Dirhodium(II) tetrakis[methyl 2-oxaazetidine-4-carboxylate]: a chiral dirhodium(II) carboxamidate of exceptional reactivity and selectivity

[formula: see text] A new chiral azetidinone-carboxylate ligand for dirhodium(II) catalysis enhances reactivity toward diazo decomposition and selectivity toward cyclopropanation enabling diazomalonates, vinyldiazoacetates, and aryldiazoacetates to be effectively used with a dirhodium(II) carboxamidate catalyst.     

Determination of atrazine, desethyl atrazine and desisopropyl atrazine in environmental water samples using hollow fiber-protected liquid-phase microextraction and high performance liquid chromatography

A new method based on hollow fiber-protected liquid-phase microextraction (LPME) was developed for the simultaneous determination of atrazine, desethyl atrazine and desisopropyl atrazine in environmental water samples. In LPME, analytes were extracted into 1-octanol immobilized in the micropores of a poly(vinylidene fluoride) porous hollow fiber membrane, and back extracted into the acceptor (4 M HCl) filled in the lumen of the hollow fiber. After LPME, the analytes trapped in the acceptor were analyzed with high-performance liquid chromatography after neutralization. The effect of extraction factors such as sample pH, acceptor pH, salinity, extraction time, stirring rate, and humic acid were studied. Under the optimized conditions, the limits of detection and relative standard deviations were respectively in the range of 0.5–1.0 μg L⁻¹ and 3.9–4.7% (n = 5). The proposed method was applied to determine atrazine, desethyl atrazine and desisopropyl atrazine in wastewater and groundwater samples. The three analytes were below the limits of detection, but good relative spiked recoveries over 90.1 ± 5.9% at 5 μg L⁻¹ spiked level were obtained.     

Experimental and computational studies of intracomplex reactions in Mg+(primary, secondary alkylamine) complexes induced by photoexcitation of Mg+

We report herein a comprehensive study of photoinduced reactions in complexes of Mg+ with primary (n-propyl- and isopropylamine) and secondary amines (dipropyl- and diisopropylamine) in the spectral range of 230-440 nm. Similar to the methyl- and ethylamine complexes studied previously, N-H bond activation of these complexes is very unfavorable. Instead, the C(alpha)-C, C-N, and C(alpha)-H bond-cleavage photoproducts are observed after photoexcitation of the Mg+ complexes (3(2)P<--3(2)S). For Mg+(primary amine) complexes, for example, Mg+-NH2CH2CH2CH3, and Mg+-NH2CH(CH3)2, the photoproducts resulting from C(alpha)--C rupture prevail after P(z) and charge-transfer excitations, whereas the Mg+ photofragment is predominant upon P(x,y) excitation. However, with further N-alkyl substitution, as in Mg+(secondary amine) complexes, for example, Mg+-NH(CH2CH2CH3)2 and Mg+-NH[CH(CH3)2]2, a novel intracomplex C-C coupling photoreaction dominates on P(x,y) excitation of Mg+, which is believed to arise from Mg+* insertion into the C-N bond. With P(z) and charge-transfer excitation, the Mg-R elimination photoproducts, arising from C(alpha)-C bond cleavage, predominate. The energetics and possible mechanisms of the intracomplex photoreactions are analyzed in detail with the help of extensive quantum mechanics calculations.     

Fluorescent sensors for the enantioselective recognition of mandelic acid: signal amplification by dendritic branching

Novel chiral bisbinaphthyl compounds have been synthesized for the enantioselective fluorescent recognition of mandelic acid. By introducing dendritic branches to the chiral receptor unit, the fluorescence signals of the receptors are significantly amplified because of the light-harvesting effect of the dendritic structure. This has greatly increased the sensitivity of the sensors in the fluorescent recognition. Study of the three generation sensors demonstrates that the generation zero sensor is the best choice for the recognition of mandelic acid because of its greatly increased fluorescence signal over the core and its high enantioselectivity. This sensor is potentially useful for the high throughput screening of chiral catalysts for the asymmetric synthesis of alpha-hydroxycarboxylic acids.     

Bis(1,2-bis(diphenylphosphino)ethane)tungsten(0) Complexes Containing Electron-Saturated Metal Centers and Singly-Coordinated Bridging Ligands

