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1.
Cathode distribution on a metal surface, depending on the total length of three-phase boundary per unit area (L tpb), is an important factor influencing corrosion behavior of metals in gas/liquid/solid multiphase corrosion systems. The effect of L tpb on cathodic oxygen reduction process was first studied by steady-state polarization technique, and the result showed that the cathodic-limiting current densities linearly increased with increasing L tpb, indicating that the cathode distribution had an important influence on the corrosion behavior of metals. On this basis, a model is developed to establish the correlation between the cathodic-limiting current and L tpb. In the model, a general expression for the cathodic-limiting current distribution in TPB zone is deduced, and a linear dependence of the total cathodic-limiting current density on L tpb is established. The simulation result is in good agreement with experimental data.  相似文献   

2.
《Analytical letters》2012,45(9):1885-1898
ABSTRACT

This paper describes a very simple device that can be used for colorimetric quantitative determinations, including spot-test analysis. The sensor is a light detector resistor (LDR) placed into a black PTFE cell and coupled to a low cost multimeter (Ohmmeter). The device has been tested and is easy and fast to use. Quantitative studies were performed with KMnO4 solutions and with the vanadium (V)/PAR/H2O2 system. Calibration curves were obtained by plotting the electric resistance of the LDR against the concentration of the colored species from 0 (blank) to 4.0 × 10-3 mol L-1 for permanganate and from 0 (blank) to 5.0 × 10-5 mol L-1 for vanadium. The detection limit (3σ) was found to be about 5.0 × 10-5 mol L-1 for permanganate and 4.0 × 10-6 mol L-1 for vanadium. The device was used to analyze total vanadium, as vanadium (V), in wastes from an adipic acid plant. The results obtained clearly show that the device can be used for accurate, precise, fast, in situ and low cost colorimetric analysis including quantitative spot-test procedures.  相似文献   

3.
For one-dimensional model of porous electrode (PE), an equation for the ideal ratio between the local conductivities of liquid phase κL(x) and solid phase κs(x), which provides uniform distributions of potential and current inside the PE, is obtained. It is shown that the principal possibilities of levering action of both phases are similar; however, the shapes of their ideal conductivity profiles are mirror-opposite. To gain a beneficial effect at the expense of conductivity of liquid phase, κL(x) should increase monotonically from the rear current lead to the frontal side of PE provided that the conductivities of phases are equal in the middle of PE. The effect of distortions of ideal κL(x) profile is analyzed. It is found that, with regard to the natural upper limit of solution conductivity, the best conditions for the levering action of ideal κL(x) profile should be expected in the porous matrices with low conductivity. It is shown that the formation of even few zones with opposite-shaped κL(x) profile inside PE (the solution conductivity decreases towards the frontal side of PE) leads to more nonuniform potential distribution and a decrease in the PE operation efficiency (especially at high total current density).  相似文献   

4.
Previous pharmacological studies have indicated that diterpenoids are the primary effective chemical cluster in the seeds of Euphorbia lathyris L. The seed products are used in traditional Chinese medicine in the forms of Semen Euphorbiae (SE) and Semen Euphorbiae Pulveratum (SEP). However, the metabolism of the plant's diterpenoids has not been well elucidated, which means that the in vivo metabolite products have not been identified. The current study screened the physiological metabolites of six diterpenes [Euphorbia factor L1 (L1), L2 (L2), L3 (L3), L7a (L7a), L7b (L7b), and L8 (L8)] in feces and urine of rats after oral administration of SE and SEP using UHPLC-Q-Exactive MS. A total of 22 metabolites were detected in feces and 8 in urine, indicating that the major elimination route of diterpenoids is via the colon. Hydrolysis, methylation, and glucuronidation served as the primary metabolic pathways of these diterpenoids. In sum, this study contributed to the elucidation of new metabolites and metabolic pathways of SE and SEP, and the new chemical identities can be used to guide further pharmacokinetic studies.  相似文献   

5.
Experimental data on initial hydrate formation conditions have been obtained for the nitrogen-propane-water system in the L1HG, L1L2H, and L1L2HG regions, where L1 is the water rich liquid phase, L2 is the hydrocarbon rich liquid phase, H is the hydrate and the G is the vapor phase. The measurements covered a range of temperatures from about 275 to 293 K and pressures from about 0.3 to 17.0 MPa. The concentrations covered for the L1HG region extended from 0.94 to 75.0 mole percent propane in the gas phase, and for the L1L2H region they extended from 83.1 to 99.0 mole percent in the condensed liquid phase. Four-phase measurements were made at concentrations of propane from 18.1 to 71.1 mole percent in the gas phase.The experimental data were used to find a fitted binary interaction parameter for predicting hydrate formation in systems containing nitrogen and propane.  相似文献   

