多级孔NiMo负载TS-1分子筛催化剂的制备及其加氢脱硫性能

钛硅(TS-1)分子筛的微孔孔道严重限制了其在复杂分子催化转化中的应用,为了克服这一问题,通过酸洗脱、碱刻蚀及二者相结合的方法制备了多级孔 TS-1 分子筛,并采用等体积共浸渍法制备了相应的 NiMo 负载型催化剂;使用 X 射线衍射(XRD)、N₂吸附-脱附、吡啶吸附红外光谱(Py-FTIR)、氢气程序升温还原(H₂-TPR)、X射线光电子能谱(XPS)和高分辨透射电子显微镜(HR-TEM)等方法对多级孔TS-1分子筛的理化性质进行了表征;以二苯并噻吩(DBT)为探针对催化剂的加氢脱硫(HDS)性能进行了评价。结果表明,和常规TS-1分子筛相比,多级孔TS-1分子筛保持了MFI拓扑结构,比表面积增大且具有介孔结构,分子筛表面形成了适量的Brønsted酸中心;相应催化剂上活性金属与载体间相互作用得以改善,MoS₂片晶长度和堆垛层数适宜,形成了更多的 NiMoS活性相;催化剂活性和选择性均有所提升,尤其是酸洗脱获得的 NiMo/AT-TS-1催化剂的活性相较未经处理的NiMo/TS-1催化剂提升了1.2倍,直接脱硫(DDS)路径选择性提升了22%。     

Magnetism‐Tunable Oligoacene Dioxide Diradicals: Promising Magnetic Oligoacene‐Like Molecules

Graphene oxide has attracted intense research interest recently because the graphene oxide synthesis route, as a promising alternative for cost‐effective mass production of graphene, has been explored. To further study the oxidation process and possible mechanism and to explore applicability of the oxidized products, we have performed a computational study on three series of oligoacene dioxides, focusing on their structures and electronic properties. Taking 1,5‐dioxidized naphthalene as a starting point, three series of oligoacene dioxides are considered as follows: 1) middle insertion by 1–2 benzene rings; 2) single‐side expansion using 1–2 benzene rings; 3) double‐side expansion using two benzene rings. On the basis of density functional theory and complete active space self‐consistent field (CASSCF) calculations, we reveal that oligoacene dioxides in the middle insertion series have a triplet ground state, whereas those in the single‐side expansion series and the double‐side expansion series have open‐shell broken‐symmetry singlet diradical ground states except for their common origin naphthalene‐1,5‐dioxide whose ground state is triplet and which is also viewed as the origin of the middle insertion series. Magnetic coupling interactions of these oligoacene dioxides are also determined. This work should help people toward an atomistic understanding of the electronic structures and properties of possible intermediates or products and even the oxidation mechanism of graphene sheets, and provides a reasonable strategy of designing novel graphene‐oxide‐based magnetic materials.     

固相萃取-亲水相互作用色谱/串联质谱法同时测定食品中三聚氰胺和三聚氰酸

建立了固相萃取-亲水相互作用色谱/串联质谱同时测定食品中三聚氰胺和三聚氰酸残留量的方法。采用乙腈和水提取试样中残留的三聚氰胺和三聚氰酸,正己烷脱脂,提取液经亲水性键合硅胶和阳离子交换树脂复合填料柱(MCT柱)净化。采用亲水相互作用色谱柱进行分离,质谱采用正、负离子切换模式电离,多反应监测模式检测,同位素内标法定量。三聚氰胺和三聚氰酸在10～2500 μg/L范围内呈线性相关,相关系数(r)均大于0.99,定量限分别为25和50 μg/kg。本方法在动物源性食品、植物源性食品、乳及乳制品等不同样品中的三聚氰胺和三聚氰酸高、中、低3个添加水平的回收率分别在70.0%～129.6%和70.0%～128.6%之间,相对标准偏差分别在1.4%～23.3%和2.8%～18.7%之间。该方法可满足食品中三聚氰胺和三聚氰酸同时定量测定的需要。     

球状多孔Pd纳米粒子超结构的合成及其对甲酸的电催化氧化

在丙酮／水混合溶剂中,以氯代十六烷基吡啶为结构导向剂,水合肼还原PdCl42-,制得了直径范围在30～50nm之间的球状多孔Pd纳米粒子超结构．实验表明,氯代十六烷基吡啶对球状多孔Pd纳米粒子超结构的形成起着重要的作用,不加该表面活性剂时,得到的是实心Pd纳米粒子;而丙酮主要影响表面活性剂胶束的尺寸．此外,本文还研究了球状多孔Pd纳米粒子超结构对甲酸氧化的电催化活性,在0．5mol／L H2SO4＋0．5mol／L HCOOH溶液中的循环伏安结果表明,球状多孔Pd纳米粒子超结构修饰电极在酸性溶液中电催化氧化甲酸的峰电流约为180mA／mg,明显优于实心Pd纳米粒子修饰电极（峰电流为120mA／mg）,且表现出较高的稳定性．     

