1. INTRODUCTION Chitin, the most abundant natural amino polysaccharide and estimated to be produced annually almost as much as cellulose, is well known to consist of 2-acetamido-2-deoxy-β-D- glucose through α, β(1→4) linkage. Chitin is the major source of surface pollution in coastalareas. Chitosan is the N-deacetylated derivative of chitin and their structures are shown in Fig. 1. Fig. 1 Structures of Chitin and Chitosan Because of the excellent properties such as biocompatibility… 相似文献
In this work, 4-diethanolaminomethyl styrene (DEAMSt) monomer was prepared by modification of 4-chloromethyl styrene with diethanolamine. The homopolymerization of styrene modificated was carried out by free radical polymerization method at 60?°C in presence of 1,4-dioxane and AIBN. The metal complexes were prepared by reaction of the homopolymer used as ligand P(DEAMSt)Ll and Ni(II), Co(II) metal ions in presence of ethanol and dilute NaOH at 65?°C for 48?h in pH 6.
The structure of modificated monomer, homopolymer used as ligand and polymer-metal complexes were characterized by (FT-IR), 1H-NMR, 13C-NMR, Raman spectroscopy tecniques, elemental analysis, SEM, XRD and magnetic measurements. Their geometric structures according to magnetic measurements of Co(II) and Ni(II) complexes were estimated that have a tetrahedral structure. P(DEAMSt)Ll polymer has a transition state between amorphous and crystalline, whereas metal complexes (Co(II) and Ni(II) are with a large crystal structure. The molecular weight of P(DEAMSt)L1 homopolymer was determined by gel permeation chromatography (GPC). The glass transition temperature (Tg) of homopolymer was measured by differantial scanning calorimeter (DSC). The thermal behaviors of both ligand and polymer-metal complexes were investigated by thermogravimetric analysis (TGA) and (DTA). The results obtained were compared with each other. Then, the dielectrical measurements (dielectric constant, dielectric loss and conductivity) of the ligand and polymer-metal complexes were investigated as a function of temperature and frequency. The activation energies (Ea) of the ligand and metal complexes were determined from the conductivity measurements. 相似文献
Rate constants for the reaction of ethyl bromoacetate with three series of substituted naphthoate ions have been measured
in an acetone-water mixture (90% v/v). Using σp values rate constants at 30o correlate well with the Hammett equation yielding ρ=−0.54, −0.19 and −0.25 for (4,1−), (6,1−) and (6,2−) series, respectively.
Comparison of these ρ values with those of the reaction of phenacyl bromide reveals the failure of the reactivity-selectivity
principle RSP in these reactions. Failure of RSP has been explained in terms of isoselective temperature. 相似文献
Proton nuclear magnetic relaxation dispersion (NMRD) profiles were recorded between 0.24 mT and 1.4 T for lanthanum(III)- and gadolinium(III)-containing [15]metallacrown-5 complexes derived from alpha-aminohydroxamic acids and with copper(II) as the ring metal. The influence of the different R-groups on the proton relaxivity was investigated, and a linear relationship between the relaxivity and the molecular mass of the metallacrown complex was found. The selectivity of the metallacrown complexes was tested by transmetalation experiments with zinc(II) ions. The crystal structure of the copper [15]metallacrown-5 gadolinium complex with glycine hydroximate ligands is reported. 相似文献
Electrophoretic mobilities of hexadecane/water emulsions containing dimyristoyl-phosphatidylcholine (DMPC) or egg yolk lecithin
(EYL) monolayers at the interface and those of liposomes prepared from the same lipids were measured as functions of the concentrations
of Ca2+, Mn2+, Cu2+, and Ni2+ cations in the aqueous phase. The surface potentials, surface charge densities (σ), and the Langmuir adsorption isotherms
for various distances from the charged surface to the slip plane (d) were calculated on the basis of the Gouy-Chapman theory for 1∶2 electrolytes and the values of ζ-potentials. The binding
constants (K) and parametersd were determined under the assumption that the maximum σ values correspond to one ion per phospholipid molecule at the interface.
In the case of DMPC, the ion binding constants (L mol−1) at 25°C are 230 and 87 for Ca2+, 31.5 and 21 for Mn2+, 11 and 6 for Cu2+, and 7.5 and 5.3 for Ni2+ in liposomes and emulsions, respectively. The affinities of Cu2+ and Ni2+ ions for EYL monolayers and bilayers are lower than those for DMPC mono- and bilayers. Thed parameters for all ions are smaller than the radii of the hydrated ions. In the case of Ca2+, Cu2+, and Ni2+, thed values for mono- and bilayers are different. The differences in K values between monolayers and bilayers as well as those
between DMPC and EYL mono- and bilayers can be attributed to the differences in the local environment and orientation of the
interfacial phosphate groups in these systems.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2490–2495, December, 1998. 相似文献
The solubilities of -, -, and -cyclodextrin have been measured in the presence of the first row transition metals: Cr3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+ and Zn2+; chlorides, nitrates and sulphates (in this case Fe2+), and, for companson, with CaCl2, the corresponding Group IIa salt. Where possible the measurements are reported as a function of the activity of the salts. In general, for the transition metals the sulphates all show a linear decrease in solubility with increasing salt activity: for the nitrates the solubility increases and then reaches a limiting value; and for the chlorides a small decrease in solubility is observed at low activity followed by an increase in solubility at higher salt activity. Circular dichroism measurements confirm that there is no direct complexation at non-basic pH.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August 1995. 相似文献
The photophysics and photochemistry of alpha-terthiophene (alphaT), compartmentalized in mixed nonionic/anionic micelles, have been investigated with focus on the influence of the micellar surface charge density on the formation of the radical coupling product alpha-hexathiophene (alphaH). By varying the ratio of nonionic-to-anionic surfactants, and assuming ideal mixing, the charge density of the mixed micelles was varied. From Poisson-Boltzmann calculations, performed using the cell model, the electrostatic potential and the counterion activity were estimated as a function of the distance from the micellar surface. Upon excitation, the triplet state of alphaT is formed, from which the alphaT radical cation can be formed by absorption of a second photon. The radical cation can form alphaH if it encounters another alphaT radical cation. