缅甸翡翠阴极发光光谱表征

利用宝石阴极发光仪,对不同种类翡翠的阴极发光及其阴极发光光谱进行了研究.结果表明:(1)白色翡翠主要发暗蓝色、浅紫色和绿黄色光,与之对应的阴极发光谱峰位于370 nm或554 nm处;(2)浅绿色-绿色翡翠多发明亮的绿色-黄绿色荧光,当绿色较深时,会发紫红色光,其阴极发光谱峰位于554 nm和760 nm处;(3)深绿色翡翠通常发暗红色荧光,阴极发光谱峰位于760 nm(主)和693 nm(次)处;(4)粉紫色、紫色翡翠发较明亮的紫红色-红紫色荧光,其阴极发光谱峰位于370 nm(主)和680 nm(次)或者370 nm(次)和680 nm(主)处,取决于紫色调的深浅;(5)蓝紫色翡翠发蓝紫色荧光,阴极发光谱峰位于370 nm(次)和508 nm(主)处.对各类翡翠阴极发光的宝石学意义和机理予以初步剖析.     

纳米碳管-钙钛石复合催化剂氧电极交换电流密度的测试与分析

以纳米碳管与钙钛石制备了复合催化剂氧电极，分析了电极中氧还原的催化机理，利用稳态阴极极化测试法，测试并分析了所制氧电极的交换电流密度．结果表明：复合催化剂催化能力优于单一催化剂；不同种类钙钛石催化能力大小顺序为：La0.8Sr0．2CoO3〉La0.6Ca0．4CoO3〉La0.6Ni0．4CoO3〉La0.8Sr0．2MnO3，正交试验确定的最佳氧电极催化剂配比为：纳米碳管0．1g，La0．6Sr0．4CoO3 0．02g，Na2SO4 0．1g，PTFE0．5mL，此时，交换电流密度最大，达0．1441 mA／cm^2；单因素试验结果显示，复合催化剂中w（La0.8Sr0．2CoO3）=9．09％，w（Na2SO4）=45．45％时电极的阴极极化程度最小．     

嵌入明文到椭圆曲线上一点的算法设计与实现

椭圆曲线密码体制(ECC)提供了当今所知密码体制中每bit位最高的安全强度。在各种用于签名方案，加密方案及密钥协商方案的椭圆曲线密码组件中，需要一些椭圆曲线范围参数。提出一种用于基点生成及明文信息编码为椭圆曲线上的点的理论计算方法，这是在有限域GF(p）上曲线生成及加密方案的一个必要步骤。并且设计和完全实现了相关的算法。通过基于INTEL CPU汇编著语言实现的结果表明，该算法是非常有效和实用的。     

高黏度荸荠羧甲基淀粉制备工艺的优化

研究了以荸荠粉 (C6H9O4OH )为原料 ,采用乙醇溶剂法 ,在碱性条件下制备高黏度荸荠羧甲基淀粉 (CMS)的工艺 ,探讨了工艺中诸因素对荸荠CMS黏度的影响。结果表明 :当x(荸荠粉 ) ∶x(乙醇 ) =1∶ 12 ,碱化时间为 0 .5h ,采用最佳工艺条件 :x(荸荠粉 )∶x(氢氧化钠 ) ∶x(氯乙酸 ) =1∶ 1.5∶ 0 .75 ,碱化温度为 3 5℃ ,醚化温度 45℃ ,醚化时间 为 2h ,可以制备黏度高达 15 5 0mPa·s的荸荠羧甲基淀粉。     

