单核锌双卟啉配合物构象平衡的理论研究及光谱分析

合成了一系列以不同长度柔韧链相连的p/p型单核锌双卟啉配合物。选用Tripos力场,利用分子动力学模拟退火和分子力学构象搜索相结合的方法对该系列双卟啉进行了能量优化和构象分析。理论计算结果表明:该类双卟啉稳定存在的最低能量构象为叠合式,最高能量构象为伸展式,并存在一系列的中间能量构象;双卟啉分子内π-π作用和能量转移与双卟啉存在的两种主要构象密切相关;分析了分子内π-π作用的本质。运用不同光谱测试手段验证了理论计算结果: 利用可见和相应二阶导数吸收光谱研究了双卟啉主要存在的叠合式和伸展式构象,通过红外光谱观察了对双卟啉构象和卟啉环间π-π作用较为敏感的吸收谱带;利用荧光光谱计算了双卟啉的分子内能量转移效率。     

5d过渡金属原子中心镶嵌Ag团簇M@Ag12(M=Hf～Hg)Ih和Oh构型的密度泛函理论研究

采用相对论密度泛函理论方法对Ih和Oh构型M@Ag12 (M＝Hf～Hg)的几何和电子结构进行了系统的研究. 研究表明, 原子半径之和与团簇的电子结构共同决定了M—Ag键长的大小. M@Ag12的成键能来自中心原子的嵌入能和Ag12笼子的形变能. 最高占据轨道为成键轨道的团簇比反键轨道的团簇的稳定性强. 我们发现在此系列中, Ih构型不一定总比Oh构型稳定. Hf@Ag12, Ir@Ag12, Au@Ag12和Hg@Ag12的Oh构型比Ih构型稳定.     

Novel Coumarin 7-Carboxamide/Sulfonamide Derivatives as Potential Fungicidal Agents: Design,Synthesis, and Biological Evaluation

Coumarin compounds have a variety of biological activities such as anti-tumor, anti-coagulation, anti-HIV, anti-fungal, and insecticidal. Amide and sulfonamide compounds have been used as fungicides for half a century, and dozens of varieties have been developed so far. This study focused on the introduction of carboxamide and sulfonamide moieties in a coumarin core to discover novel derivatives. Based on this strategy, we synthesized two series of novel carboxamide and sulfonamide substituted coumarin derivatives, and their fungicidal activity was also investigated. Some designed compounds possessed potential activities against six phytopathogenic fungi in the primary assays, highlighted by compound 6r. Compound 6r exhibited stronger fungicidal activity against Botrytis cinerea (EC₅₀ = 20.52 µg/mL) and will be the lead structure for further study.     

Synthesis and Crystal Structure of a New Double 2D Layer Complex Assembled by H4btec

Assembly of H4btec with cobalt（Ⅱ） acetate afforded a new double 2D layer coordination polymer, [Co（bteC）1/2（H2O）4·2H2O]n （H4btec = benzene-1,2,4,5-tetracarboxylic acid） 1. The polymeric structure has been characterized by single-crystal X-ray diffraction, FT-IR and thermal analysis. The crystal is of triclinic, space group PI with a = 10.8762（2）, b = 11.1411（1）, c = 11.5084（3） A, a = 82.8950（10）, β = 63.0050（10）, γ = 62.1500（10）°, V = 1091.72（4） A^3, C5H13CoO10, Mr= 292.08, Z = 4, Dc = 1.777 g/cm^3, μ = 1.612 mm^-l, F（000） = 600, R = 0.0578, and wR = 0.2162 for 3576 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Complex 1 consists of a new double 2D layer structure [Co（btec）1/2（H2O）4]n, both consisting of 4 ＋ 4 grids with the sizes of 11.3667（2）A × 11.5084（3）A （Co（1）-Co（1A） × Co（2A）-Co（2B）） and 11.5084（3）A × 11.3667（2）A （Co（3）-Co（3C） × Co（4）- Co（4A））, respectively. The phenyl rings are at the comers while the Co（Ⅱ） atoms are in the sides of the grids, and lattice water molecules decorate between the layers. Hydrogen bonds between the layers and lattice water molecules result in the final 3D framework.     

First total synthesis of isoquinolinone alkaloid marinamide and its methyl ester

The first total synthesis of isoquinolinone alkaloid marinamide 1 and its methyl ester 2 was described. The key steps involved a regioselective Frieclel-Crafts reaction of 1-benzyl-1H-pyrrole to form the intermediate 8.     

