铜的+1,+2两种价态化合物稳定性的比较

铜可以形成氧化态为+l,+2,+3三种价态的化合物。铜的+3价态的化合物有较强的氧化性,而稳定性差。例如淡绿色的K3CuF6氧化性很强,遇水即发生强烈的反应并放出氧气,本身还原为Cu2+。铜的+3价态的化合物如Cu2O3、KCuO2比较少见,常见的是铜的+1、+2两种价态的化合物,这两种价态的化合物,哪个稳定?这是在教学铜和铜化合物时会碰到的问题。如何回答这个问题,笔者认为,具体问题要作具体分析,稳定与不稳定都是相对的,有条件的。这可以从以下几个方面看出。

灵芝子实体中三萜酸的提取及其稳定性

研究不同提取方法对灵芝（Ganodermalingzhi）子实体中三萜酸提取率的影响，结果表明，采用乙醇回流法所得三萜酸的提取得率最大，影响提取的关键因素为液料比、提取时间和提取次数；采用Box．Behnken设计及响应面分析法对这3个因素进行优化，并通过回归拟合，建立了预测灵芝三萜酸提取的多项式模型，可预测灵芝子实体中三萜酸提取率的回归模型如下：Y=0．335-0．003125X1＋0．021X2—0．014X3＋0．0005X1 X2—0．019X1X3—0．005X2X3—0．044X12—0．040X2^2-0．032X3^2经响应面最优分析，获得3个因素的最佳水平为：液料比25：1，提取时间2h，提取次数3次。经实际试验验证，在该条件下，灵芝子实体三萜酸提取率可达0．335mg／g，与预测值相比，实测值低1．18％。稳定性试验结果表明，在较低温度下（25℃以下），三萜酸化合物较稳定；但在50℃及以上温度条件下，三萜酸存在明显的降解现象，三萜酸的稳定性与温度及保藏时间呈负相关。

稳定同位素标记化合物二氢吡啶-^13C4的合成与表征

目的建立稳定性同位素标记的化合物二氢吡啶-^13C4(二乙基-1,4-二氢-2,6-二甲基-3,5-吡啶二羧酸酯-^13C4)的合成方法。方法以同位素标记的乙酰乙酸乙酯-1,3-^13C2为原料,经Hantzsch反应合成得到稳定性同位素标记的化合物二氢吡啶-^13C4(二乙基-1,4-二氢-2,6-二甲基-3,5-吡啶二羧酸酯-^13C4),并对其结构经1HNMR、^13CNMR和MS(ESI)进行表征。结果所合成的目标产品,化学纯度大于99.0%, ^13C丰度为99.4%(atom ^13C)。结论该化合物可作为食品安全领域检测用同位素内标试剂,具有重要的应用价值。

应用气-质联机和同位素双标记技术对土壤微生物吸收有机氮的研究

土壤微生物对小分子有机氮的直接吸收和利用是目前微生物氮素营养研究的新方向。本研究通过气相色谱-质谱(GC-MS)对双标记氨基酸(^(13)C,^(15)N)的测定技术探讨土壤微生物对有机氮分子的直接吸收和利用。结果表明:加入土壤中的甘氨酸被微生物迅速利用,半衰期为2.9h。培养4h后在微生物体内检测到最大量的双标记甘氨酸(相当于甘氨酸加入量的10%),说明甘氨酸可以被微生物以完整分子形式所吸收。通过此手段也可检测到土壤溶液和微生物体内的单标记a-酮酸(双标记甘氨酸分解后的产物),但含量极少,说明加入的甘氨酸主要向微生物提供C源供其生命活动。本研究证明专性化合物同位素双标记手段结合氯仿熏蒸技术是检测微生物吸收小分子有机氮的有效手段。

Cobalt carbonyl ionic liquids based on the 1,1,3,3-tetra-alkylguanidine cation:Novel, highly efficient, and reusable catalysts for the carbonylation of epoxides

