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1.
Low-angle x-ray methods have been used to evaluate some macromolecular parameters of the scattering particles in tussah, a silk fiber. A low-angle Kratky camera of recent design has been used for the experimental measurements of the scattering intensities. The sample under investigation is taken as a densely packed colloidal system belonging to general micelle system and the well known theories of Kratky and Kratky and Porod have been utilized. The parameters determined are specific inner surface of the dispersed phase (O/V), transverse lengths like the length of inhomogeneity (lr) and the length of coherence (lc), and the air fraction of the scattering particles in tussah fiber; these were found to be 7.084 × 10?6 Å?1, 100.6 Å, 367.7 Å, and 0.02%, respectively.  相似文献   

2.
Various macromolecular parameters of Agave sisalana (sisal) fiber were investigated by the low-angle x-ray scattering method. The well known Kratky camera of the latest design was utilized for the experimental measurements. The sample studied was a densely packed colloidal system belonging to a general micelle system, and the theories of Kratky and Kratky and Porod were utilized to estimate the parameters. Pore analysis of the substance yields a value for the specific inner surface of the dispersed phase of 0.406 × 10?1 m2/cm3; the transversal length is the same as the length of inhomogeneity, 107.31 Å, and the length of coherence is 342.21 Å. The air fraction of the scattering particles was found to be 0.01%.  相似文献   

3.
Small-angle x-ray scattering methods were applied to calculate macromolecular parameters like specific inner surface (O/V), length of coherence (lc), and the percentage of air present in agave hybrid, treating it as a densely packed colloidal system belonging to a general micelle system. The parameters were equal to O/V = 8.50 × 10?6 Å?1, lc = 150 Å, and the percentage of air = 0.03. The Kratky camera with latest design was used for the experimental measurement. Because the sample agave ybrid is a natural fiber and a highly oriented system that is celluosic in character, the theories of Kratky and Porod have been used to evaluate these parameters.  相似文献   

4.
Air-dired kangaroo tail tendon (KTT) is a protein sample similar to collagen and has been investigated by small-angle x-ray scattering treating it as a densely packed colloidal system which belongs to a general micelle system. Pore analysis of the substance yields a specific inner surface of 0.6282 × 10?5 Å?1, a range of inhomogeneity of 69.11 Å, a length of coherence of 248.2 Å, and air-fraction percentage of 0.011. A Kratky camera of the latest design has been used for experimental measurements. As the log? vs. logX curve gives a slope of ?3, KTT belongs to a densely packed two-phase system. Here the theory of small-angle scattering by densely packed systems as developed by Porod has been applied to find different physical parameters of KTT.  相似文献   

5.
Low-angle x-ray scattering methods have been applied to determine the parameters of the scattering materials in horn keratin. A low-angle camera of Kratky's latest design has been used for the experimental measurements. By treating the substance as a densely packed system, the evaluation of the parameters has been made after theories of Porod and Kratky. Pore analysis of the substance yields a specific inner surface of 4.7 × 10?1m2/cm3, a heterogeneity distance lc = 290.2Å and a reduced inhomogeneity length lr = 99.4Å. The volume of the pores has also been determined approximately.  相似文献   

6.
Changes in light scattering induced by a strong laser beam, as predicted theoretically by Kielich, were measured for unfractionated yeast transfer ribonucleic acid (tRNA) solutions. The vertically polarized electric field of a strong laser pulse (λ = 1060nm) amounted to 4.5 × 103 esu cgs; its duration was 10 nsec. A weak incident laser beam (λ = 630nm) was also polarized vertically and the vertical and horizontal intensity components of the light scattered through 90° at the latter wavelength were measured. These measurements together with previous results from measurements of Rayleigh light scattering and light scattering in a magnetic field permitted evaluation of the tensor of third-order polarizability (c = 3 × 10?30 esu cgs, c = ?373 × 10?30 esu cgs) and the anisotropy of the third-order polarizability components with its sign (δc = +56 × 10?2, δc = +0.25 × 10?2 for tRNA monomer and aggregate, respectively). The new method described may be useful for studies of macromolecules and macromolecular complexes of biological importance.  相似文献   