钌-菲罗啉卟啉的合成及与DNA的相互作用

以5-(4-羟基苯基)-10,15,20-三苯基卟啉和钌-菲罗啉衍生物为原料, 合成了3个两亲性钌-菲罗啉卟啉化合物, 并通过核磁共振波谱、红外光谱、紫外-可见光谱、质谱和元素分析等对化合物的结构进行了确证. 采用紫外-可见光谱、 荧光发射光谱和圆二色光谱考察了目标化合物与ct-DNA的相互作用, 研究了它们与DNA的结合模式. 实验结果表明, Por1, Por2和Por3与DNA的结合常数分别为1.46×10⁵, 2.75×10⁵和5.69×10⁵ L/mol. 此外, 在不同DNA浓度下, Por1和Por2与DNA的结合模式为插入模式和外部结合模式共存, Por3与DNA的结合模式主要为自堆积的外部键合和静电作用. 结果表明, 钌-菲罗啉卟啉化合物是新型的光动力治疗试剂.     

亚临界水萃取及气相色谱-串联质谱法检测红茶中多种农药残留

建立了亚临界水萃取及气相色谱-串联质谱(GC-MS/MS)检测红茶中21种有机氯和拟除虫菊酯农药残留的方法。在萃取压力为5 MPa条件下,样品经150 ℃的亚临界水提取15 min后,将目标物转移至丙酮-正己烷(1:1, v/v)中,经ENVI-Carb固相萃取净化小柱净化,DB-5毛细管气相色谱柱分离,在多反应监测(MRM)模式下进行MS/MS检测,基质匹配溶液内标法定量。各目标物在5.0～320.0 μg/L范围内线性关系良好,相关系数均大于0.99,其定量限(信噪比(S/N)＞10)为50 ng/g,检出限(S/N＞3)为10 ng/g。茶叶基质中添加50、100和200 ng/g的标准品时,21种农药的回收率为70.18%～119.98%,相对标准偏差(RSD)为5.01%～11.76%。该方法的灵敏度、准确度和精密度均符合农药残留测定的技术要求,适用于红茶中有机氯和拟除虫菊酯农药残留的检测。     

Electronic and Optical Properties of KNbO3,NaNbO3 and K0.5 Na0.5 NbO3 in Paraelectric Cubic Phase：a Comparative First-principles Study

The structural,electronic and optical properties of KNbO 3 (KN),NaNbO3(NN)and K05 Na0.5NbO3(KNN) in paraelectric cubic phase were calculated employing the plane-wave pseudopotential method based on density functional theory (DFT).The calculated electronic structures of the three crystals show similar features in the valence bands and the lower conduction bands.However,the structures in higher conduction bands differ markedly due to the effect of Na and K atoms.The calculated optical properties reveal that the features of optical spectrum at low energy are dominated by the transitions from O2p valence bands to Nb 4d conduction bands and those at high energy are related to the transitions to K 4s4p and/or Na 3s3p states.Moreover,the optical constants of KNN are approximately the average of KN and NN at high energy.Therefore,the optical properties of KNN in high energy region can probably be altered by changing the ratio of Na/K.     

白藜芦醇类似物与人血清白蛋白的相互作用

采用荧光光谱、三维荧光光谱、紫外吸收光谱研究白藜芦醇类似物(Z)-2-(3,4-二甲氧苯基)-3-(4-二甲氨基苯基)丙烯腈(HCQ)与人血清白蛋白(HSA)的相互作用,探讨其作为抗肿瘤药物的可能。结果发现HCQ与HSA形成了基态配合物,HCQ主要结合于HSA的位点Ⅰ,与位点Ⅱ也有微量的结合,反应为自发的放热反应,其ΔH、ΔS、ΔG均小于零,二者之间的结合力为氢键或者范德华力,结合常数为104～105数量级。HCQ与HSA的结合使HSA构象发生变化,Trp-214所处的环境疏水性增加,使得其内源性荧光显著降低。说明合成的白藜芦醇类似物能够与人血清白蛋白结合。     

均苯四甲酸酐改性花生壳粉吸附阳离子红染料的研究

以花生壳粉(PS)为生物基质,甲苯-2,4-二异氰酸酯(TDI)为交联剂,均苯四甲酸酐(PMDA)为改性剂,制备了均苯四甲酸酐改性花生壳粉(PMPS)吸附剂,并研究了PMPS对阳离子红染料吸附效果的影响因素。结果表明,在25℃,吸附时间3 h,pH值为2.0时,PMPS处理浓度为400.0 mg/mL的阳离子红溶液25 mL,最大吸附容量Q为177.2 mg/g,是未改性花生壳粉的2.2倍。改性花生壳粉吸附模式为Langmuir单分子层化学吸附。     

氨酪酸与邻硝基酚的荷移反应研究

采用分光光度法研究了氨酪酸与邻硝基酚的荷移反应。由实验得知,用二甲亚砜做溶剂,室温下反应10 min后,可生成稳定的1∶1型的黄色络合物,其最大吸收波长λmax=446 nm,氨酪酸的浓度在2～16μg/mL的范围内遵循比尔定律,表观摩尔吸光系数ε=3.7×103L·mol-1·cm-1,桑德尔灵敏度S=0.028μg·cm-2。用拟定的方法测定氨酪酸片的含量,回收率在97.0%～102.7%范围内,相对标准偏差不大于2.1%。