Reaction of 1,4-diisocyanobenzene or 4-isocyanobenzonitrile with trans-W(N(2))(2)(DPPE)(2) (DPPE = 1,2-bis(diphenylphosphino)ethane) produced cis-WL(2)(DPPE)(2), where L = 1,4-diisocyanobenzene or 4-isocyanobenzonitrile. cis-(CNC(6)H(4)NC)(2)W(DPPE)(2) crystallizes in the triclinic space group P&onemacr;, with a = 12.848(3) ?, b = 13.596(3) ?, c = 19.072(3) ?, alpha = 78.99(2) degrees, beta = 70.66(2) degrees, gamma = 65.26(2) degrees, V = 2849.8(11) ?(3), and Z = 2. cis-(NCC(6)H(4)NC)(2)W(DPPE)(2) crystallizes in the triclinic space group P&onemacr;, with a = 12.712(3) ?, b = 13.700(3) ?, c = 19.109(3) ?, alpha = 77.91(2) degrees, beta = 70.63(2) degrees, gamma = 64.76(2) degrees, V = 2830.7(13) ?(3), and Z = 2. Both compounds possess a distorted octahedral geometry about the metal center, with the two isocyanide ligands cis to one another. The isocyanide ligands are substantially bent along the CNC axis of the isocyanide group coordinated to tungsten. For the complex containing the symmetric ligand, CNC(6)H(4)NC, the mean CNC angle for the coordinated end of the isocyanide is 139.1(11) degrees, the average W-C bond length is 1.86(1) ?, and the C&tbd1;N bond lengths have a mean value of 1.30(2) ?. These data indicate substantial back-donation from an electron-saturated tungsten atom. This is supported spectroscopically, with substantial shifts to lower wavenumbers for the C-N stretching frequencies of the coordinated isocyanide groups. Similar trends are observed in cis-(NCC(6)H(4)NC)(2)W(DPPE)(2). Both compounds contain electron-rich metals surrounded by large ligands which apparently protect the metals from atmospheric oxidation. The isocyanide ligands in both complexes contain a second coordinating group pointing away from the metal into the environment surrounding the molecules, providing the potential for polymetallic complexes containing metals in a variety of oxidation states.     

聚丙烯与SBS嵌段共聚物共混时的结晶行为

用偏光显微镜,小角光散射,动态力学测量和DSC等方法研究了聚丙烯和SBS共混物的结晶行为。结果表明,SBS的混入可以降低聚丙烯的结晶程度和阻碍球晶的形成,因而有利于提高聚丙烯塑料的抗冲击性能。从DSC实验也看到共混物中的聚丙烯具有较高的结晶速率。     

Spectrophotometric flow injection determination of trace iodide in table salt and laver through the reaction of iodate with 3,5-Br2-PADAP and thiocyanate

A new simple, rapid and sensitive spectrophotometric flow injection method for the determination of trace iodide is described based on an ion associate of iodate (IO₃ ^–) with 2- (3,5-dibromo-2-pyridylazo)-5-diethylamino-phenol (3,5-Br₂-PADAP) and thiocyanate (SCN^–). In a strongly acidic medium, this unstable violet product was formed with an absorption maximum at 605 nm. Flow injection is an ideal method to reproducibly monitor the transient signal. Various parameters were optimized using the Super Modified Controlled Weighted Centroid Simplex Method (SMCWC). Under the optimum experimental conditions, iodide could be determined in the range of 1.00 × 10^–6 and 2.4 × 10^–5 mol l^–1. The correlation coefficient of the calibration curve is 0.9991. With a sampling frequency of 80 h^–1, the detection limit for iodide is 5.0 × 10^–7 mol l^–1. The proposed method has been applied to the determination of trace iodide after oxidizing I^– in table salt or laver to IO₃ ^–. In addition, the mechanisms of the ion association reaction was studied. Received: 15 August 1996 / Revised: 10 October 1996 / Accepted: 16 October 1996     

Hydrothermal synthesis and crystal structure of a layered vanadium oxide with an interlayer metal coordination complex: [Co(phen)3][V10O26]·H2O

A novel compound, [Co(phen)₃][V₁₀O₂₆]·H₂O, was hydrothermally synthesized and characterized by single-crystal X-ray diffraction. This compound crystallizes in the orthorhombic space group Ccca with a=13.447(3), b=29.936(6), c=23.252(5) Å, V=9360(3) Å³, Z=8 and R=0.0285. Data were collected on a Rigaku R-AXIS RAPID IP diffractometer at 293 K in the range of 1.36<θ<24.99°. The structure of the compound consists of vanadium oxide layers, which are built up from the infinite VO₄ chains by corners and edges sharing. The [Co(phen)₃]²⁺ complexes occupy the interlayer space and contact each other via π−π stacking interactions of the phen groups to form infinite one-dimensional chains.     

胆汁酸盐对胆红素钙沉淀过程的影响

研究了六种人胆汁主要胆汁酸盐对胆红素钙沉淀形成过程的影响。用曲线拟合法处理数据取得热力学及动力学参数。结果表明,六种胆汁酸盐都表现动力学和热力学抑制,而且抑制作用有浓度依赖关系。在一定条件下出现诱导期。虽然不同胆汁酸盐的作用结果相似,但在相同条件下,二羟基胆汁酸和三羟基胆汁酸影响程度不同。