抗坏血酸对小麦面片色泽影响的研究

本文以农大152、扬麦158等2个高PPO活性小麦品种（系）为材料，研究了抗坏血酸（Vc）对鲜湿面片色泽的影响，结果表明：在0．2％～0．6％含量范围内，面片白度和亮度随着Vc含量的增加，其Hunter白度（Wh）、亮度（L^＊）值也相应增大，而红绿度（a^＊）则降低，它们之间存在较好的线性关系；加入0．5％（W／W）含量的Vc可有效延缓或阻止面片褐变，在恒温恒湿下静置12h后，其白度Wh（75．44）、亮度L^＊（79．09）仍显著高于不加Vc的对照（其值分别为65．92、68．84），而红绿度（a^＊，1．34）和黄蓝度（b^＊，15．09）则低于对照（其值分别为4．17、17．54）。12h内，加入0．5％Vc的面片白度及亮度的降幅显著低于对照，仍保持较白亮的色泽。加入0．5％Vc对面片多酚氧化酶（PPO）活性的影响，结果表明，在12h内，Vc对面片PPO活性抑制明显；与对照相比，PPO活性面积（活性曲线下包含的面积）显著较低，始终保持在较低的活性水平。上述说明加入适量的Vc可有效地抑制面片中PPO活性、阻止或延缓其褐变，从而改善外观品质。     

牛奶内酯的合成研究

以正丁醛、环己酮为原料,通过羟醛缩合,催化氢化,Baeyer-Villiger氧化和皂化脱水反应,得到目标产物5(6)-癸烯酸混合物,即牛奶内酯。对各步骤中影响产率的因素进行了分析,并得出了优化条件:(1)羟醛缩合:聚乙二醇400作为相转移催化剂,n(正丁醛):n(环己酮)=1:1.8,温度为30℃;(2)催化氢化:氢压为2.5MPa,温度为30℃;(3)Baeyer-Villiger氧化:n(2-丁基环己酮):n(过氧化尿素)=1:1.8,温度为30℃;(4)皂化脱水:碱浓度为30%(质量分数),皂化温度为110℃。反应的总产率为30.8%。     

Spectroscopic investigation of the uptake of arsenite from solution by synthetic mackinawite

As(III) uptake from solution by synthetic mackinawite is examined as a function of pH and initial As(III) concentration using X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD). XAS data indicate that when mackinawite is reacted at pH 5, 7, and 9 with 5 x 10(-4) M As(III), arsenic is reduced from its original +3 valence state and is primarily coordinated as As-S (approximately 2.26 angstroms) and As-As (approximately 2.54 angstroms), which is consistent with the formation of a realgar-like phase in agreement with XRD data. At 5 x 10(-5) M As(III), samples are markedly different from those collected at an order of magnitude higher concentration and differ at each pH value. The XAS analysis of mackinawite samples reacted with 5 x 10(-5) M As(III) shows a transition from As-O coordination to As-S coordination as pH decreases, with the sample reacted at pH 5 resembling realgar. Under alkaline conditions, arsenic retains its original valence state of +3 and is primarily coordinated to oxygen at a distance of 1.75 angstroms. This may be attributed to uptake by adsorption as an As(III) oxyanion. These results provide the basis for selecting the reactions needed for modeling and are beneficial in understanding the mechanisms of arsenite uptake by mackinawite under anoxic sulfidic conditions.     

Effect of cold temperature on the composition of different lipid classes of the foodborne pathogen Listeria monocytogenes: focus on neutral lipids

In this work a thorough consideration of the membrane lipid composition of Listeria monocytogenes together with DSC analysis is described in order to estimate the biological importance of lipid changes during low-temperature adaptation. Furthermore, these studies provide comparative data for fatty acid changes for neutral, NL and polar lipids, PL separately. The cold adaptation (5 degrees C) response of L. monocytogenes showed (i) an increase in the level of NL content (30%) among the total lipids, TL and (ii) that the increase (7-fold) in the anteiso-15:0/anteiso-17:0 fatty acid ratio, FAr, for cold NL was at variance with the ratio for TL and PL (about 10-fold). We correlated our findings with DSC studies on phase transition temperature (Tc), enthalpy difference (DeltaH) and peak range of the transition for TL, PL, NL (from cultures at 30 and 5 degrees C); The decrease of Tc (10.5 degrees C) and DeltaH (51%) for TL is a reflection of the decrease of Tc (11.5 degrees C) and DeltaH (56%) for PL. This large decrease is interpreted by the high (10-fold) increase of a-15:0/a-17:0 FAr of PL5 degrees C. In NL the decrease of Tc (3 degrees C) and of DeltaH (42%) is interpreted by both adaptation mechanisms: the (lower) 7-fold increase of anteiso-15:0/anteiso-17:0 FAr and the NL percentage calculated from increased mass values. The peak range of TL5 degrees C (from -15 to 25 degrees C) is a reflection of the peak range of NL5 degrees C, which is unchanged, as is the peak range of NL30 degrees C.     