7.
Results are presented of neutron incoherent scattering experiments on isotropic linear polyethylene samples of high (80%) and low (48%) crystallinity in the temperature range between ?180°C and +85°C for values of the scattering vector between 0.29 Å?1 and 1.81 Å?1 obtained with a high resolution backscattering spectrometer (Δ?ω = 0.25 ? 1.0 μeV) and between 0.57 Å?1 and 2.4 Å?1 with a time-of-flight spectrometer (Δ?ω = 420 μeV). From a comparison of the results on these samples one concludes that relaxation takes place predominantly in the noncrystalline regions. This motion cannot be adequately accounted for by any of the existing models for the γ-process. Therefore, a more liquidlike motion is suggested. Diffusion of shorter chain segments has also been ruled out since it is too slow to be observed. A simplified model of protonic jumps between equidistant sites located on the periphery of a circle of radius 2.5 Å reproduces the experimental results well. For the average time between successive CH2-group reorientations one obtains τ1 = τ0 exp(EactRT) with τ0 = (2.0 ± 1.5) × 10?13 sec and Eact = (4.5 ± 1.0) kcal/mole. The values join up well with those for the γ-process observed by NMR. It has been concluded that 60–90% of the protons in the noncrystalline regions participate in this motion.  相似文献   

8.
For the first time the small-angle neutron scattering (SANS) from mixtures of protonated and totally deuterated syndiotactic polystyrene (sPS) has been studied. Two amorphous samples with similar molecular weights have been measured at various concentrations of the protonated part. All measurements were performed at room temperature using the scattering equipment of two different laboratories. The molecular weight Mw evaluated from SANS data agreed with those obtained by gel permeation analysis (GPC). In the Kratky representation the scattering contribution due to the contrast scattering shows a plateau behavior up to q = 0.45 Å?1, where q is magnitude of the scattering vector. This observation is in evident contrast to what is expected from the rotational isomeric state (RIS) model. In addition the characteristic ratios C, derived either from the plateau height or from radii of gyration of the Zimm regime and being in reasonable agreement with each other, show strong deviations from the predictions of the RIS model. © 1994 John Wiley & Sons, Inc.  相似文献   

9.
Three complexes, Na4[DyIII(dtpa)(H2O)]2?·?16H2O, Na[DyIII(edta)(H2O)3]?·?3.25H2O and Na3[DyIII (nta)2(H2O)]?·?5.5H2O, have been synthesized in aqueous solution and characterized by FT–IR, elemental analyses, TG–DTA and single-crystal X-ray diffraction. Na4[DyIII(dtpa)(H2O)]2?·?16H2O crystallizes in the monoclinic system with P21/n space group, a?=?18.158(10)?Å, b?=?14.968(9)?Å, c?=?20.769(12)?Å, β?=?108.552(9)°, V?=?5351(5)?Å3, Z?=?4, M?=?1517.87?g?mol?1, D c?=?1.879?g?cm?3, μ?=?2.914?mm?1, F(000)?=?3032, and its structure is refined to R 1(F)?=?0.0500 for 9384 observed reflections [I?>?2σ(I)]. Na[DyIII(edta)(H2O)3]?·?3.25H2O crystallizes in the orthorhombic system with Fdd2 space group, a?=?19.338(7)?Å, b?=?35.378(13)?Å, c?=?12.137(5)?Å, β?=?90°, V?=?8303(5)?Å3, Z?=?16, M?=?586.31?g?mol?1, D c?=?1.876?g?cm?3, μ?=?3.690?mm?1, F(000)?=?4632, and its structure is refined to R 1(F)?=?0.0307 for 4027 observed reflections [I?>?2σ(I)]. Na3[DyIII(nta)2(H2O)]?·?5.5H2O crystallizes in the orthorhombic system with Pccn space group, a?=?15.964(12)?Å, b?=?19.665(15)?Å, c?=?14.552(11)?Å, β?=?90°, V?=?4568(6)?Å3, Z?=?8, M?=?724.81?g?mol?1, D c?=?2.102?g?cm?3, μ?=?3.422?mm?1, F(000)?=?2848, and its structure is refined to R 1(F)?=?0.0449 for 4033 observed reflections [I?>?2?σ(I)]. The coordination polyhedra are tricapped trigonal prism for Na4[DyIII(dtpa)(H2O)]2?·?16H2O and Na3[DyIII(nta)2(H2O)]?·?5.5H2O, but monocapped square antiprism for Na[DyIII(edta)(H2O)3]?·?3.25H2O. The crystal structures of these three complexes are completely different from one another. The three-dimensional geometries of three polymers are 3-D layer-shaped structure for Na4[DyIII(dtpa)(H2O)]2?·?16H2O, 1-D zigzag type structure for Na[DyIII(edta)(H2O)3]?·?3.25H2O and a 2-D parallelogram for Na3[DyIII(nta)2(H2O)]?·?5.5H2O. According to thermal analyses, the collapsing temperatures are 356°C for Na4[DyIII(dtpa)(H2O)]2?·?16H2O, 371°C for Na[DyIII(edta)(H2O)3]?·?3.25H2O and 387°C for Na3[DyIII(nta)2(H2O)]?·?5.5H2O, which indicates that their crystal structures are very stable.  相似文献   