A series of novel cobalt carbonyl ionic liquids based on1,1,3,3‐tetra‐alkyl‐guanidine,such as[1,1‐dimethyl‐3,3‐diethylguanidinium][Co(CO)4](3a),[1,1‐dimethyl‐3,3‐dibutylguanidinium][Co(CO)4](3b),[1,1‐dimethyl‐3,3‐tetramethyleneguanidinium][Co(CO)4](3c),and[1,1‐dimethyl‐3,3‐pentamethyleneguanidinium][Co(CO)4](3d),were synthesized in good yields and were also characterized using infrared spectroscopy,ultraviolet‐visible spectroscopy,1H nuclear magnetic resonance(NMR)spectroscopy,13C NMR spectroscopy,high‐resolution mass spectrometry,differential scanning calorimetry,and thermogravimetric analysis.The four compounds exhibited high thermal and chemical stability.In addition,the catalytic performance of these compounds was investigated in the carbonylation of epoxides,with3a exhibiting the best catalytic activity without the aid of a base as the additive.The catalyst could be reused at least six times without significant decreases of the selectivity or conversion rate.Moreover,the catalyst system exhibited good tolerance with terminal epoxides bearing alkyl,alkenyl,aryl,alkoxy,and chloromethyl functional groups.

Effect of Nitrogen Compounds on the Oxidation Stability of Saturate Fractions

A custom built dynamic oxygen uptake tester was used to study theinfluence of nitrogen compounds on the oxidation characteristics ofthe saturate fractions from mineral base oils. Experimental resultsindicate that nitrogen compounds, especially quinoline and indole,take part in the oxidation of saturates. It is also found that indoleis more active than quinoline. The latter can be oxidized partly intoketoimine, and the former is more rapidly oxidized into acylamide.The oxidation products, ketoimine or acylamide, could inhibit theoxidation of the saturates by decomposing hydroperoxide.

Easy removing of phenol from wastewater using vegetable oil-based organic solvent in emulsion liquid membrane process

Phenol is considered as pollutant due to its toxicity and carcinogenic effect.Thus,variety of innovative methods for separation and recovery of phenolic compounds is developed in order to remove the unwanted phenol from wastewater and obtain valuable phenolic compound.One of potential method is extraction using green based liquid organic solvent.Therefore,the feasibility of using palm oil was investigated.In this research,palm oil based organic phase was used as diluents to treat a simulated wastewater containing 300×10^(-6) of phenol solution using emulsion liquid membrane process(ELM).The stability of water-in-oil(W/O) emulsion on diluent composition and the parameters affecting the phenol removal efficiency and stability of the emulsion;such as emulsification speed,emulsification time,agitation speed,surfactant concentration,pH of external phase,contact time,stripping agent concentration and treat ratio were carried out.The results of ELM study showed that at ratio7 to 3 of palm oil to kerosene,5 min and 1300 r·min^(-1) of emulsification process the stabile primary emulsion were formed.Also,no carrier is needed to facilitate the phenol extraction.In experimental conditions of500 r·min^(-1) of agitation speed,3%Span 80,pH 8 of external phase,5 min of contact time,0.1 mol·L^(-1) NaOH as stripping agent and 1:10 of treat ratio,the ELM process was very promising for removing the phenol from the wastewater.The extraction performance at about 83%of phenol was removed for simulated wastewater and an enrichment of phenol in recovery phase as phenolate compound was around 11 times.

First Principles Study of AI-Li Intermetallic Compounds

The structural properties, heats of formation, elastic properties, and electronic structures of four compositions of binary A1-Li intermetallics, A13Li, A1Li, A12Li3, and A14Li9, are ana- lyzed in detail by using density functional theory. The calculated formation heats indicate a strong chemical interaction between A1 and Li for all the A1-Li intermetallics. In partic- ular, in the Li-rich A1-Li compounds, the thermodynamic stability of intermetallics linearly decreases with increasing concentration of.Li. According to the computational single crystal elastic constants, all the four A1-Li intermetallic compounds considered here are mechani- cally stable. The polycrystalline elastic modulus and Poisson＇s ratio have been deduced by using Voigt, Reuss, and Hill approximations, and the calculated ratios of bulk modulus to shear modulus indicate that the four compositions of binary A1-Li intermetallics are brittle materials. With the increase of Li concentration, the bulk modulus of A1-Li intermetallics decreases in a linear manner.