Influence of nitrate on microbial reduction of pertechnetate

Factors influencing microbial reduction of Tc(VII) in nitrate and radionuclide contaminated aquifer sediments were investigated using sediment microcosms containing organic electron donor, nitrate and Tc(VII). Microcosms underwent nitrate reduction followed by Tc(VII) reduction. During this transition, the microbial community changed from being dominated by bacteria affiliated with the genus Paenibacillus during the nitrate reduction phase, to those affiliated with genera Agrobacterium, Geothrix, and Desulfosporosinus during the Tc(VII) reduction phase. To investigate the mechanism of Tc(VII) reduction, the nitrate reducing strains Agrobacterium FRC-A2, Azoarcus FRC-B1, and a fermentative Clostridium FRC-C11 were isolated from sediment microcosms undergoing Tc(VII) reduction. Nitrate reducing bacteria reduced Tc(VII) effectively only in the presence of Fe(lll) and after nitrate was reduced, implying a major role for Fe(ll) as an electron shuttle in Tc(VII) reduction. It is likely that accumulation of nitrite blocks Fe(ll) production and hence Tc(VII) reduction during the active nitrate reduction phase. The pure culture of Clostridium FRC-C11 is able to reduce Tc(VII) enzymatically with H2 or glucose as electron donor and deposits insoluble Tc compounds within the cells in a manner that is not significantly influenced by the presence of nitrate. These results provided a possible mechanism for Tc(VII) reduction independent of Fe(III) and not influenced by nitrate.     

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.     

Thermodynamic stabilization of hydrous ferric oxide by adsorption of phosphate and arsenate

Hydrous ferric oxide (HFO) is an X-ray amorphous compound with a high affinity for anions under strongly or mildly acidic conditions. Because of the usually small particle size of HFO, the adsorption capacity is high and adsorption may significantly impact the thermodynamic properties of such materials. Here we show that adsorption of phosphate and arsenate stabilizes HFO by experimental determination of enthalpies of formation (by acid-solution calorimetry) and estimates of standard entropies for six phosphate- or arsenate-enriched HFO samples. At pH values lower than ～5, the phosphate-doped HFO is not only less soluble than ferrihydrite (anion-free HFO) but also crystalline FeOOH polymorphs feroxyhyte and lepidocrocite. The arsenate-doped HFO is also stabilized with respect to the ferrihydrite. Phosphate availability in soils can be controlled by the phosphate-enriched HFO which is many orders of magnitude less soluble than apatite or crystalline Fe(III) phosphates, for example strengite (FePO(4)·2H(2)O). Thermodynamic dissolution models for scorodite (FeAsO(4)·2H(2)O) and As-enriched HFO show that under mildly acidic or circumneutral conditions, scorodite dissolves, As-HFO precipitates, and a substantial amount of As(V) is released into the aqueous solution (at pH 7, log m(As) ～ -2.5). The data presented in this paper can be used to model the equilibrium concentration of Fe(III), P(V), or As(V) in soil solutions or in natural or anthropogenic sediments polluted by arsenic.     

