镁与氨水的摩尔比为4:1～6:1;(3)最佳反应温度为30℃;(4)氨水的加料速度为10ml/min～20ml/min;(5)最佳陈化温度为50℃～60℃,最佳陈化时间为48h～72h.制备得到了长径比≥100碱式氯化镁晶须.     

The formation of 2,5-dimethyl-4-hydroxy-2H-furan-3-one by cell-free extracts of Methylobacterium extorquens and strawberry (Fragaria × ananassa cv. Elsanta)

The formation of 2,5-dimethyl-4-hydroxy-2H-furan-3-one (DMHF), using the bacterial cells of Methylobacterium extorquens (strain with CABI registration number: IMI 369321) and strawberry cells (Fragaria × ananassacv. Elsanta), was studied. A combined mixture of the bacterial cell-free extract plus the strawberry extract was used as the enzymatic source. The pH of all the experimental aliquots was pH 6.0. The studied substrates were short-chain alcohols, carbohydrates and one amino acid. DMHF was analyzed by HPLC with UV detection at 280 nm. When 1,2-propanediol, 1-propanol, sucrose and fructose were used as substrates, the best production rates of DMHF were achieved, having a combined mixture of the bacterium and strawberry (minus the achenes) as the enzymic source. On the other hand, glucose, 1,2-propanediol, 2-propanol and fructose were the best substrates for the production of DMHF when a combined mixture of the bacterium and achenes served as the enzymic source. All results were obtained by comparing the production of DMHF from the strawberry extract alone and the bacterium plus the strawberry, without the achenes (in the first case) and the production of DMHF from the achene extract alone and the bacterium plus the achenes (in the second case). Moreover, the dehydrogenation activities of these three enzyme sources were determined by measuring the absorption of NADH at 340 nm. The substrate which was used for this series of the experiments was 1,2-propanediol. These results indicate the undoubted cooperation between the plant and the bacterial cells. This paper reports, for the first time, the formation of DMHF by bacterial and plant cell-free extracts.     

On the role of 2,3-dihydro-3,5-dihydroxy-6-methyl-(4<Emphasis Type="Italic">H</Emphasis>)-pyran-4-one in antioxidant capacity of prunes

Despite available reports on phenolic composition and antioxidant capacity (AOC) of fresh plums and prunes, there is a scarcity of published knowledge on the antioxidants formed and/or released during the drying process in the literature. To evaluate the compounds participating in reducing capacity of prunes, we compared aqueous and methanol extracts of fresh plums, commercial prunes and home-made prunes prepared at different drying temperatures using an HPLC method with amperometric detection (HPLC-ECD). The prunes dried at high temperature (90 °C, 18 h) in kitchen or laboratory oven with restricted ventilation gave up to 3.3 times higher electrochemical capacity (EC) than fresh plums (dry matter; P. domestica cv. Domestica) in dependence on production protocol. Drying at 60 °C (low-temperature drying) for 18 h did not change the EC significantly. Yet, lower EC was found in commercial tenderized prunes with sorbate; they were by a factor of 1.1–8.2 lower in EC than the prepared low-temperature prunes. The principle responsible for the increase in EC in the prunes prepared at high temperatures is 2,3-dihydro-3,5-dihydroxy-6-methyl-(4H)-pyran-4-one (DDMP). It was not detected until 74 °C was set during isothermal 18 h drying or until 6 h of drying passed at 90oC drying. The ultimate acceptable dwell-time for the preparation of conveniently eatable prunes dried at 90oC under the conditions used was assessed to 12 h. The EC of plums and prunes as well as the role of DDMP was confirmed by the use of several methods for the assessment of AOC-DPPH^• assay, β-carotene bleaching method, Oxipres test and Schaal oven test.     

Photopyroelectric observation of melting in valeric (C5 : 0), linoleic (C18 : 2), linolenic (C18 : 3) and tricosanoic (C23 : 0) free fatty acids

Photopyroelectric (PPE) study of some saturated (C5 : 0, and C23 : 0) and unsaturated (C18 : 2 and C18 : 3) free fatty acids was performed in a temperature range that included their melting points. The standard PPE configuration was used consistently during the experiment; the special PPE case requests thermally thick sample and sensor and optically opaque sample. For those fatty acids for which literature data on volume-specific heat were available (C18 : 2, C18 : 3), the behaviour around the melting point of all static and dynamic thermal parameters (specific heat, thermal conductivity, diffusivity and effusivity) was obtained. Since no data for volume-specific heat of C5 : 0 and C23 : 0 were found in the literature, only the temperature behaviour of the thermal diffusivity was obtained for these specimens. © 1998 Society of Chemical Industry