6.
In the present work, the two‐dimensional (2D) polymer poly[[μ4‐2‐(4‐nitrobenzenesulfonamido)benzoato‐κ4O1:O1:O1′:N6]silver(I)] (AgL), [Ag(C13H9N2O6S)]n, was obtained from 2‐(4‐nitrobenzenesulfonamido)benzoic acid (HL), C13H10N2O6S. FT–IR, 1H and 13C{1H} NMR spectroscopic analyses were used to characterize both compounds. The crystal structures of HL and AgL were determined by single‐crystal X‐ray diffraction. In the structure of HL, O—H…O hydrogen bonds between neighbouring molecules result in the formation of dimers, while the silver(I) complex shows polymerization associated with the O atoms of three distinct deprotonated ligands (L?). Thus, the structure of the Ag complex can be considered as a coordination polymer consisting of a one‐dimensional linear chain, constructed by carboxylate bridging groups, running parallel to the b axis. Neighbouring polymeric chains are further bridged by Ag—C monohapto contacts, resulting in a 2D framework. Fingerprint analysis of the Hirshfeld surfaces show that O…H/H…O hydrogen bonds are responsible for the most significant contacts in the crystal packing of HL and AgL, followed by the H…H and O…C/C…O interactions. The Ag…Ag, Ag…O/O…Ag and Ag…C/C…Ag interactions in the Hirshfeld surface represent 12.1% of the total interactions in the crystal packing. Studies of the interactions of the compounds with human serum albumin (HSA) indicated that both HL and AgL interact with HSA.  相似文献   

7.
We study the self‐entanglement of a single linear polymer chain with N monomers confined to a cubic box (L × L × L) using the bond‐fluctuation lattice model and primitive path analysis. We probe chains with N between 30 and 750 and vary the degree of confinement L/Rg0 between 0.4 and 12, where Rg0 is the radius of gyration of an unconfined polymer. We find that the conformational properties Rg/Rg0 and Lp/Rg0, where Lp is the average primitive path length, collapse onto a single master curve as a function of the degree of confinement. In the strongly confined regime, L/Rg0 < 1, we find that Rg/Rg0 ~ (L/Rg0)0.8 and (Lp/Rg0) ~ (L/Rg0)?2. We verify that the simulation methodology used is quantitatively consistent with experimental data, and the Colby‐Rubinstein entanglement model for unconfined concentrated polymer solutions. The most significant difference between unconfined and confined systems is the variation of Lp with monomer density ?; Lp ~ ?5/9, in the former, and Lp ~ ?2/3, in the latter. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1283–1290  相似文献   

8.
Procedures have been developed to generate molecular electrostatic potentials based on correlated wave function from ab initio or semiempirical electronic structure programs. A new algorithm for point-wise sampling of the potential is described and used to obtain partial atomic charges via a linear, least squares fit between classical and quantum mechanical electrostatic potentials. The proposed sampling algorithm is efficient and promises to introduce less rotational variance in the potential derived partial charges than algorithms applied previously. Electrostatic potentials and fitted atomic charges from ab initio (HF/6–31G* and MP2/6-31G*) and semiempirical (INDO/S; HF, SECI, and SDCI) wave functions are presented for the electronic ground (S0) and excited (1Lb, 1La) states of 3-methylindole. © 1992 by John Wiley & Sons, Inc.  相似文献   

9.
Although tryptophan is a natural probe of protein structure, interpretation of its fluorescence emission spectrum is complicated by the presence of two electronic transitions, 1La and 1Lb. Theoretical calculations show that a point charge adjacent to either ring of the indole can shift the emission maximum. This study explores the effect of pyrrole and benzyl ring substitutions on the transitions' energy via absorption and fluorescence spectroscopy, and anisotropy and lifetime measurements. The survey of indole derivatives shows that methyl substitutions on the pyrrole ring effect 1La and 1Lb energies in tandem, whereas benzyl ring substitutions with electrophilic groups lift the 1La/1Lb degeneracy. For 5‐ and 6‐hydroxyindole in cyclohexane, 1La and 1Lb transitions are resolved. This finding provides for 1La origin assignment in the absorption and excitation spectra for indole vapor. The 5‐ and 6‐hydroxyindole excitation spectra show that despite a blue‐shifted emission spectrum, both the 1La and 1Lb transitions contribute to emission. Fluorescence lifetimes of 10 ns for 5‐hydroxyindole are consistent with a charge acceptor‐induced increase in the nonradiative rate (1).  相似文献   