Monitoring of the generation of non-mutagenic benzoic acid compounds during the manufacture of erythrosine

The generation of 2-(2',4'-dihydroxybenzoyl) benzoic acid (DHBBA) and 2-(2',4'-dihydroxy-3',5'-diiodobenzoyl) benzoic acid (DHDIBBA) during the manufacture of erythrosine (Food Red No. 3) was examined. DHBBA is formed as an intermediate during the synthesis of fluorescein, and as fluorescein is produced, it is gradually consumed. However, under inappropriate reaction conditions, it remains in the resulting fluorescein at the termination of synthesis. DHDIBBA is easily obtained by the iodination of DHBBA. These compounds are also found when erythrosine is heated in excessive alkali. The results of the Ames test using DHBBA and DHDIBBA showed they did not possess mutagenic activity. The results clearly demonstrated that establishment of an upper limit for DHBBA and DHDIBBA is important in the quality control of fluorescein and erythrosine.     

Effect of impurities on the corrosion behavior of CO2 transmission pipeline steel in supercritical CO2-water environments

The corrosion property of carbon steel was evaluated using an autoclave under CO(2)-saturated water phase and water-saturated CO(2) phase with impurities (O(2) and SO(2)) at 80 bar CO(2) and 50 °C to simulate the condition of CO(2) transmission pipeline in the carbon capture and storage (CCS) applications. The results showed that the corrosion rate of carbon steel in CO(2)-saturated water was very high and it increased with adding O(2) in the system due to the inhibition effect of O(2) on the formation of protective FeCO(3). It is noteworthy that corrosion took place in the water-saturated CO(2) phase under supercritical condition when no free water is present. The addition of O(2) increased the corrosion rates of carbon steel in water-saturated CO(2) phase. The addition of 0.8 bar SO(2) (1%) in the gas phase dramatically increased the corrosion rate of carbon steel from 0.38 to 5.6 mm/y. This then increased to more than 7 mm/y with addition of both O(2) and SO(2). SO(2) can promote the formation of iron sulfite hydrate (FeSO(3)·3H(2)O) on the steel surface which is less protective than iron carbonate (FeCO(3)), and it is further oxidized to become FeSO(4) and FeOOH when O(2) is present with SO(2) in the CO(2)-rich phase. The corrosion rates of 13Cr steel were very low compared with carbon steel in CO(2)-saturated water environments with O(2), whereas it was as high as carbon steel in a water-saturated CO(2) phase with O(2) and SO(2).     

广州市26种水果中硒含量特征分析

通过酸消解,原子荧光-氢化物发生法测定了广州市26种市售水果中硒的含量,由标准物质(GBW08551猪肝)和回收率控制检测质量。结果表明,不同水果中硒含量有较大差异,含量范围为1.03～13.2μg/kg,平均含量为4.97μg/kg,不同类型水果中硒含量变化特征是:热带亚热带水果(6.03±2.59μg/kg)>浆果类(5.53±0.87μg/kg)>仁果类(5.18±0.33μg/kg)>核果类(4.78±0.97μg/kg)>柑橘类(3.92±0.50μg/kg)>瓜果类(3.43±0.94μg/kg)。     

Wavelength dependence of the photochemical reduction of iron in arctic seawater

Chemiluminescence measurements of the photochemical reduction of iron in cold, high-latitude waters (79 degrees N) show that a significant fraction (20%) of the dissolved iron is reduced when exposed to sunlight. The reduction is immediately initiated and the transition to a steady-state concentration of approximately 200 pM photochemical Fe(II) is achieved within approximately 40 s. The photochemical Fe(ll) is reoxidized to Fe(III) in less than a minute upon blocking the sunlight, much faster than expected, which is ascribed to reaction with photochemically produced oxidants. Using filters to block different ranges of the incident sunlight it was found that 35% of the photochemical Fe(II) was produced in the UV-B range (300-315 nm), 30% in the range 315-360 nm, and 30% at higher wavelengths. Measurements of light attenuation as a function of depth indicate that photochemical Fe(II) at a depth of 5 m in high-latitude waters should amount to approximately10% of that at the surface. The fast kinetics modulate the paramount importance that photochemical reactions may have on the bioavailability of iron in surface waters.     

