连续流动-分光光度法测定固体废物中氰化物浸出毒性的研究

建立了一种利用连续流动-分光光度法测定固废中氰化物的浸出毒性的方法,当氰化物浓度在0~200μg/L范围内,校准曲线的相关系数r为0.9998;方法的检出限可以达到0.33μg/L;不同浓度样品测定的相对标准偏差低于2.6%,实际固体废物样品加标回收率为96%~103%,方法精密度良好并且准确度较高;通过实际样品测定结果比对,证明方法与传统国家标准方法测定结果有着较高的吻合度,具有良好的应用前景。     

Discontinuous solid solutions of anthracene–phenanthrene: Thermodynamics and crystallization kinetics

We explored such issues as the formation mechanism, structure and propriety of the solid solutions of anthracene (ANT)–phenanthrene (PHE). Solution crystallization and solid-state grinding were employed to prepare solid solutions under different conditions. The thermal behavior and PXRD scanning results revealed the formation of discontinuous solid solutions, whose melting points and crystal lattices varied linearly with mixed ratio. Combing with Materials Studio, the formation possibility of solid solutions were investigated by evaluating the change of the energy. The crystal morphology of the solid solutions have a positive correlation with the change of the major part. Finally, the solution crystallization process of solid solution were studied using the population balance model.     

WO3/ZrO2固体酸催化苯与1-己烯烷基化反应

 用浸渍法制备了WO3/ZrO2及碱金属K或碱土金属Sr掺杂改性的WO3/ZrO2固体酸催化剂. 采用X射线衍射、 N2吸附、 NH3程序升温脱附和吸附吡啶的红外光谱等技术表征了K或Sr对WO3/ZrO2催化剂结构和表面酸性质的影响. 研究了WO3/ZrO2及K或Sr掺杂改性的WO3/ZrO2固体酸对苯与1-己烯烷基化反应的催化性能. 考察了催化剂制备条件和反应条件对催化剂活性的影响以及催化剂的重复使用性. 结果表明,引入K或Sr可调变WO3/ZrO2固体酸中的ZrO2晶相和固体酸的酸强度、酸量以及Lewis酸中心与Brnsted酸中心的比值. 适量K或Sr掺杂改性可提高WO3/ZrO2催化剂对苯与1-己烯烷基化反应的催化活性和稳定性,在常压和80 ℃的温和条件下,反应10 min后, 1-己烯的转化率可达99%, 单烷基选择性为100%. 该催化剂可多次重复使用,催化活性稳定.     

Synthesis of Oligomeric Axially Bridged Ruthenium Phthalocyanines and 2,3-Naphthalocyanines

Bridged 2,3-naphthalocyaninatoruthenium oligomers {[MacRu(L)] _n } were synthesized and characterized using solid-state methods. For comparison, soluble t-butyl substituted phthalocyaninatoruthenium oligomers were prepared and their chain length examined by ¹H NMR spectroscopy. The powder conductivities of all bridged compounds ([MacRu(L)] _n ) were measured and the dependence of the conductivities on the bridging ligands is discussed.     

Emission Quenching in Tetraphenylfuran Crystal: Why This Propeller-Shaped Molecule Does Not Emit in the Condensed Phase

Due to their substantial fluorescence quantum yields in the crystalline phase, propeller-shaped molecules have recently gained significant attention as potential emissive materials for optoelectronic applications. For the family of cyclopentadiene derivatives, light-emission is highly dependent on the nature of heteroatomic substitutions. In this paper, we investigate excited state relaxation pathways in the tetraphenyl-furan molecule (TPF), which in contrast with other molecules in the family, shows emission quenching in the solid-state. For the singlet manifold, our calculations show nonradiative pathways associated with C-O elongation are blocked in both vacuum and the solid state. A fraction of the population can be transferred to the triplet manifold and, subsequently, to the ground state in both phases. This process is expected to be relatively slow due to the small spin-orbit couplings between the relevant singlet-triplet states. Emission quenching in crystalline TPF seems to be in line with more efficient exciton hopping rates. Our simulations help clarify the role of conical intersections, population of the triplet states and crystalline structure in the emissive response of propeller-shaped molecules.     