10.
Let Ln denote the linear hexagonal chain containing n hexagons. Then identifying the opposite lateral edges of Ln in ordered way yields TUHC[2n, 2] , the zigzag polyhex nanotube, whereas identifying those of Ln in reversed way yields Mn, the hexagonal Möbius chain. In this article, we first obtain the explicit formulae of the multiplicative degree-Kirchhoff index, the Kemeny's invariant, the total number of spanning trees of TUHC[2n, 2] , respectively. Then we show that the multiplicative degree-Kirchhoff index of TUHC[2n, 2] is approximately one-third of its Gutman index. Based on these obtained results we can at last get the corresponding results for Mn.  相似文献   

11.
AM1 calculations have been performed on all‐trans polyacetylene (PA) oligomers with an increasing number of unit cells to study the effect of donor or acceptor groups capped at opposite ends of PA chains, substituents included in the monomers, substituents' number and position in the monomers, on the molecular structures, and the static longitudinal polarizabilities (αL) and second‐order hyperpolarizabilities (γL). Substitution of CH3, Cl, or F group at opposite ends of an oligomer results in an increase of αL and γL, but the substitution effects on ΔαL(N) and ΔγL(N) are very small. The asymptotic limit values are unaffected by the substitution. F substituent included in the monomer of an oligomer enhances the ΔαL(N) and ΔγL(N) values, especially at large N, but including monomers with CH3 or Cl substituents substantially reduces the ΔαL(N) and ΔγL(N) values. We alter the number of F substituents included in the monomers of oligomers and find that including two F substituents in the monomer leads to the larger enhancement of ΔγL(N). The effect of F substituents' position in the monomers of oligomers on ΔαL and ΔγL is obvious. The results may be helpful for the design of new materials for applications in nonlinear optics, particularly in the area of poled polymer films. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001  相似文献   

12.
Few novel mixed ligand copper(II) complexes of the type [Cu(L)(Cl)2(H2O)], [Cu(L)2]Cl2, [Cu(L)L1] and [Cu(L)(phen)H2O]Cl2 (where L is the ligand obtained from the condensation of N-(2-aminoethyl)-1,3-propanediamine with m-nitrobenzaldehyde (La)/o-chlorobenzaldehyde (Lb)/benzaldehyde (Lc)/p-methoxybenzaldehyde (Ld)/p-hydroxybenzaldehyde (Le)/furfuraldehyde (Lf)/pyrrole-2-carboxaldehyde (Lg); L1 is another ligand obtained from the condensation of anthranilic acid with salicyaldehyde; phen = 1,10-phenanthroline) have been synthesized and characterized by the spectral and analytical techniques. From these data, it is found that the ligands adopt distorted octahedral geometry on metalation with Cu(II) ion. The XRD data indicate that the complexes are polycrystalline with nanosized grains. The SEM images of [Cu(La)phen(H2O)]Cl2 and [Cu(Lf)2]Cl2 complexes show that they have leaf and cauliflower like morphology. The in vitro biological screening effects of the investigated compounds have been tested against the bacteria such as Escherichia coli, Klebsiella pneumoniae, Salmonella typhi, Pseudomonas aeruginosa and Staphylococcus aureus and fungi such as Aspergillus niger, Rhizopus stolonifer, Aspergillus flavus, Rhizoctonia bataicola and Candida albicans by the well diffusion method. A comparative study of MIC values of the Schiff base ligands and their complexes indicates that the complexes exhibit higher antimicrobial activity than the free ligands. An electrochemical study of the copper complexes containing electron withdrawing substituted ligands reveals that they prefer to bind to DNA in Cu(II) rather than Cu(I) oxidation state.  相似文献   

13.
Previous studies of the occurrence of acid soaps in systems containing a longchain sodium soap and the corresponding fatty acid, and the study of phase equilibria in the system sodium octanoate — octanoic acid — water, performed by our group at the beginning of the 1960s, show that the isotropic liquidL 2-phase of the last mentioned system in its whole region of existence is situated in that part in which acid soaps occur. This provides an explanation for the fact that theL 2-phase itself contains acid sodium octanoates in all regions. TheL 2-phase has its origin in the water-free melt of fatty acid and neutral soap in which these components react with each other under the formation of an acid soap. When water is added to the system, this water-free acid soap is transformed into different hydrated acid soaps. In a large region of concentration, there is an extremely close relation between theL 2-phase and the liquid-crystalline lamellarD-phase, which itself consists of hydrated acid soaps. At its outermost water-rich tip, theL 2-phase is in equilibrium with theL 1-phase of the system, just above the+LAC, that is, with the most dilute aqueous soap solution in which acid soap still may be formed in aqueous environment. Formation of acid soap is a fundamental requirement for the existence of this isotropic liquidL 2-phase.  相似文献   