Design and Selection of High Energy Materials based on 4,8-Dihydrodifurazano[3,4-b,e]pyrazine

In order to search for high energy density materials,various 4,8-dihydrodifurazano[3,4-b,e]pyrazine based energetic materials were designed.Density functional theory was employed to investigate the relationships between the structures and properties.The calculated results indicated that the properties of these designed compounds were influenced by the energetic groups and heterocyclic substituents.The-N3 energetic group was found to be the most effective substituent to improve the heats of formation of the designed compounds while the tetrazole ring/-C(NO_(2))_(3) group contributed much to the values of detonation properties.The analysis of bond orders and bond dissociation energies showed that the addition of-NHNH2,-NHNO_(2),-CH(NO_(2))_(3) and-C(NO_(2))_(3) groups would decrease the bond dissociation energies remarkably.Compounds A8,B8,C8,D8,E8,and F8 were finally screened as the potential candidates for high energy density materials since these compounds possess excellent detonation properties and acceptable thermal stabilities.Additionally,the electronic structures of the screened compounds were calculated.

Synthesis and ionic conductivity of Li_6La_3BiSnO_(12) with cubic garnet-type structure via solid-state reaction

The synthesis and transport properties of the Li6La3BiSnO1212 solid electrolyte by a solid-state reaction were reported. The condition to synthesize the Li6La3BiSnO1212 is 785 °C for 36 h in air. The refined lattice constant of Li6La3 BiSnO1212 is 13.007A. Qualitative phase analysis by X-ray powder diffraction patterns combined with the Rietveld method reveals garnet type compounds as major phases. The Li-ion conductivity of the prepared Li6La3BiSnO12 is 0.85×10^-4 S/cm at 22 °C, which is comparable with that of the Li5La3Bi2O12. The Li6La3BiSnO1212 compounds are chemically stable against Li CoO2 which is widely used as cathode material up to 700 °C but not against the Li Mn2O4 if the temperature is higher than 550 °C. The Li6La3 BiSnO1212 exhibits higher chemical stability than Li5La3Bi2O12, which is due to Sn substitution for Bi.

Comparative Studies of Thermal Stability of Coal Tar Pitches

In the present work, three medium softening point coal tar pitches were used for comparative thermal stability and under-storage stability investigation. Powders of the pitches were found to be different under storage： one of the pitches was caked and slumped after 7-day or longer storage. For thermal stability investigation the soft temperature treatment （265℃） of coal tar pitches was used. Detailed study of initial and treated pitches was carried out. Experimental results demonstrated that LMW-HC （high low-molecular-weight hydrocarbons） and oxygen content influence pitch quality characteristics in a negative way under long-term storage and lead to highest properties change after thermal stability treatment.

Experimental Study on Hydrocarbon Fuel Thermal Stability

The.thermal stability characteristics of kerosine-type fuels are examined using a heated-tube apparatus which allows independent control of fuel pressure,fuel temperature,tube-wall temperature and fuel flow rate.This method is identified simply as a“constant wall temperature method”.It is different from a previous widely used method,which is identified as a“constant heat flux method”.It is a single-pass system.Rate of deposition on the tube walls are measured by weighing the test tube before and after each test. For a fuel temperature of 250℃,it is found that deposition rates increase continuously with increase in tube- wall temperature.This finding contradicts the results of previous studies which had led to the conclusion that deposition rates increase with increase in wall temperature up to a certain value(around 650 K)beyond which any further increase in wall temperature causes the rate of deposition to decline. The present results show clearly that the constant wall temperature method is more suitable for assessing the thermal stability of gas turbine fuels.

Protection strategy for improved catalytic stability of silicon photoanodes for water oxidation

Silicon-based electrodes have attracted great attention in the artificial photosynthetic systems that mimic natural photosynthesis and directly convert the solar energy into chemical energy. Despite significant efforts to date,catalytic stability of the silicon photoelectrodes is limited by their poor electrochemical stability. The formation of passivation or protective layers provides a feasible strategy to improve the photocatalytic stability of silicon photoelectrodes. Many candidates including metals, metal oxides, metal silicides and polymers have been explored as the protection layers for silicon photoelectrodes. The present review gives a concise overview of the protected silicon photoanodes for water oxidation with a focus on the relationship between the structural architecture of silicon photoanodes and their photocatalytic activity and stability.