10.
Two metal complexes, [NiII(mscinn)2(pda)2] (1) and [CdII(mscinn)2(dmeda)2·2H2O] (2) (mscinn?=?4-methylsulfonyl cinnamate, pda?=?propane-1,3-diamine, dmeda?=?N′,N′-dimethylethane-1,2-diamine), were synthesized by reacting 4-methylsulfonyl cinnamate with the diamines and metal salts. Their structures were determined by single-crystal X-ray diffraction analysis. Crystal parameters of 1: C26H38N4NiO8S2, M?=?657.43, monoclinic, P21/c, a?=?16.6123(8)?Å, b?=?8.5956(4)?Å, c?=?11.2047(5)?Å, β?=?107.423(1)°, V?=?1526.54(12)?Å3, Z?=?2, D calcd?=?1.430?g?cm?3, F(000)?=?692, μ?=?0.825?mm?1, R 1?=?0.0257, wR 2?=?0.0669. Crystal data of 2: C28H42CdN4O8S2?·?2(H2O), M?=?775.24, monoclinic, P21/c, a?=?9.8278(4)?Å, b?=?11.6611(5)?Å, c?=?15.3972(7)?Å, β?=?96.195(1)°, V?=?1754.26(13)?Å3, Z?=?2, D calcd?=?1.468?g?cm?3, F(000)?=?804, μ?=?0.798?mm?1, R 1?=?0.0299, wR 2?=?0.0770. Antimicrobial activities for 1 and 2 against Escherichia coli, Pseudomonas putida, Bacillus subtilis, and Bacillus cereus had better antibacterial activity than their parent carboxylic acid against Gram-positive bacteria (B. subtilis and B. cereus). The cadmium complex of the cinnamate displayed high inhibitory activity with an MIC value of 5?µg?mL?1 against P. putida, while the nickel complex also exhibited good inhibitory potency with an MIC value of 5?µg?mL?1 against B. subtilis.  相似文献   

11.
Abstract

A new binuclear complex, [Zn2L2Cl4]·2H2O {L?=?N-aldehyde-N-(4-(benzyloxy)benzyl)-1,4,7triazacyclononane}, was synthesized and characterized by X-ray, elemental analysis, infrared and electronic spectroscopy, and mass spectrometry. The central ion is bridged by the L and lies in a tetrahedral configuration with Zn···Zn distance of 6.283 Å. The complex crystallizes in the triclinic space group Pī. ESI-MS of the complex indicates that the protonated ligand HL+ is the active species. The interaction of HL+ with calf thymus–DNA (CT–DNA) and bovine serum albumin (BSA) was studied by means of various spectroscopic methods, which revealed that HL+ could interact with CT–DNA through groove-binding mode and could quench the intrinsic fluorescence of BSA in a static quenching process. DNA–cleavage experiments indicate that HL+ exhibits efficient DNA–cleavage activity in the presence of H2O2, hydroxyl radical (HO?) may serve as the major cleavage active species, and the pseudo-Michaelis–Menten kinetic parameters (Kcat, KM, Vmax); 2.47?h?1, 2.70?×?10?4 M and 6.68?×?10?4 Mh?1.  相似文献   

12.
The surface segregation of In and S from a dilute Cu(In,S) ternary alloy were measured using Auger electron spectroscopy coupled with a linear programmed heater. The alloy was linearly heated and cooled at constant rates. Segregation data of a linear heat run showed surface segregation of In that reached a maximum surface coverage of 25% followed by S, which reached a coverage of 30%. It was found that after In had reached a maximum surface coverage, it started to desegregate as soon as the S enriched the surface until In was completely replaced by S. The segregation parameters, namely, the pre‐exponential factor (D0), activation energy (Q), segregation energy (ΔG?) and interaction energy (Ω) were extracted from the measured segregation data for both In and S segregation in Cu by simulating the measured segregation data with a theoretical segregation model (modified Darken model). The segregation parameters obtained for In segregation in Cu are D0 = 1.8 ± 0.5 × 10?5 m2 s?1, Q = 184.3 ± 1.0 kJ.mol?1, ΔG? = ?61.4 ± 1.4 kJ.mol‐1, ΩCu?In = 3.0 ± 0.4 kJ.mol?1; for S segregation in Cu the parameters are D0 = 8.9 ± 0.5 × 10?3 m2 s?1, Q = 212.8 ± 3.0 kJ.mol?1, ΔG? = ?120.0 ± 3.5 kJ.mol?1, ΩCu?S = 23.0 ± 2.0 kJ mol?1 and the In and S interaction parameter is ΩIn?S = ?4.0 ± 0.5 kJ.mol?1. The initial parameters used for the Darken calculations were extracted from fits performed with the Fick's and Guttmann model. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