14.
Metal-driven self-assembly is one of the most effective approaches to lucidly design a large range of discrete 2D and 3D coordination architectures/complexes. Palladium(II)-based self-assembled coordination architectures are usually prepared by using suitable metal components, in either a partially protected form (PdL′) or typical form (Pd; charges are not shown), and designed ligand components. The self-assembled molecules prepared by using a metal component and only one type of bi- or polydentate ligand (L) can be classified in the homoleptic series of complexes. On the other hand, the less explored heteroleptic series of complexes are obtained by using a metal component and at least two different types of non-chelating bi- or polydentate ligands (such as La and Lb). Methods that allow the controlled generation of single, discrete heteroleptic complexes are less understood. A survey of palladium(II)-based self-assembled coordination cages that are heteroleptic has been made. This review article illustrates a systematic collection of such architectures and credible justification of their formation, along with reported functional aspects of the complexes. The collected heteroleptic assemblies are classified here into three sections: 1) [(PdL′)m(La)x(Lb)y]-type complexes, in which the denticity of La and Lb is equal; 2) [(PdL′)m(La)x(Lb)y]-type complexes, in which the denticity of La and Lb is different; and 3) [Pdm(La)x(Lb)y]-type complexes, in which the denticity of La and Lb is equal. Representative examples of some important homoleptic architectures are also provided, wherever possible, to set a background for a better understanding of the related heteroleptic versions. The purpose of this review is to pave the way for the construction of several unique heteroleptic coordination assemblies that might exhibit emergent supramolecular functions.  相似文献   

15.
A conductometric system with a multipumping module and a gas-diffusion cell has been developed to determine free and total sulfur dioxide (SO2) in wine. The developed method has two protocols to determine both types of SO2 using the same system. For free SO2, sulfite is converted to H2SO4 by acidification and diffusion with H2O2 in an acceptor channel. The sample was previously hydrolyzed by mixing the sample with NaOH and heated at 70?°C prior making the determination of total SO2 in order to break the bonds of the combined SO2. Free and total SO2 were determined in the ranges of 2.5–25.4 and 10.2–76.2?mg L?1 with a sample throughput of 13 and 12?h?1, respectively. The calibration curves of free and total SO2 were in the range of ΔG (mS cm?1)?=?(–1.0242?±?0.2871)?+?(0.6613?±?0.0201) [SO2, mg L?1], r2 of 0.997 and ΔG (mS cm?1)?=?(–0.5850?±?0.1678)?+?(0.1236?±?0.0033) [SO2, mg L?1], r2 of 0.997. The proposed automated method is simple and easy to apply for the determination of SO2 in wine using simple reagents.  相似文献   

16.
Abstract

Ternary copper(II) complexes of the type [Cu(His)A] (HisH=L-histidine, A=glycinato, L-valinato, L-alaninato, L-threoninato, L-serinato, or L-asparaginato) and [Cu(Glu)B]n- (GluH2=L-glutamic acid, B=glycinato, L-alaninato, L-valinato (n=1) or an amino-acid with positively charged protonated side chain such as L-asparagine, L-lysine, or L-ornithine (n=0)) have been investigated in aqueous solution by means of ESR and absorption spectra. It is suggested that in the ternary species the histidinate ion adopts a histamine-like bonding mode giving rise to CuN3O chromophores in the metal plane. Coordination in the bis-(glycine)-like mode is detected in the Glu-containing species. The spectral results have been used to postulate plausible structures for the bis-(histidinato)copper(II) complexes.  相似文献   

17.
X-ray diffraction of the UHMWPE gel-films has shown that high heating rate annealing of the films causes deformation of the crystallites. The apparent crystal sizes change with the annealing temperature (Ta). With Ta below 110°C, the dimensions of the crystallites in c-axis (Lc) increase associated with the decreasing in a-axis (La) and b-axis (Lb), but the changes are small because of the higher energy barrier. When Ta is raised to 138°C, Lc is nearly doubled its value at 60°C whereas Lb increases and La remains unchanged. IR spectral subtraction was applied to reveal the morphological changes of the gel-films upon annealing. It has been found that bands of the same type of conformation have different sensitivities subject to the thermal treatment at different annealing temperatures. The results can be understood by assuming the changing process being completed through chain segments sliding along the (020) sectors. © 1995 John Wiley & Sons, Inc.  相似文献   