石墨炉原子吸收光谱法测定海藻制品中的砷

应用石墨炉原子吸收光谱技术建立了在海藻制品中测定总砷和三价无机砷的方法,为开展海藻制品中无机砷的监测和食品安全风险评估提供准确的检测方法。采用湿法消解和微波消解为测定总砷的前处理方式,9m ol/L盐酸浸泡后乙酸丁酯萃取和纯水反萃取作为海藻制品中三价无机砷的提取方式,分别利用塞曼扣背景和氘灯扣背景的石墨炉原子吸收光谱法测定总砷和三价无机砷。塞曼扣背景测定砷的线性范围为3.0—60μg/L,定量限(LOQ)为2.9μg/L,精密度为3.6%,回收率为90%—102%;氘灯扣背景测定砷的线性范围为4.0—80μg/L,定量限(LOQ)为3.6μg/L,精密度为4.1%,回收率为88%—109%。本法对三价无机砷的提取方法简便实用、提取效率高。原子吸收光谱法的两种背景校正方式测定总砷及三价无机砷的结果准确可靠。为基层实验室开展食品中总砷以及三价无机砷的测定提供实用、可靠的分析方法。     

Generation of a mid-infrared broadband polarized supercontinuum in As₂Se₃ photonic crystal fibers

A simplified structure of birefringent chalcogenide As 2 Se 3 photonic crystal fiber(PCF) is designed.Properties of birefringence,polarization extinction ratio,chromatic dispersion,nonlinear coefficient,and transmission are studied by using the multipole method,the finite-difference beam propagation method,and the adaptive split-step Fourier method.Considering that the zero dispersion wavelength of our proposed fiber is about 4 μm,we have analysed the mechanism of spectral broadening in PCFs with different pitches in detail,with femtosecond pulses at a wavelength of 4 μm as the pump pulses.Especially,mid-infrared broadband polarized supercontinuums are obtained in a 3-cm PCF with an optimal pitch of 2 μm.Their spectral width at 20 dB reaches up to 12 μm.In the birefringent PCF,we find that the supercontinuum generation changes with the pump alignment angle.Research results show that no coupling between eigenpolarization modes are observed at the maximum average power(i.e.,37 mW),which indicates that the polarization state is well maintained.     

Analysis of the characteristics of the polarization splitter based on tellurite glass dual-core photonic crystal fiber

A novel kind of polarization splitter based on tellurite glass dual-core photonic crystal fiber is proposed. The characteristics of the polarization splitter have been studied by the finite element method. By adjusting the ellipticity of the dual-core PCF, a very high value of birefringence can be reached. The high birefringence can increase the D-value of coupling length in the two orthogonal polarization directions, then the polarization-independent splitter can be achieved. Comparing with the SF57 glass dual-core PCF, the tellurite glass dual-core PCF has higher extinction ratio, the extinction ratio can reach ?31 dB at the wavelength $\lambda =1.55\mathrm{\mu }\mathrm{m}$. The 0.36-mm-long splitter is proposed to achieve extinction ratio better than ?10 dB and a bandwidth of 20 nm.     

全光学高灵敏度铷原子磁力仪的研究

报道了一种全光学的高灵敏度铷原子磁力仪.其原理是基于激光束与处于微弱磁场中的铷原子的相互作用.这种相互作用与铷原子所处的环境中的磁场有关,因而通过测量透过铷原子气体的激光强度的变化可以获得磁场信息.分析了该磁力仪的工作原理,建立了相应的实验装置,并对其性能进行了测试.结果表明实验结果与理论相符合.进一步研究了影响磁力仪灵敏度的一些因素,提出了优化各参数来提高磁力仪灵敏度的方法.     

Coupling characteristics of high birefringence dual-core As2S3 rectangular lattice photonic crystal fiber

A type of As₂S₃ chalcogenide glass mid-infrared dual-core photonic crystal fiber has been proposed. The dual-core photonic crystal fiber (PCF) consists of two asymmetric cores. The high polarization property and the coupling characteristics have been studied by using the finite element method and mode coupling theory. Numerical results show that the birefringence at wavelength λ = 10 μm is up to 0.01386 and the coupling length can reach wavelength λ = 5 μm, 261 μm and 271.44 μm for x-polarized mode and y-polarized mode, respectively. It demonstrates that a 6.786-mm-long fiber can exhibit an extinction ratio of better than -10 dB and a bandwidth of 180 nm.