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941.

Abstract  

A new mixed-ligand nickel(II) coordination compound [Ni(bz)2(phen)2] (1) (bz = benzilate and phen = 1,10-phenanthroline) has been synthesized by refluxing nickel(II) acetate with benzilic acid and 1,10-phenantholine. Compound 1 has been characterized by elemental analysis, IR and electronic absorption spectroscopy, magnetic measurements, thermogravimetric analysis and single-crystal X-ray diffraction The crystal of 1 belongs to monoclinic crystal system, space group C2/c and its unit cell parameters are a = 25.881(3), b = 11.1728(15), c = 17.609(2) ? and β = 124.104(3)°. The effect of non-covalent interactions, such as π···π and C–H···π, on the 3D supramolecular organization of this molecular complex is analyzed.  相似文献   
942.
943.
It is well known that the static caching algorithm that keeps the most frequently requested documents in the cache is optimal in case when documents are of the same size and requests are independent and identically distributed. However, it is hard to develop explicit and provably optimal caching algorithms when requests are statistically correlated. In this paper, we show that keeping the most frequently requested documents in the cache is still optimal for large cache sizes even if the requests are strongly correlated.  相似文献   
944.
The compound Ru(bpy)2(dppz-R)(PF6)2, where bpy is 2,2'-bipyridine and dppz-R is 11-(diethoxyphosphorylmethyl)dipyrido[3,2-a:2',3'-c]phenazine, was prepared and anchored to mesoporous nanocrystalline (anatase) TiO2 thin films as a probe of the effects of interfacial water on excited-state charge transfer processes at semiconductor interfaces. In nitrogen-saturated fluid acetonitrile, the Ru(bpy)2(dppz-R)(PF6)2 compound was found to be highly photoluminescent. Water was found to quench the excited state by a mechanism adequately described by the Perrin model, from which the radius of quenching was abstracted, 75 +/- 2 A. The Ru(bpy)2(dppz-R)(PF6)2 compounds were found to bind to the TiO2 thin films in high surface coverages, 5 x 10(-8) mol cm(-2). When these films were immersed in acetonitrile, long-lived excited states (tau = 825 ns) that were quenched by the addition of water were observed. About 30% of the excited states could not be quenched by water. Efficient electron injection, phi(inj) = 0.8, was observed after light excitation of Ru(bpy)2(dppz-R)/TiO2 in a 0.1 M LiClO4/acetonitrile solution. The addition of large concentrations of water, >0.5 M, was found to decrease the injection yield to phi(inj) = 0.3.  相似文献   
945.
An analytical method for the simultaneous determination of codeine, morphine and 6-acetylmorphine (6AM) in human oral fluid was developed. The method involves liquid-liquid extraction in Toxitubes A, derivatization with 99:1 (v/v) N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA)/trimethylchlorosilane (TMCS), and gas chromatography/mass spectrometry with positive chemical ionization (GC/PCI-MS) determination. The detector response was linear over the concentration range 30-500 ng/mL with coefficients of correlation higher than 0.99. The precision was acceptable with coefficients of variation less than 7.5%. The limits of detection achieved were 0.7 ng/mL for codeine, 2.0 ng/mL for morphine, and 0.6 ng/mL for 6AM. The method proposed was applied to 80 oral fluid samples from opiates users, 98% of which were positive for the three analytes. Human oral fluid is a suitable biological fluid for the determination of opiates by GC/PCI-MS.  相似文献   
946.
A series of epoxy cured samples, with different molar composition of 1,4-butanediol diglycidyl ether (EP), cis-1,2-cyclohexanedicarboxylic anhydride (CH) and triethylamine (TEA) as initiator, was studied by Electrical Impedance Spectroscopy (EIS) in the frequency range 10−2-105 Hz. The resistivity of the system was evaluated by using the complex impedance analysis method. Resistivity values in the range between 107 and 1013 Ω cm were obtained and related to the composition (molar fraction xEP or xCH) of the epoxy system. The gel formation characteristics of the samples were obtained as theoretically described by Flory.  相似文献   
947.
We report on alkaline hydrolysis of tetraethoxysilane (St?ber synthesis) inside a macroporous polymer matrix resulting in a homogeneous coverage of silica onto the polymer surface. The encapsulation of the polymer struts by a continuous silica crust allows further functionalization with hydrophilic and hydrophobic silylating agents. The porous silica polymeric hybrid material combines the morphological control and mechanical flexibility of the polymeric matrix with the convenient surface modifications developed for glass and amorphous silica. This concept is applied to macroporous membranes where alteration in surface functionality allows tuning of hydrophobicity (contact angle and liquid entry pressure), streaming potential, and adsorption capacity of double-stranded DNA.  相似文献   
948.
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   
949.
In this paper, a multiresidue method for the analysis in soils of metribuzin (M) and its major conversion products, deaminometribuzin (DA), diketometribuzin (DK) and deaminodiketometribuzin (DADK) is developed. Considering the neutral and charged nature of the molecules, micellar electrokinetic chromatography (MEKC) is a very efficient method for the separation of these compounds, providing high efficiency and short analysis times. Different electrophoretic parameters were studied to optimize the separation, such as the buffer pH and concentration, sodium dodecyl sulphate (SDS) concentration, injection conditions and applied voltage. Excellent separation of the studied compounds was achieved within about 7 min. Soil samples were previously extracted using methanol in an ultrasonic bath and then a SPE procedure was applied to pre-concentrate the analytes by passage through a LiChrolut EN sorbent column. Detection limits at the low microgkg(-1) level were obtained. The proposed method has been satisfactorily applied in soil samples showing recoveries ranging from 86.7% to 104.2% and represents a valuable alternative to high-performance liquid chromatography (HPLC).  相似文献   
950.
Catanionic surfactants result from the pairing of oppositely charged amphiphilic molecules, forming a new class of surfactant molecules with various interesting lyotropic and thermotropic properties. With the aim of probing the role of both headgroup chemical nature/structure and molecular shape, a series of catanionic surfactants were synthesized. The cationic portion of the molecule is kept constant, being the dioctadecyldimethylammonium double chain. Different single-chained surfactants with varying headgroups and chain lengths are used as the anionic pair. The thermotropic behavior has been studied by DSC and the mesophase structural investigated by polarized light microscopy. The results indicate that, for a given chain length, parameters such as headgroup polarity and charge density, as well as volume, influence the catanionic surfactant behavior. The thermodynamic parameters are qualitatively evaluated, considering the headgroup chemical nature and the overall molecular structure.  相似文献   
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