18.
A graphical representation of matrix elements of spin-free one- and two-electron operators is used for deriving a simple algorithm for the evaluation of their values. The method covers all the cases which may occur when wave functions are taken as mutually orthogonal antisymmetrized products of spinorbitals (which are assumed to form an orthonormal set) and are eigenfunctions of L 2 and L z operators. The resulting formulas are suitable as well for computer programming as for hand calculations.
Zusammenfassung Mit Hilfe einer graphischen Darstellung wird ein einfacher Algorithmus zur Bestimmung der Werte der Matrix-Elemente von spinfreien Ein- und Zweielektronenoperatoren abgeleitet. Durch diese Methode werden alle Fälle erfaßt, die auftreten, wenn die Wellenfunktionen wechselweise orthogonale, antisymmetrisierte Produkte von Spinorbitalen (von denen angenommen wird, daß sie einen orthogonalen Satz bilden) darstellen und Eigenfunktion der L 2 und L z Operatoren sind. Die erhaltenen Formeln eignen sich für Rechnungen mit und ohne Verwendung eines Computers.


Sponsored by the Mathematical Institute, Polish Academy of Sciences.  相似文献   

19.
The reaction of CdBr2·4H2O with ancillary ligands, N,N‐bis(1H‐pyrazolyl‐1‐methyl)aniline ( L1 ), N,N‐bis(1H‐pyrazolyl‐1‐methyl)‐p‐methylaniline ( L2 ), N,N‐bis(1H‐pyrazolyl‐1‐methyl)‐3,5‐dimethylaniline ( L3 ), N,N‐bis(3,5‐dimethyl‐1H‐pyrazolyl‐1‐methyl)aniline ( L4 ) and N,N‐bis(1H‐pyrazolyl‐1‐methyl)‐2,6‐dimethylaniline ( L5 ) in ethanol yields novel Cd(II) bromide complexes, [L1CdBr2]2 , [L2CdBr2]2 , [L3CdBr2]2 , [L4CdBr2] and [L5CdBr2] . The X‐ray crystal structures of [L1CdBr2]2 , [L2CdBr2]2 and [L3CdBr2]2 reveal a bromo‐bridged dimeric species with crystallographic inversion symmetry. Conversely, [L4CdBr2] and [L5CdBr2] exist as monomeric complexes, presumably due to the steric hindrance between the methyl substituents of the two pyrazole groups in the ligand and cadmium centre for [L4CdBr2] , and crowding around the cadmium metal by methyl substituents on the aniline residue in the ligand for [L5CdBr2] . The geometry at each Cd(II) centre for [L1CdBr2]2 , [L2CdBr2]2 and [L3CdBr2]2 is best described as a distorted trigonal bipyramid. A distorted trigonal bipyramid is achieved in [L4CdBr2] by coordinative interaction of the nitrogen atom of the aniline unit and the cadmium atom with a σ plane of symmetry, based on the bond length of Cd―Naniline (2.759(7) Å). [L5CdBr2] exists with a distorted tetrahedral geometry involving non‐coordination of the nitrogen atom of aniline and the Cd centre, resulting in the formation of an eight‐membered chelate ring. The catalytic activity of monomeric, five‐coordinated [L4CdBr2] in the polymerization of methyl methacrylate (MMA) in the presence of modified methylaluminoxane (MMAO) at 60°C resulted in a higher molecular weight and a narrower polydispersity index (PDI) than those obtained with dimeric [LnCdBr2]2 (Ln = L1 , L2 , L3 ) or monomeric tetrahedral [L5CdBr2] . Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

20.
A rod-core complex, (αβ)6PC. LRC29.5,(αβ)3APC.LC8.9, composed of hexameric phycocyanin (PC) and trimeric allophycocyanin (APC) subcomplexes associated to the CpcG2 gene product, has been isolated from the phycobilisome of Mastigocladus laminosus. Exactly the same complex was obtained by reconstitution using the subcomplexes(αβ)3PC. LRC 29.5 and (aβ)3APC.LC8.9 as educts. Spectroscopic analysis of the isolated PC-LR and PC-LRC complexes from M. laminosus shows that the LRC cause the largest red-shift in the absorbance and fluorescence emission maxima of PC. These results indicate that LRC mediate PC-APC interactions in vitro. Only the CpcG2 polypeptide was able to promote this specific interaction, as neither CpcG3-PC nor, as a negative control, CpcC-PC complexes showed any reconstitution products with the core subcomplex (αβ)3APC.Lc8.9. This is an indication that each of the four LRC in the phycobilisomes of M. laminosus and Anabaena sp. PCC 7120 attaches two peripheral rods specifically to one of four different core binding sites.  相似文献   

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