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91.
Gaspar AB Ksenofontov V Reiman S Gütlich P Thompson AL Goeta AE Muñoz MC Real JA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(36):9289-9298
The crystal structure of the complex [{Fe(bt)(NCS)(2)}(2)bpym] (1) (bt=2,2'-bithiazoline, bpym=2,2'-bipyrimidine) has been solved at 293, 240, 175 and 30 K. At all four temperatures the crystal remains in the P space group with a=8.7601(17), b=9.450(2), c=12.089(3) A, alpha=72.77(2), beta=79.150(19), gamma=66.392(18) degrees , V=873.1(4) Angstrom(3) (data for 293 K structure). The structure consists of centrosymmetric dinuclear units in which each iron(II) atom is coordinated by two NCS(-) ions in the cis position and two nitrogen atoms of the bridging bpym ligand, with the remaining positions occupied by the peripheral bt ligand. The iron atom is in a severely distorted octahedral FeN(6) environment. The average Fe--N bond length of 2.15(9) Angstrom indicates that compound 1 is in the high-spin state (HS-HS) at 293 K. Crystal structure determinations at 240, 175 and 30 K gave a cell comparable to that seen at 293 K, but reduced in volume. At 30 K, the average Fe--N distance is 1.958(4) Angstrom, showing that the structure is clearly low spin (LS-LS). At 175 K the average Fe--N bond length of 2.052(11) Angstrom suggests that there is an intermediate phase. M?ssbauer investigations of the light-induced excited spin state trapping (LIESST) effect (lambda=514 nm, 25 mW cm(-2)) in 1 (4.2 K, H(ext)=50 kOe) show that the excited spin states correspond to the HS-HS and HS-LS pairs. The dynamics of the relaxation of the photoexcited states studied at 4.2 K and H(ext)=50 kOe demonstrate that HS-HS pairs revert with time to both HS-LS and LS-LS configurations. The HS-LS photoexcited pairs relax with time back to the ground LS-LS configuration. Complex [{Fe(0.15)Zn(0.85)(bt)(NCS)(2)}(2)bpym] (2) exhibits a continuous spin transition centred around 158 K in contrast to the two-step transition observed for 1. The different spin-crossover behaviour observed for 2 is due to the decrease of cooperativity (intermolecular interactions) imposed by the matrix of Zn(II) ions. This clearly demonstrates the role of the intermolecular interactions in the stabilization of the HS-LS intermediate state in 1. 相似文献
92.
The triazine-based charring agent (CFA) with perfect charring ability was synthesized and characterized. The synergistic effects between CFA and aluminum phosphinate (AlPi) on flame retardancy, thermal degradation, and flammability properties of thermoplastic polyester-ether elastomer (TPEE) were investigated by limiting oxygen index (LOI), vertical burning test (UL-94), cone calorimeter test (CCT), thermogravimetric analysis (TGA), laser Raman spectroscopy (LSR) and scanning electron microscopy (SEM). The results from UL-94 test showed that, by compounding 14 wt% AlPi and 4 wt% CFA with TPEE, the LOI value reached 28.5% and the UL-94 rating reached V-0 (1.6 mm). TGA results indicated that there is good synergistic charring ability between CFA and AlPi, especially the increased residues at high temperature (T > 700 °C). The CCT test results showed that CFA could change the combustion behavior of TPEE and effectively accelerate the formation of expanded carbon layers. The residues after combustion were measured by LRS and SEM, demonstrating that CFA can promote the formation of dense and stable carbon layers during the combustion, which could inhibit the melt dropping and improve the fire retardancy of TPEE composites. Thus, CFA was a promising synergistic agent in halogen-free flame retardant TPEE. 相似文献
93.
Li‐Yuan Wu Yan‐Fei Mu Xiao‐Xuan Guo Wen Zhang Zhi‐Ming Zhang Min Zhang Tong‐Bu Lu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(28):9591-9595
Improving the stability of lead halide perovskite quantum dots (QDs) in a system containing water is the key for their practical application in artificial photosynthesis. Herein, we encapsulate low‐cost CH3NH3PbI3 (MAPbI3) perovskite QDs in the pores of earth‐abundant Fe‐porphyrin based metal organic framework (MOF) PCN‐221(Fex) by a sequential deposition route, to construct a series of composite photocatalysts of MAPbI3@PCN‐221(Fex) (x=0–1). Protected by the MOF the composite photocatalysts exhibit much improved stability in reaction systems containing water. The close contact of QDs to the Fe catalytic site in the MOF, allows the photogenerated electrons in the QDs to transfer rapidly the Fe catalytic sites to enhance the photocatalytic activity for CO2 reduction. Using water as an electron source, MAPbI3@PCN‐221(Fe0.2) exhibits a record‐high total yield of 1559 μmol g?1 for photocatalytic CO2 reduction to CO (34 %) and CH4 (66 %), 38 times higher than that of PCN‐221(Fe0.2) in the absence of perovskite QDs. 相似文献
94.
The equilibrium solubility of acetaminophen in methanol + water binary mixtures at 298.15 K was determined and correlated with the Jouyban–Acree model. Preferential solvation parameters by methanol (δx1,3) were derived from their thermodynamic solution properties by means of the inverse Kirkwood–Buff integrals method. δx1,3 values are negative in water-rich mixtures but positive in compositions from 0.32 in mole fraction of methanol to pure methanol. It is conjecturable that in the former case, the hydrophobic hydration around non-polar groups plays a relevant role in the solvation. The higher solvation by methanol in mixtures of similar cosolvent compositions and methanol-rich mixtures could be explained in terms of the higher basic behavior of this cosolvent. 相似文献
95.
