微乳液的热力学性质 I: 芳烃类的侧链链长对微乳液热力学函数影响

本文研究以非离子型表面活性剂-正辛醇-水-芳烃类所组成的微乳液, 探讨醇从油相转移到界面相时的自由能变化, 以及温度对自由能的影响。计算出熵和焓的变化, 发现在实验范围内, 上述热力学函数的对数值与芳烃侧链的碳原子数(n)呈线性关系。这些关系式对微乳液的构成和稳定性的讨论是重要的, 还对几种芳烃异构体所构成的微乳液的热力学函数进行了实验和讨论。     

Influence of a lateral electric field on the optical properties of InAs quantum dots

We have performed single dot photoluminescence and time-resolved ensemble photoluminescence measurements on InAs quantum dots embedded in a lateral in-plane p–i–n or n–i–n device, respectively, which makes the application of lateral electric fields, i.e. field direction perpendicular to the growth direction, feasible. Time-resolved measurements show an increase in the radiative lifetime of up to 30% with increasing field. We attribute this to the reduced overlap between the electron and hole wave functions. Single dot spectroscopy revealed a small red-shift of the emission energies of maximum 0.5 meV. This shift can be explained by the quantum confined Stark effect taking into account that the red-shift due to the band-tilting is partly compensated by a decrease in exciton binding energy.     

抗坏血酸和尿酸在甘氨酸-壳聚糖修饰玻碳电极上的电化学行为及测定

制备了甘氨酸-壳聚糖复合膜修饰玻碳电极(Gly-CTS/GCE),研究了抗坏血酸(AA)和尿酸(UA)在该修饰电极上的电化学行为。结果表明在pH=5.59的磷酸盐缓冲溶液中,AA、UA在Gly-CTS/GCE上均产生灵敏的不可逆氧化峰,其峰电流与浓度在一定范围内呈良好的线性关系。对AA和UA混合溶液平行测定7次,相对标准偏差分别为4.6%、2.9%,表明该电极重现性和稳定性良好。AA、UA在Gly-CTS/GCE电极上的氧化峰峰电位相差340mV,据此可实现对二者的同时检测,并可应用于实际样品测定。     

C70X2(X=H,F, Cl)的稳定性和电子光谱

用INDO方法研究C70H2四种异构体的稳定性, 表明其最稳定异构体为1, 9-C70H2和7, 8-C70H2, 两者能量差为16.3KJ.mol^-^1, 与实验值及ab initio计算值接近; 光谱计算表明, 其特征吸收峰与实验值一致。在此基础上预测C70F2和C70Cl2的稳定性和电子光谱, 表明C70F2四种异构体的稳定性顺序与C70H2一致, 而C70Cl2则以21, 42-异构体最为稳定。二者的电子光谱与C70H2极其相似只是在500nm以上有细微差别。     

氢原子在镍台阶面上吸附、振动和表面扩散行为的理论研究

本文用对势方法研究了氢原子在Ni(510)台阶面上的吸附和振动, 计算结果与实验符合得很好。并考察了氢原子在Ni(997)台阶面上的吸附和扩散, 结果表明,台阶对下台面上扩散的氢原子开成捕获势阱, 对上台面扩散的氢原子形成反射势,这也很好地支持了实验结果。     

A comparison between the sonochemical and thermal reaction of 5H,5Cl-dibenz[a,d]cycloheptatriene with nitrobenzene

The reaction of 5H,5Cl-dibenzo[a,d]cycloheptatriene with nitrobenzene was investigated under both thermal (210 degrees C) and ultrasonic (50 degrees C, 40 kHz) activation. The reaction products of both procedures are similar, but their amounts depend on the activation source. To account for the products a common electron transfer reaction is postulated through the dibenzotropylium cation. The differences between the thermal and ultrasonic process is thought to arise from the role of nitrobenzene as oxidant. Under thermal conditions this occurs throughout the reaction mixture but under sonication it occurs only in the cavitation bubble and in its immediate vicinity.     

Ultrasonically driven continuous process for vegetable oil transesterification

A bench scale continuous process for the manufacture of biodiesel from neat vegetable oils under high power low frequency ultrasonic irradiation was investigated. The experimental studies explored variations in alcohol-oil stoichiometry and type of oil. Important parameters such as residence time and reaction volume were considered. The highest conversion was achieved when short residence time was employed. The transesterification under ultrasonic irradiation is mainly influenced by the residence time in the reactor and alcohol-oil molar ratio.     

Sonolysis of chlorobenzene in Fenton-type aqueous systems

The influence of ultrasounds (200 kHz frequency) on the decomposition of chlorobenzene (CB) in a water solution (around 100 ppm concentration) containing iron or palladium sulfates was investigated. The intermediates of the sonolysis were identified, thus allowing a deeper insight into the degradation mechanism. It was established that CB degradation starts by pyrolysis inside the cavitation bubbles. The initial sonolysis product is benzene, formed in a reaction occurring outside the cavitation from phenyl radicals and the hydrogen atoms sonolytically generated from the water. Polyphenols as products of the CB sonochemical degradation are reported for the first time. The palladium salt was found to be a useful and sensitive indicator for differentiating the sites and mechanisms of the product formation. An alternative mechanism for the CB sonolysis is advanced, explaining the formation of phenols, polyphenols, chlorophenols and benzene.     

Ultrasonic versus silent methylation of vegetable oils

The profile of fatty acid methyl esters (FAME) of different vegetable oils produced under ultrasonic irradiation and conventional heating were compared. In the presence of potassium hydroxide as catalyst, the distribution of FAME was quite similar for both procedures, while in the case of sodium hydroxide ultrasonic irradiation gave better results. The FAME profile resulted from the reaction catalyzed by sulfuric acid was almost the same with the one resulted from the reaction catalyzed by KOH, while boron trifluoride can give rise to many artifacts, thus is not a reliable catalyst.     

Coherent dynamics in InGaAs quantum dots and quantum dot molecules

We measure the dephasing time of the exciton ground state transition in InGaAs quantum dots (QD) and quantum dot molecules (QDM) using a sensitive four-wave mixing technique. In the QDs we find experimental evidence that the dephasing time is given only by the radiative lifetime at low temperatures. We demonstrate the tunability of the radiatively limited dephasing time from 400 ps up to 2 ns in a series of annealed QDs with increasing energy separation of 69–330 meV from the wetting layer continuum. Furthermore, the distribution of the fine-structure splitting δ₁ and of the biexciton binding energy δ_B is measured. δ₁ decreases from 96 to with increasing annealing temperature, indicating an improving circular symmetry of the in-plane confinement potential. The biexciton binding energy shows only a weak dependence on the confinement energy, which we attribute to a compensation between decreasing confinement and decreasing separation of electron and hole. In the QDM we measured the exciton dephasing as function of interdot barrier thickness in the temperature range from 5 to 60 K. At 5 K dephasing times of several hundred picoseconds are found. Moreover, a systematic dependence of the dephasing dynamics on the barrier thickness is observed, showing how the quantum mechanical coupling in the molecules affects the exciton lifetime and acoustic-phonon interaction.