Ce∶YAG透明陶瓷的制备及性能研究

以高纯Al_2O_3、Y_2O_3和CeO_2为原料,采用固相法制备Ce∶YAG(掺铈钇铝石榴石)透明陶瓷,研究了稀土离子掺杂浓度以及烧结温度对陶瓷样品光学性能的影响。结果表明:陶瓷片透过率随着烧结温度的升高而增大,1750℃烧结获得的0.5%Ce∶YAG陶瓷片的透过率高达81.7%。Ce∶YAG陶瓷片的激发峰和发射峰分别位于350nm和530nm处,在白光LED领域具有极大的应用价值。     

SUNIST装置中磁探针出气率测量

通过出气率测量装置评价了SUNIST装置的内部磁探针出气特性,实验结果表明其出气量和出气气体成分不足以影响SUNIST真空特性。其后的放电实验验证了这一结论。     

Neutron Spectroscopic Factors of ^7Li and Astrophysical ^6Li（n,γ）^7Li Reaction Rates

Angular distributions of the ^7Li（^6Li, ^6Li）^7Li elastic scattering and the ^7Li（^6Li, ^7Lig.s.）^6Li, ^7Li（^6Li, ^7Li0.48）^6Li transfer reactions at Ec.m. = 23.7 MeV are measured with the Q3D magnetic spectrograph. The optical potential of ^6Li ＋ ^7Li is obtained by fitting the elastic scattering differential cross sections. Based on the distorted wave Born approximation （DWBA） analysis, spectroscopic factors of ^7Li =^6Li n are determined to be 0.73 ± 0.05 and 0.90 ± 0.09 for the ground and first exited states in ^7Li, respectively. Using the spectroscopic factors, the cross sections of the ^6 Li（n, γ0,1）^7 Li direct neutron capture reactions and the astrophysical ^6Li（n, γ）^7 Li reaction rates are derived.     

倾斜光纤光栅谱特性

基于倾斜光纤光栅耦合模理论,采用数值分析法研究了前后向导模耦合时倾斜角度和调制深度对倾斜光纤光栅反射谱的影响,以及导模和辐射模耦合时针对不同的入射光偏振态在倾斜角度、调制深度、光栅长度等不同时倾斜光纤光栅透射谱(或反射谱)的特性.研究结果表明,在前后向导模耦合时,不同偏振态入射光的光谱几乎相同;而对于辐射模耦合,由于反射谱的包络受消光系数的调制,而不同偏振态入射光的消光系数不同,并且倾斜角度越大不同偏振态的入射光的消光系数差别越大,故在研究辐射模耦合时需要将偏振态予以考虑.     

乙醇-硫酸铵双水相萃取镉-碘化钾-丁基罗丹明B离子缔合物

以紫外-可见分光光度法为检测手段,研究了乙醇-硫酸铵双水相体系萃取镉-碘化钾-丁基罗丹明B的离子缔合物的最佳条件.在0.5mol·L-1 H2SO4介质中,镉-碘化钾-丁基罗丹明B在乙醇-硫酸铵双水相体系中形成稳定的蓝紫色缔合物.Cd2+在0-3μg/10mL范围内呈线性关系,相关系数r=0.9984,表观摩尔吸光系数ε=1.28×106L·mol-1·cm-1.在最佳萃取条件下,离子缔合物的最大萃取率可达98％,Cd2+能与干扰离子Zn2+、Fe3+、Co2+、Cu2+、Ni2+分离完全.该法不仅灵敏度高、选择性好,而且环保、简便快速、分相清晰,无需进行反萃取,具有很强的实用性.     

超高效液相色谱-串联质谱法测定蜂蜜中抗生素和农药浓度

基于快速有效的基质净化方法,结合超高效液相色谱-串联质谱技术,建立了测定蜂蜜中39种抗生素及25种农药的检测方法.蜂蜜样品经乙腈+水（v/v=8：2）提取,用PRiME HLB净化,超高效液相色谱-串联质谱（ultra-performance liquid chromatography tandem mass spectrometry,UPLC-MS/MS）分析测定,通过多反应监测模式（MRM）分析目标化合物,并进行基质标准曲线定量.在测定浓度范围内呈良好线性关系,相关系数大于0.99;农兽药的检出限为0.02~3.8 μg·kg^-1,定量限为0.1~11.5 μg·kg^-1;在3档浓度的添加回收实验中,39种抗生素的回收率在72%~119%内,25种农药的回收率在72%~115%内,相对标准偏差均小于15%.随机抽取浙江市场上在售的52份蜂蜜样进行检测分析和膳食暴露评估,共检出罗红霉素、诺氟沙星和环丙沙星3种抗生素,检出率分别为2.6%,8.6%和3.9%,浓度分别为59.6~214.4,4.7~1 486.3和5.9~215.1 μg·kg^-1.膳食暴露评估结果表明,蜂蜜中抗生素残留对10岁以下组群的风险高于其他组群、女性消费者高于男性消费者;% ADI<100,说明膳食暴露评估风险水平尚可接受.因在计算中存在诸多不确定性因素,对组群的风险评估尚需进一步分析.     