96.
This work presents an automatic system, based on an electronic tongue, for resolution of mixtures of three pesticides. Inhibition detections were performed during the steady state of biosensors response. Three biosensors were built using two enzymes, electric eel (EE), genetically-modified Drosophila melanogaster (B131), and electric eel co-immobilized with drosophila melanogaster (BH). Calibrations curves for paraoxon, dichorlvos, and carbofuran were performed in the ranges 0.4–50.4 µM, 0.01–1.01 µM, 0.01–0.41 µM with LOD of 3.91 × 10?8, 6.30 × 10?11, and 5.84 × 10?10, respectively. An artificial neural network (ANN) was used to model the combined response of three pesticides. A set of 19 mixtures were prepared in order to train the artificial neural network, the modeling was validated with a set of 6 spiked samples of river water. The error and recovery yields were found in consistent with expected values. 相似文献
97.
The lack of authentic standards limits the quantitative analysis of herbal drugs in biological samples. This present work demonstrated a practicable assay of herbs and their metabolites independent of the availability of authentic standards. A liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) method for the qualitative and quantitative determination of the metabolites after oral administration of Evodiae fructus and Zuojinwan preparation in rat urine has been developed. Urine samples extracted with a protein precipitation procedure were separated on a C(18) column using a mixture of water (containing 0.1% formic acid) and acetonitrile (30:70, v/v) as mobile phase. The detection was performed by MS with electrospray ionization interface in positive selected reaction monitoring (SRM) mode. One urine sample after administration was selected as 'standard'. The method validation was carried out according to a conventional method that was calibrated by authentic standards. The fully validated method was applied to the pharmacokinetic study of the metabolites in rat urine. The results could provide evidence to explain the combination of Coptidis rhizoma and Evodiae fructus in terms of elimination. 相似文献
98.
Alicia Monleón Prof. Dr. Gonzalo Blay Prof. Dr. Luis R. Domingo Prof. Dr. M. Carmen Muñoz Prof. Dr. José R. Pedro 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):14852-14860
A very efficient synthesis of 5‐halogen‐1,3‐oxazin‐2‐ones has been accomplished by the halocyclisation reaction of chiral nonracemic N‐carbobenzyloxy (N‐Cbz)‐protected propargylic amines by using I2, Br2 and Cl2 as electrophile sources. The nature of the halogen influences the reaction time and yield. However, in all cases the reaction is totally regioselective taking place through a 6‐endo‐dig process regardless of the nature of the halogen and of the substituents in the starting material. To rationalise the experimental results, theoretical studies at the B3LYP/6‐311G* level have been performed. 相似文献
99.
Dai Y Mu X Tan Y Lin K Yang Z Zheng N Fu G 《Journal of the American Chemical Society》2012,134(16):7073-7080
Carbon monoxide can adsorb specifically on Pd(111) to induce the formation of unique Pd nanostructures. In the copresence of CO and H(2), single-crystalline Pd tetrapod nanocrystals have now been successfully prepared. The Pd tetrapods are enclosed by (111) surfaces and are yielded through hydride formation. Density functional theory calculations revealed that the formation of PdH(x) in the presence of H(2) reduces the binding energy of CO on Pd and thus helps to decrease the CO coverage during the synthesis, which is essential to the formation of the PdH(x) tetrapod nanocrystals. In addition to tetrapod nanocrystals, tetrahedral nanocrystals were also produced in the copresence of CO and H(2) when the reaction temperature was ramped to further lower the CO coverage. Upon aging in air, the as-prepared PdH(x) nanocrystals exhibited a shape-dependent hydrogen releasing behavior. The conversion rate of PdH(x) tetrapod nanocrystals into metallic Pd was faster than that of tetrahedral nanocrystals. 相似文献
100.
Supercritical fluid chromatography with photodiode array detection for pesticide analysis in papaya and avocado samples 下载免费PDF全文
Norma S. Pano‐Farias Silvia G. Ceballos‐Magaña Jorge Gonzalez José M. Jurado Roberto Muñiz‐Valencia 《Journal of separation science》2015,38(7):1240-1247
To improve the analysis of pesticides in complex food matrices with economic importance, alternative chromatographic techniques, such as supercritical fluid chromatography, can be used. Supercritical fluid chromatography has barely been applied for pesticide analysis in food matrices. In this paper, an analytical method using supercritical fluid chromatography coupled to a photodiode array detection has been established for the first time for the quantification of pesticides in papaya and avocado. The extraction of methyl parathion, atrazine, ametryn, carbofuran, and carbaryl was performed through the quick, easy, cheap, effective, rugged, and safe methodology. The method was validated using papaya and avocado samples. For papaya, the correlation coefficient values were higher than 0.99; limits of detection and quantification ranged from 130–380 and 220–640 μg/kg, respectively; recovery values ranged from 72.8–94.6%; precision was lower than 3%. For avocado, limit of detection values were ?450 μg/kg; precision was lower than 11%; recoveries ranged from 50.0–94.2%. Method feasibility was tested for lime, banana, mango, and melon samples. Our results demonstrate that the proposed method is applicable to methyl parathion, atrazine, ametryn, and carbaryl, toxics pesticides used worldwide. The methodology presented in this work could be applicable to other fruits. 相似文献