13.
A novel chemiluminescence (CL) method for the determination of hydrogen peroxide is described. Method is based on the transition metals in highest oxidation state complex, which include diperiodatoargentate (DPA) and diperiodatonickelate (DPN) and show excellent sensitisation on the luminol-H2O2 CL reaction with low luminol concentration in alkaline medium. In particular, the sensitiser which was previously reported (such as Co2+, Cu2+, Ni2+, Mn2+, Fe3+, Cr3+, KIO4, K3Fe(CN)6 etc.) to be unobserved CL due to poor sensitisation with such low concentration of luminol which makes the method hold high selectivity. Based on this observation, the detection limits were 6.5?×?10?9?mol?L?1 and 1.1?×?10?8?mol?L?1 hydrogen peroxide for the DPN- and DPA-luminol CL systems, respectively. The relative CL intensity was linear with the hydrogen peroxide concentration in the range of 2.0?×?10?8–6.0?×?10?6?mol?L?1 and 4.0?×?10?8–4.0?×?10?6?mol?L?1 for the DPN- and DPA-luminol CL systems, respectively. The proposed method had good reproducibility with a relative standard deviation of 3.4% (8.0?×?10?7?mol?L?1, n?=?7) and 1.0% (2.0?×?10?6?mol?L?1, n?=?7) for the DPN- and DPA-luminol CL systems, respectively. A satisfactory result has been gained for the determination of H2O2 in rainwater and artificial lake water by use of the proposed method.  相似文献   

14.
A new dinuclear manganese complex, [Mn2L2(N3)2], was prepared by reaction of bis-Schiff base N,N'-bis(5-fluoro-2-hydroxybenzylidene)ethane-1,2-diamine (H2L) with manganese acetate and sodium azide in methanol. Both the Schiff base and the complex were characterized by physico-chemical methods and single crystal X-ray determination. The Schiff base crystallized in the orthorhombic space group Pbca with unit cell dimensions a?=?7.3191(7)?Å, b?=?6.0948(6)?Å, c?=?35.382(3)?Å, V?=?1578.3(3)?Å3, Z?=?4, R1?=?0.0481, wR2?=?0.1488. The manganese complex crystallized in the monoclinic space group P21/c with unit cell dimensions a?=?8.802(1)?Å, b?=?14.928(2)?Å, c?=?14.478(2)?Å, β?=?105.517(2)°, V?=?1833.0(4)?Å3, Z?=?2, R1?=?0.0768, wR2?=?0.1640. There are crystallographic inversion centers in both the ligand and the complex. The ligand coordinates to Mn through all the phenolate oxygens and imino nitrogens. The two Mn in the complex are bridged by two phenolate oxygens with separation of 3.549(1)?Å. Each Mn is octahedral with four donors of the Schiff base ligand defining the equatorial plane, and with one azido nitrogen and one phenolate oxygen of an adjacent Schiff base ligand occupying the axial positions. The Schiff base and the complex were tested in vitro for their antibacterial activities.  相似文献   

15.
A new salt, [NO2BzDMAP]3[Cu2Cl7]?·?H2O (1), has been synthesized, where [NO2BzDMAP]+ is 1-(4′-nitrobenzyl)-4-dimethylaminopyridinium. Herein, the synthesis, spectral and structural characterization, and magnetic behavior of 1 are reported. It is orthorhombic, with space group Pca21, and a?=?26.639(2)?Å, b?=?9.638(1)?Å, and c?=?20.011(2)?Å with V?=?5137.5(7)?Å3 for Z?=?4. The anion shows a chloride-bridged binuclear structure with Cu?···?Cu distance of 3.872?Å; the two Cu(II) ions have a tetrahedral geometry. The cations stack through p?···?π and π?···?π interactions, and a complicated hydrogen-bonding network structure is formed through C–H?···?Cl and C–H?···?O hydrogen bonds. The variable temperature magnetic susceptibility measurements reveal that 1 exhibits strong antiferromagnetic interaction with J?=??193.0?cm?1.  相似文献   

