有机过氧化物中过氧键的建立(引入)方法

有机过氧化物目前已发展成非常重要的一类抗疟药物.形成/引入过氧键是合成有机过氧化物的关键步骤和难点所在.对合成有机过氧化物时常见的建立或引入过氧键的方法、各方法的适用范围及优劣所在作了简要的综述.

新型飞机燃油抗氧剂膦化物的氧化反应的研究

膦化物为高性能飞机燃油潜在的抗氧剂,能显著地改善飞机燃油的高温稳定性能。实验结果表明,膦化物在燃油介质中的氧化反应有两种反应类型同时进行,即:自由基链反应及膦化物与氧气的直接作用。在相对较低温度时,膦化物与基态氧发生自由基链反应,膦化物很快被氧化为氧化膦;在相对较高的温度,膦化物与激发态氧直接作用,通过三元环状中间体而最终生成氧化膦和次磷酸酯。

微波无极光降解甲硫醚

采用微波无极灯(MEDL)光解甲硫醚气体,结果表明,随着进气浓度的增加,甲硫醚去除率相应降低,但其绝对处理量却相应增加;停留时间越长,去除率越大,停留时间为10 s时,降解率高达94.3%。微波无极光化学反应系统中主要产生直接光解、光诱导产生的激发态氧原子O(1D)和羟基自由基的氧化作用,可将甲硫醚降解转化为硫酸盐、二氧化碳和水等无机化合物,其中激发态氧原子O(1D)的含量是影响甲硫醚降解的关键因素。

Characterization of the Excited State on Methanol/Ti02（110） Interface

The electronic structure of methanol/TiO2（ll0） interface has been studied by photoemis- sion spectroscopy. The pronounced resonance which appears at 5.5 eV above the Fermi level in two-photon photoemission spectroscopy （2PPE） is associated with the photocatalyzed dissociation of methanol at fivefold coordinated Ti sites （Ti5c） on TiO2 （110） surface [Chem- ical Science 1, 575 （2010）]. To check whether this resonance signal arises from initial or intermediate states, photon energy dependent 2PPE and comparison between one-photon photoemission spectroscopy and 2PPE have been performed. Both results consistently sug- gest the resonance signal originates from the initially unoccupied intermediate states, i.e., excited states. Dispersion measurements suggest the excited state is localized. Time-resolved studies show the lifetime of the excited state is 24 fs. This work presents comprehensive char- acterization of the excited states on methanol/TiO2（110） interface, and provides elaborate experimental data for the development of theoretical methods in reproducing the excited states on TiO2 surfaces and interfaces.

Facet Dependence of Photochemistry of Methanol on Single Crystalline Rutile Titania

The crystal phase, morphology and facet significantly influence the catalytic and photocat- alytic activity of TiO2. In view of optimizing the performance of catalysts, extensive efforts have been devoted to designing new sophisticate TiO2 structures with desired facet exposure, necessitating the understanding of chemical properties of individual surface. In this work, we have examined the photooxidation of methanol on TiO 2 （011）- （ 2 × 1 ） and TiO 2 （110） - （1 ×1） by two-photon photoemission spectroscopy （2PPE）. An excited state at 2.5 eV above the Fermi level （EF） on methanol covered （011） and （110） interface has been detected. The excited state is an indicator of reduction of TiO2 interface. Irradiation dependence of the excited resonance signal during the photochemistry of methanol on TiO2（011）-（2×1） and TiO2（110）-（1× 1） is ascribed to the interface reduction by producing surface hydroxyls. The reaction rate of photooxidation of methanol on TiO2（110）-（1× 1） is about 11.4 times faster than that on TiO2（011）-（2×1）, which is tentatively explained by the difference in the surface atomic configuration. This work not only provides a detailed characterization of the electronic structure of methanol/TiO2 interface by 2PPE, but also shows the importance of the surface structure in the photoreactivity on TiO2.

Reaction of C2HCl2＋O2： Combined TR-FTIR Spectroscopy and Electronic Structure

The product channels and mechanisms of the C2HC12＋O2 reaction are investigated by step-scan time-resolved Fourier transform infrared emission spectroscopy and the G3MP2// B3LYP/6-311G（d,p） level of electronic structure calculations. Vibrationally excited products of HCI, CO, and CO2 are observed in the IR emission spectra and the product vibrational state distribution are determined which shows that HCI and CO are vibrationally excited with the nascent average vibrational energy estimated to be 59.8 and 51.8 kJ/mol respectively. In combination with the G3MP2//B3LYP/6-311G（d,p） calculations, the reaction mechanisms have been characterized and the energetically favorable reaction pathways have been suggested.

Broadband Visible Light Harvesting BODIPY-Perylene Dyad and Triad:Synthesis,Photophysical Properties,and Photooxidation Applications

In this study,diodo boron dipyrromethene(BODIPY)is employed a8 the energy donor and 3,4,9,10-perylene tetracarboxylic dianhydride(PDA)as the energy acceptor,enabling the synthesis of two new compounds:a BODIPY-perylene dyad named P1,and a triad named P2.To investigate the impact of the energy donor on the photophysical processes of the system,P1 comprises one diodo-BODIPY unit and one PDA unit,whereas P2 contains two diodo-BODIPY moieties and one PDA unit.Due to the good spectral complementarity between diiodo-BODIPY and PDA,these two compounds exhibit excellent light-harvesting capabilities in the 400-620 nm range.Steady-state fluorescence spectra demonstrate that when preferentially exciting the diodo-BODIPY moiety,it can effectively transfer energy to PDA;when selectively exciting the PDA moiety,quenching of PDA fluorescence is observed in both P1 and P2.Nanosecond transient absorption results show that both compounds can efficiently generate triplet excited states,which are located on the PDA part.The lifetimes of the triplet states for these two compounds are 103 and 89μs,respectively,significantly longer than that of diiodo-BODIPY.The results from the photooxidation experiments reveal that both P1 and P2 demonstrate good photostability and photooxidation capabilities,with P2 showing superior photooxidative efficiency.The photooxidation rate constant for P2 is 1.3 times that of P1,and its singlet oxygen quantum yield is 1.6 times that of P1.The results obtained here offer valuable insights for designing new photosensitizers.

O(~1D)与CF_2HCl的反应研究

研究了CF2HCl-O3体系在253．7nm紫外光照射下所引发的O（1D）与CF2HCl的反应．O（1D）与CF2HCl的反应最终产物为CF2O、HCl．对O（3P）与CP2HCl的反应可能性、O（1D）与CF2HCl的反应机理、外加气体对反应的影响等方面进行了讨论．

Effects of Mo on phase structure and up-conversion emissions of Er:Al_2O_3 nanocrystals

A simple and efficient approach was presented to enhance up-conversion emissions significantly for the Er：Al2O3 nanocrystals by Mo support （Er-Mo：Al2O3） with a 976 nm laser diode excitation. Mo support had evident effects on the phase structure and up-conversion emissions for the Er：Al2O3 nanocrystals, which promoted the θ-（Al,Er）2O3 transformed to α-（Al,Er,Mo）203 phase, Compared with the Er：Al2O3, the maximal green and red up-conversion emissions intensities increased about 3×10^3 and 1.4×10^2 times for the Er-Mo：Al2O3 nanocrystals, respectively. It suggests that the enhancement of up-conversion emissions is caused by the high excited state energy transfer process from [4115/2, 3T2） state of the Er3＋-MoO2- dimer to the 4F7/2 level of E3＋.