超大硅胺基氯锗宾的反应性与立方四锗卡宾的成键解析

超大硅胺基取代的低价锗化合物可以构建新颖的化学结构,提供有学术价值的新发现。二配位的超大硅胺基氯锗宾Ge(N(SiⁱPr₃)₂)Cl (1)具有空的4p轨道和孤电子对。针对这2个特点,研究了化合物1的热构型转换和菲醌氧化加成反应。1的温热分解生成了立方四锗卡宾 Ge₄(NSiⁱPr₃)₄ (2),与菲醌(L)定量氧化加成生成了胺基一氯菲二酚合锗(Ⅳ)：[Ge(N(SiⁱPr₃)₂)(L)Cl] (3)。表征了2个产物的单晶结构与组成。四锗卡宾2本质上是锗异腈的四聚体,分子呈现出畸变的立方体构型,4个Ge原子和4个N原子构成了中心立方体的 8个顶点。其中 Ge—N键长为 0.203 6(3) nm,N—Ge—N与 Ge—N—Ge的键角分别为 85.51(18)°和94.32(16)°,立方体的侧面接近平行四边形。理论计算首次揭示了四锗卡宾2的成键面貌。自然键轨道(NBO)给出Ge₄N₄骨架上的20个分子轨道。轨道定域化的计算结果完好地呈现出4对Ge孤对电子、12个Ge—N键和4个Si—N键的定域轨道,能量分别为-12.22、-15.12 和-20.12 eV。Ge 孤对电子主要保留了 4s 电子的特性,而 Ge—N 键主要由 N 的 2s 轨道(18.4%)和 2p 轨道(71.3%)、Ge的4s轨道(0.75%)和4p轨道(9.43%)综合贡献形成。在化合物3的分子中,Ge^Ⅳ采取sp³杂化,由于空间位阻与非对称配位,与另外4个配位原子形成非对称四面体构型。     

Ultrasound-Directed Symmetry Breaking and Spin Filtering of Supramolecular Assemblies from only Achiral Building Blocks

Herein we describe the self-assembly of an achiral molecule into macroscopic helicity as well as the emergent chiral-selective spin-filtering effect. It was found that a benzene-1,3,5-tricarboxamide (BTA) motif with an aminopyridine group in each arm could coordinate with Ag^I and self-assemble into nanospheres. Upon sonication, symmetry breaking occurred and the nanospheres transferred into helical nanofibers with strong CD signals. Although the sign of the CD signals appeared randomly, it could be controlled by using the as-made chiral assemblies as a seed. Furthermore, it was found that the charge transport of the helical nanofibers was highly selective with a spin-polarization transport of up to 45 %, although the chiral nanofibers are composed exclusively from achiral building blocks. This work demonstrates symmetry breaking under sonication and the chiral-selective spin-filtering effect.     

Theoretical Study of Small Water Clusters of Sulfur Dioxide

The intermolecular clusters of sulfur dioxide with water, SO2(H2O)n (n = 2～5), are studied by using B3LYP density functional theory and MP2 ab initio methods along with the large basis sets (6-311++G(d,p) and aug-cc-pVDZ). The equilibrium geometries, intermolecular binding energies, and anharmonic frequencies of the clusters are calculated and compared with those of pure water clusters and available experiments. SO2 tends to form cyclic hydrogen-bonded complexes with two or three water molecules. In the larger clusters, however, water molecules begin to retain the structure of pure water clusters and segregate from SO2. Infrared absorption assignments for the small clusters are discussed to resolve a possible incorrect assignment in a recent spectroscopic experiment on the clusters.     

1,10-邻菲咯啉衍生物La(Ⅲ)配合物的电子结构与抗癌活性

对一系列1,10-邻菲咯啉衍生物La（Ⅲ）配合物,用密度泛函（DFT）法,在B3LYP／LanL2DZ水平进行理论研究。探讨了配合物的电子结构与其抗癌活性的关系,发现偶极矩（μ）和原子净电荷（Q）都对配合物的抗癌活性有影响,但不起决定性作用,而配合物的LUMO的能量（ELUMO）是决定其抗癌活性强弱的主要因素。并且揭示了配体上侧链烷基链的增长并不是获得高活性分子的最佳途径,而侧链上苯环引入却为设计活性更强的分子提供了可能性。基于理论研究结果,设计了三个具有更高抗癌活性的新配合物。