应用HPLC反相色谱快速测定增鲜味精中的鸟苷酸和肌苷酸

本文描述了一种快速测定增鲜味精中的５’－鸟苷酸（５’－ＧＭＰ）和５’－肌苷酸（５’－ＩＷＰ）的方法。样品经过简单的前处理溶解、衍生并由ＯＤＳＣ－１８反相柱分离。流动相为０．５％ＫＨ_２ＰＯ_４缓冲液（ｐＨ４．５～５．０）。ＵＶ（紫外）－检测器波长为２５４ｎｍ。增鲜味精中的５００μｇ／１００ｇ５’－ＧＭＰ和５００μｇ／１００ｇ５’－ＩＭＰ能全部分离并定量测定。相关系数分别为０．９９８９（５’－ＧＭＰ）和０．９９９６（５’－ＩＭＰ）。回收率达分别达１０２．２％（５’－ＧＭＰ）和１０１．９％／（５’－ＩＭＰ）。变异系数分别为４．７％（５’－ＧＭＰ）和２．６％（５’－ＩＭＰ）。     

Formation of Cu(I) in estuarine and marine waters: application of a new solid-phase extraction method to measure Cu(I)

Cu(II) is a key species with respect to the bioavailability and hence toxicity of copper. Therefore, it is important to elucidate the factors that control Cu(I) steady-state concentrations in natural waters. In this study, a solid-phase-extraction-based method was developed that allows Cu(I) measurements at ambient concentrations. Cu(I) is selectively enriched as a bathocuproine complex on a hydrophobic polymer column, whereas Cu(II), bound to ethylenediamine, is not retained on the column. After elution with acidic methanol, Cu is analyzed with graphite-furnace atomic absorption spectroscopy. The detection limit of the whole analytical procedure is below 1 x 10(-9) M, and the mean recovery of Cu(I) is approximately 70%. We then applied this method to determine Cu(I) in water samples collected from the River Scheldt estuary and the North Sea. Upon irradiation of these filtered water samples in the laboratory (with approximately 5 kW m(-2)), Cu(I) steady-state concentrations ([Cu(I)]ss) were established within a few minutes, and [Cu(I)]ss ranged from 5% to 80% of total dissolved copper, depending on the origin of the water samples. Measured [Cu(I)]ss can be interpreted by considering light-induced reduction of Cu(II) and stabilization of Cu(I) by chloride at high salinity, thermal reduction of Cu(II) by sulfide-containing compounds at low salinity, and fast reoxidation of Cu(I) due to stabilization of Cu(II) by strong organic ligands present at intermediate salinity.     

Kinetics of hydrolysis and precipitation of ferric iron in seawater

We have investigated the kinetics of iron hydrolysis and precipitation and dissolution of the solid formed via a novel chemical method, namely accessibility of iron to the fungal siderophore desferrioxamine B (DFB), with spectrophotometric detection of the ferrioxamine complex. Our results support a mechanism in which precipitation of dissolved inorganic iron in seawater is first order with respect to total (dissolved and precipitated) iron, with a second-order rate constant of (4.1 +/- 1.1) x 10(7) M(-1) s(-1) at pH 8.1. The rate of dissolution was first order with respect to the total iron concentration and the first-order rate constant decreased from 2.3 x 10(-4) s(-1) after aging for 1 min to 4.8 x 10(-6) s(-1) after aging for 1 week. The proposed reaction mechanism simulated a solubility limit condition in agreement with experimental observations, from which we calculated the solubility of ferric iron to be 1.2 x 10(-13) M when the precipitate had been aged for 1 week. This is approximately 2 orders of magnitude less than reported in previous studies, possibly due to the chemically based method for dissolved iron determination used here compared with traditional physical separation methods. Our results confirm that Fe(III) hydrolysis in seawater is fast and show thatthe precipitated solid is quite labile initially but rapidly becomes much less so, with important implications for sequestration by organic ligands such as siderophores.     