Non-phospholipid liposomes with high sterol content display a very limited permeability

We demonstrate that it is possible to form non-phospholipid fluid bilayers in aqueous milieu with a mixture of palmitic acid (PA),cholesterol (Chol),and cholesterol sulfate (Schol) in a molar proportion of 30/28/42.These self-assemblies are shown to be bilayers in the liquid ordered phase.They are stable between pH 5 and 9.Over this pH range,the protonation/deprotonation of PA carboxylic group is observed but this change does not appear to alter the stability of these bilayers,a behavior contrasting with that observed for binary mixtures of PA/Chol,and PA/Schol.The multilamellar dispersions formed spontaneously from the PA/Chol/Schol mixture could be successfully extruded to form Large Unilamellar Vesicles (LUVs).These LUVs show interesting permeability properties,linked with their high sterol content.These non-phospholipid liposomes can sustain a pH gradient (pH internal 8/pH external 6) 100 times longer than LUVs made of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and cholesterol,with a molar ratio of 60/40.Moreover,the non-phospholipid LUVs are shown to protect ascorbic acid from an oxidizing environment (1 mM iron(III)).Once entrapped in liposomes,ascorbic acid displays a degradation rate similar to that obtained in the absence of iron(III).These results show the possibility to form novel nanocontainers from a mixture of a monoalkylated amphiphile and sterols,with a good pH stability and showing interesting permeability properties.

Effects of leaf age,elevation and light conditions on photosynthesis and leaf traits in saplings of two evergreen conifers,Abies veitchii and A.mariesii

Aims Subalpine coniferous species are distributed over a wide range of elevations in which they must contend with stressful conditions,such as high elevations and extended periods of darkness.Two evergreen coniferous species,Abies veitchii and Abies mariesii,dominate at low and high elevations,respectively,in the subalpine zone,central Japan.The aim of this study is to examine the effects of leaf age,elevation and light conditions on photosynthetic rates through changes in morphological and physiological leaf traits in the two species.Methods We here examined effects of leaf age,elevation and light conditions on photosynthesis,and leaf traits in A.veitchii and A.mariesii.Saplings of the two conifers were sampled in the understory and canopy gaps at their lower(1600 m)and upper(2300 m)distribution limits.Important Findings The two species showed similar responses to leaf age and different responses to elevation and light conditions in photosynthesis and leaf traits.The maximum photosynthetic rate of A.veitchii is correlated negatively with leaf mass per area(LMA)and non-structural carbohydrate(NSC)concentration.LMA increased at high elevations in the two species,whereas NSC concentrations increased only in A.veitchii.Therefore,the maximum photosynthetic rate of A.veitchii decreased at high elevations.Furthermore,maximum photosynthetic rates correlate positively with nitrogen concentration in both species.In the understory,leaf nitrogen concentrations decreased and increased in A.veitchii and A.mariesii,respectively.LMA decreased and the chlorophyll-to-nitrogen ratio increased in understory conditions only for A.mariesii,suggesting it has a higher light-capture efficiency in dark conditions than does A.veitchii.This study concluded that A.mariesii has more shade-tolerant photosynthetic and leaf traits and its photosynthetic rate is less affected by elevation compared with A.veitchii,allowing A.mariesii to survive in the understory and to dominate at high elevations.

Effect of Intense Laser Irradiation on the Lattice Stability of Al_2Au

The structural, electronic and lattice-dynamical properties of the intermetallic Al 2 Au at different electronic temperatures have been investigated via density functional calculations. The results of electronic density of state indicate that, although its value changes considerably, Al2Au is still of metal with the increasing of electronic temperature. The acoustic mode of Al2Au gets negative which leads to lattice dynamical instability when the electronic temperature is beyond 1.44 eV. Moreover, with the increasing of the electronic temperature, the vibrational frequencies of the T1u optical mode (triply degenerate) of Al2Au at Γ point decrease first and increase then, the turning point is at Te = 1.40 eV. T2g optical mode at Γ point has a similar situation, but the turning point is at Te = 1.80 eV. The predicted melting temperatures of Al2Au undergo a sharp decrease from 1333K at normal temperature to 1172 K at Te = 1.8 eV after intense laser irradiation.