meso—四（4—磺酸苯基）卟啉与铅显色反应及其应用

研究了铅与meso-四(4-磺酸苯基)卟啉(TPPS_4)的显色反应条件,试验发现,在盐酸羟胺存在下和碱性(pH 12)介质中,铅与TPPS_4在室温即可络合完全,络合比为1:1,摩尔吸光系数ε=2.64X10~5,铅含量在0～2.0μg/10ml范围内呈线性,经APDC/MIBK 萃取分离,排除干扰后,用于自来水、桃叶中痕量铅的测定,结果满意.     

A "nanonecklace" synthesized from monofunctionalized gold nanoparticles

Gold nanoparticles with a single carboxylic acid group on the surface were prepared from a solid phase place exchange reaction and then coupled to polylysine using an in situ activation agent, diisopropylcarbodiimide (DIPCDI). The covalent amide bond linkage between the nanoparticles and polylysine and the ring closure of the polylysine chain have led to the formation of a nanoparticle/polymer hybrid material with "nanonecklace" structures.     

Quantum study of the N+N(2) exchange reaction: state-to-state reaction probabilities, initial state selected probabilities, Feshbach resonances, and product distributions

We report a detailed three-dimensional time-dependent quantum dynamics study of the state-to-state N+N(2) exchange scattering in the 2.1-3.2 eV range using a recently developed ab initio potential energy surface (PES). The reactive flux arrives at the dividing surface in the asymptotic product region in a series of six packets, instead of a single packet. Further study shows that these features arise from the "Lake Eyring" region of the PES, a region with a shallow well between two transition states. Trappings due to Feshbach resonances are found to be the major cause of the time delay. A detailed analysis of the Feshbach resonance features is carried out using an L(2) calculation of the metastable states in the "Lake Eyring" region. Strong resonance features are found in the state-to-state and initial state selected reaction probabilities. The metastable states with bending motions and/or bending coupled with stretching motions are found to be the predominant source of the resonance structure. Initial state selected reaction probabilities further indicate that the lifetimes of the metastable states with bending motions in the "Lake Eyring" region are longer than those of states with stretching motions and thus dominate the reactive resonances. Resonance structures are also visible in some of the integral cross sections and should provide a means for future experimental observation of the resonance behavior. A study of the final rotational distributions shows that, for the energy range studied here, the final products are distributed toward high-rotational states. Final vibrational distributions at the temperatures 2000 and 10,000 K are also reported.     

Crystal structures of anil of benzoylferrocene and its derivative of mercury: Specific arrangement of the ferrocenyl and phenyl groups around the C=N bond

The crystal structures of [(phenylimino) phenylmethyl]ferrocene (1) and 2-chloromercurio-1-[(phenylimino)phenylmethyl]ferrocene (2) have been determined by X-ray diffraction methods to obtain structural information on the anils of benzoylferrocene and their mercurated derivatives. The most striking feature is the specific arrangements of the phenyl and cyclopentadienyl rings around the C=N bond. It has been found that the N-phenyl ring adopts a trans conformation with the ferrocenyl moiety, and the twist angles of both the N-phenyl and C-phenyl rings out of the plane of C=N bond are much larger than that of the s substituted ferrocenyl ring out of this plane. A comparison between the structures of 1 and 2 is presented. The intramolecular coordination between the Hg and N in compound 2 is confirned, showing an N---Hg distance of 2.870 Å, shorter than the sum of van der Waals radii of N and Hg (3.05–3.15 Å).     

Liquid phase oxidation of benzene to phenol over K2Cr2O7/SiO2

MoO₃/Al₂O₃ is reduced at least partly by sulfur which is formed from H₂S in sulfidation with H₂S/N₂ mixture. SO₂ formation during TPD of MoO₃/Al₂O₃ with presorbed H₂S provides evidence for the explanation.

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MoO₃/Al₂O₃ , H₂S/N₂. SO₂ MoO₃/Al₂O₃, H₂S, .

     

Brønsted acid-catalyzed radical CH functionalization of acetone with N-allyl anilines to give 3-(3-oxobutyl)indolines

K₂S₂O₈ was unprecedentedly used instead of tert-butyl hydroperoxide (TBHP) in Brønsted acid-assisted catalytic strategy for ketonic radical generation, and the first Brønsted acid-catalyzed radical CH functionalization of acetone across unactivated alkenes is presented. In the presence of TsOH and K₂S₂O₈, N-allyl anilines underwent addition/cyclization cascade with acetone to afford 3-(3-oxobutyl)indolines with exo-selectivity and broad substrate scope at a relatively low temperature.     

Preparation of N,N'-bisethoxyethane[12]amideferrocenophane and its application in anion recognition

Novel N,N'-bisethoxyethane[12]amideferrocenophane has been synthesized by a condensation reaction and characterized by (1)H NMR and mass spectrum. The anion recognition properties of the compound are evaluated via (1)H NMR, FT-IR, and electrochemical measurement. It is found that N,N'-bisethoxyethane[12]amideferrocenophane exhibits remarkable electrochemical response to H(2)PO(4-) anion in CH(2)C(l2) or CH(3)CN solution, and response to anions can also be observed in CH(3)CN solution containing up to 15% water. Binding constants between the compound and HSO(4-) in different solutions have been determined by UV-vis spectrum titration experiments. The results indicate that the compound shows a selective recognition trend of H(2)PO(4-) > HSO(4-) (F(-)) > Br(-).     

Determination of nitroimidazole antibiotics based on dispersive solid-phase extraction combined with capillary electrophoresis

For a long time, the detection of nitroimidazole antibiotics (NIABs) has been a research focus in environmental analytical chemistry. In this work, a novel technique for the analysis of nitroimidazoles was established based on capillary electrophoresis (CE). UiO-66, synthesized using a solvothermal method, was utilized as an adsorbent in the dispersive solid-phase extraction (DSPE) of five different NIABs. The separation and detection of NIABs in environmental water samples were accomplished using the CE diode array detection method. The optimal extraction conditions were obtained after systematically studying the effects of adsorption time, the amount of extractant, and elution solvent on extraction efficiency. According to the results of the study, the limit of detections of the five NIABs were between 16 and 97 ng/mL, the relative standard deviations were between 0.32% and 0.55%, and the spike recoveries were between 87.43% and 104.8%. This study presents a novel technique for measuring NIABs in complex water samples.     

Synthesis,Crystal Structure,and Emission Spectra of Lanthanum(III) Coordination Polymer with 1,5‐Naphthalenedisulfonate Ligand

The first two‐dimensional lanthanum(III) coordination polymer, [La(1,5‐NDS)_1.5(H₂O)₅]_n (1) (1,5‐NDS^2? = 1,5‐naphthalenedisulfonate), was synthesized and structurally characterized by single‐crystal X‐ray diffraction analysis. The disulfonate ligands act in the η¹:η¹:μ₂ and η¹:η¹:η¹:μ₃ binding modes to link the LaO₉ tricapped trigonal prisms into a lamellar structure. It exhibits strong purple emission in the solid state.