Oxidation of flame retardant tetrabromobisphenol A by singlet oxygen

Wide use of flame retardants can pose an environmental hazard, and it is of interest to investigate how they may degrade. We report here that 3,3',5,5'-tetrabromobisphenol A (TBBPA) is subject to photosensitized oxidation involving singlet molecular oxygen ((1)O2). By using visible light and rose bengal or methylene blue as 102 photosensitizers, we have found that TBBPA is a 102 quencher. The quenching rate constant, k(q), depends on TBBPA ionization (pK = 7.4). In acetonitrile, where TBBPA is undissociated, the kq value is 6.1 x 10(5) M(-1) s(-1) for a TBBPA monomer and decreases to 2.9 x 10(4) M(-1) s(-1) for TBBPA dimers and/or aggregates. TBBPA dissociates in aqueous solutions, and its kq value is 1.44 x 10(9) M(-1) s(-1) in alkaline solution, decreasing to 3.9 x 10(8) M(-1) s(-1) at pH 7.2. The strong 102 quenching by TBBPA anion initiates an efficient oxidation of TBBPA, which results in oxygen consumption in aqueous micellar (e.g., Triton X-100) solutions containing photosensitizer. This oxygen consumption is mediated by transient radical species, which we detected by using EPR spectroscopy. We observed two major radicals and one minor radical generated from TBBPA by reaction with 102 at pH 10. One was identified as the 2,6-dibromo-p-benzosemiquinone radical (a2H = 2.36 G, g = 2.0056). A second radical (aH = 2.10 G, g = 2.0055) could not be identified butwas probably a 2,6-dibromo-p-benzosemiquinone radical containing an EPR-silent substituent at the 3-position. Spin trapping with 5,5-dimethyl-1-pyrroline N-oxide (DPMO) showed that other minor radicals (hydroxyl, carbon-centered) are also generated during the reaction of TBBPA with (1)O2. The photosensitized production of radicals and oxygen consumption were completely inhibited by the azide anion, an efficient physical (1)O2 quencher. Because TBBPA is a stable compound that at neutral pH does not absorb much of the atmosphere-filtered solar radiation, its photosensitized oxidation by (1)O2 may be the key reaction initiating or mediating TBBPA degradation in the natural environment.     

Bioreduction of uranium: environmental implications of a pentavalent intermediate

The release of uranium and other transuranics into the environment, and their subsequent mobility, are subjects of intense public concern. Uranium dominates the inventory of most medium- and low-level radioactive waste sites and under oxic conditions is highly mobile as U(VI), the soluble uranyl dioxocation (UO2)2+. Specialist anaerobic bacteria are, however, able to reduce U(VI)to insoluble U(IV), offering a strategy for the bioremediation of uranium-contaminated groundwater and a potential mechanism for the biodeposition of uranium ores. Despite the environmental importance of U(VI) bioreduction, there is little information on the mechanism of this transformation. In the course of this study we used X-ray absorption spectroscopy (XAS) to show that the subsurface metal-reducing bacterium Geobacter sulfurreducens reduces U(VI) by a one-electron reduction, forming an unstable (UO2)+ species. The final, insoluble U(IV) product could be formed either through further reduction of U(V) or through its disproportionation. When G. sulfurreducens was challenged with the chemically analogous (NpO2)+, which is stable with respect to disproportionation, it was not reduced, suggesting that it is disproportionation of U(V) which leads to the U(IV) product. This surprising discrimination between U and Np illustrates the need for mechanistic understanding and care in devising in situ bioremediation strategies for complex wastes containing other redox-active actinides, including plutonium.