Cobalt Element Effect of Ternary Mesoporous Cerium Lanthanum Solid Solution for the Catalytic Conversion of Methanol and CO2 into Dimethyl Carbonate

A citric acid ligand assisted self-assembly method is used for the synthesis of ternary mesoporous cerium lanthanum solid solution doped with metal elements (Co, Zr, Mg). Their textural property was characterized by X-ray diffraction, transmission electron microscopy, N₂ adsorption-desorption, X-ray photoelectron spectroscopy and TPD techniques, and so on. The results of catalytic testing for synthesis of dimethyl carbonate (DMC) from CH₃OH and CO₂ indicated that the DMC yield reached 316 mmol/g on Ce-La-Co solid solution when the reaction temperature was 413 K and the reaction pressure was 8.0 MPa. It was found that Co had synergistic effect with La and Ce, doping of Co on the mesoporous Ce-La solid solution was helpful to increase the surface area of the catalyst, promote CO₂ adsorption and activation, and improve the redox performance of solid solution catalyst. The conversion of Co²⁺ to Co³⁺ resulted in the continuous redox cycle between Ce⁴⁺ and Ce³⁺, and the oxygen vacancy content of the catalyst was increased. Studies have shown that the catalytic performance of Ce-La-Co solid solution is positively correlated with oxygen vacancy content. On this basis, the reaction mechanism of DMC synthesis from CO₂ and CH₃OH on the catalyst was speculated.     

Beta-Cyclodextrin-Decorated Magnetic Activated Carbon as a Sorbent for Extraction and Enrichment of Steroid Hormones (Estrone, β-Estradiol,Hydrocortisone and Progesterone) for Liquid Chromatographic Analysis

A β-cyclodextrin-decorated magnetic activated carbon adsorbent was prepared and characterized using various analytical techniques (X-ray diffraction (XRD), scanning electron microscopy–electron diffraction spectroscopy (SEM-EDS) and transmission electron microscopy (TEM)), and the adsorbent was used in the development of a magnetic solid-phase microextraction (MSPE) method for the preconcentration of estrone, β-estradiol, hydrocortisone and progesterone in wastewater and river water samples. This method was optimized using the central composite design in order to determine the experimental parameters affecting the extraction procedure. The quantification of hormones was achieved using high-performance liquid chromatography equipped with a photodiode array detector (HPLC-DAD). Under optimum conditions, the linearity ranged from 0.04 to 300 µg L⁻¹ with a correlation of determinations of 0.9969–0.9991. The limits of detection and quantification were between 0.01–0.03 and 0.033–0.1 µg L⁻¹, with intraday and interday precisions at 1.1–3.4 and 3.2–4.2. The equilibrium data were best described by the Langmuir isotherm model, and high adsorption capacities (217–294 mg g⁻¹) were obtained. The developed procedure demonstrated high potential as an effective technique for use in wastewater samples without significant interferences, and the adsorbent could be reused up to eight times.     

pH-Responsive N^C-Cyclometalated Iridium(III) Complexes: Synthesis,Photophysical Properties,Computational Results,and Bioimaging Application

Herein we report four [Ir(N^C)₂(L^L)]ⁿ⁺, n = 0,1 complexes (1–4) containing cyclometallated N^C ligand (N^CH = 1-phenyl-2-(4-(pyridin-2-yl)phenyl)-1H-phenanthro[9,10-d]imidazole) and various bidentate L^L ligands (picolinic acid (1), 2,2′-bipyridine (2), [2,2′-bipyridine]-4,4′-dicarboxylic acid (3), and sodium 4,4′,4″,4‴-(1,2-phenylenebis(phosphanetriyl))tetrabenzenesulfonate (4). The N^CH ligand precursor and iridium complexes 1–4 were synthesized in good yield and characterized using chemical analysis, ESI mass spectrometry, and NMR spectroscopy. The solid-state structure of 2 was also determined by XRD analysis. The complexes display moderate to strong phosphorescence in the 550–670 nm range with the quantum yields up to 30% and lifetimes of the excited state up to 60 µs in deoxygenated solution. Emission properties of 1–4 and N^CH are strongly pH-dependent to give considerable variations in excitation and emission profiles accompanied by changes in emission efficiency and dynamics of the excited state. Density functional theory (DFT) and time-dependent density functional theory (TD DFT) calculations made it possible to assign the nature of emissive excited states in both deprotonated and protonated forms of these molecules. The complexes 3 and 4 internalize into living CHO-K1 cells, localize in cytoplasmic vesicles, primarily in lysosomes and acidified endosomes, and demonstrate relatively low toxicity, showing more than 80% cells viability up to the concentration of 10 µM after 24 h incubation. Phosphorescence lifetime imaging microscopy (PLIM) experiments in these cells display lifetime distribution, the conversion of which into pH values using calibration curves gives the magnitudes of this parameter compatible with the physiologically relevant interval of the cell compartments pH.     

纳米色料的制备及应用

纳米色料是一类可以结合颜料和染料两者优点的新型色料,除了在传统的着色领域具有独特优势外,在光电高新技术领域也具有广阔的应用前景。本文综述了国内外有机纳米色料在制备和应用上的最新研究进展,归纳出几种有代表性的制备有机纳米色料以及有机色料/无机物杂合纳米色料的最新研究方法。着重论述了细乳液聚合法制备纳米色料,对各种制备方法作出比较评价,并结合研究现状对纳米色料在光电领域的应用提出了一些设想。