16.
17.
This paper compares rates of charge transport by tunneling across junctions with the structures AgTSX(CH2)2nCH3 //Ga2O3 /EGaIn (n=1–8 and X= ? SCH2? and ? O2C? ); here AgTS is template‐stripped silver, and EGaIn is the eutectic alloy of gallium and indium. Its objective was to compare the tunneling decay coefficient (β, Å?1) and the injection current (J0, A cm?2) of the junctions comprising SAMs of n‐alkanethiolates and n‐alkanoates. Replacing AgTSSCH2‐R with AgTSO2C‐R (R=alkyl chains) had no significant influence on J0 (ca. 3×103 A cm?2) or β (0.75–0.79 Å?1)—an indication that such changes (both structural and electronic) in the AgTSXR interface do not influence the rate of charge transport. A comparison of junctions comprising oligo(phenylene)carboxylates and n‐alkanoates showed, as expected, that β for aliphatic (0.79 Å?1) and aromatic (0.60 Å?1) SAMs differed significantly.  相似文献   

18.
Bis[tris(trimethylsilyl)cyclopentadienyl]europium, Eu{C5H2[Si(CH3)3]3}2 (1) , has been synthesized by a modified transmetallation route between Tl{C5H2[Si(CH3)3]3} and europium powder in toluene. 1 crystallizes in the monoclinic space group C2/c (No. 15) with a = 20.293(5) Å, b = 20.221(5) Å, c = 9.654(2) Å, β = 106.412(5)°, V = 3800.1(15) Å3, Z = 4. The unit cell contains monomeric molecules that adopt a bent metallocene conformation with two partially staggered Cp? ligands. Magnetic susceptibility measurements in the temperature range 2–300 K display ideal Curie paramagnetic behaviour of the 4f7 system with Curie constant C = 9.6 × 10?5 m3 K mol?1 corresponding to temperature independent μeff = 7.8.  相似文献   

19.
Highly crystalline samples of cellulose triacetate I (CTA I) were prepared from highly crystalline algal cellulose by heterogeneous acetylation. X‐ray diffraction of the prepared samples was carried out in a helium atmosphere at temperatures ranging from 20 to 250 °C. Changes in seven d‐spacings were observed with increasing temperature due to thermal expansion of the CTA I crystals. Unit cell parameters at specific temperatures were determined from these d‐spacings by the least squares method, and then thermal expansion coefficients (TECs) were calculated. The linear TECs of the a, b, and c axes were αa = 19.3 × 10?5 °C?1, αb = 0.3 × 10?5 °C?1 (T < 130 °C), αb = ?2.5 × 10?5 °C?1 (T > 130 °C), and αc = ?1.9 × 10?5 °C?1, respectively. The volume TEC was β = 15.6 × 10?5 °C?1, which is about 1.4 and 2.2 times greater than that of cellulose Iβ and cellulose IIII, respectively. This large thermal expansion could occur because no hydrogen bonding exists in CTA I. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 517–523, 2009  相似文献   

20.
《Electroanalysis》2005,17(23):2129-2136
The investigation of the dissolved iron(III)–nitrilotriacetate–hydroxide system in the water solution (I=0.1 mol L?1 in NaClO4; pH 8.0±0.1) using differential pulse cathodic voltammetry, cyclic voltammetry, and sampled direct current (DC) polarography, was carried out on a static mercury drop electrode (SMDE). The dissolved iron(III) ion concentrations varied from 2.68×10?6 to 6×10?4 mol L?1 and nitrilotriacetate concentrations were 1×10?4 and 5×10?4 mol L?1. By deconvoluting of the overlapped reduction voltammetric peaks using Fourier transformation, four relatively stable, dissolved iron(III) complex species were characterized, as follows: [Fe(NTA)2]3?, mixed ligand complexes [FeOHNTA]? and [Fe(OH)2NTA]2?, showing a one‐electron quasireversible reduction, and binuclear diiron(III) complex [NTAFeOFeNTA]2?, detected above 4×10?4 mol L?1 of the added iron(III) ions, showing a one‐electron irreversible reduction character. The calculations with the constants from the literature were done and compared with the potential shifts of the voltammetric peaks. Fitting was obtained by changing the following literature constants: log β2([Fe(NTA)2]3?) from 24 to 27.2, log β1([FeNTA]?) from 8.9 to 9.2, log β2([Fe(NTA)2]4?) from 11.89 to 15.7 and log β2([Fe(OH)2NTA]3?) from 15.63 to 19. The determination of the electrochemical parameters of the mixed ligand complex [FeOHNTA]?, such as: transfer coefficient (α), rate constant (ks) and formal potential (E°') was done using a sampled DC polarography, and found to be 0.46±0.05, 1.0±0.3×10?3 cm s?1, and ?0.154±0.010 V, respectively. Although known previously in the literature, these four species have now for the first time been recorded simultaneously, i.e. proved to exist simultaneously under the given conditions.  相似文献   

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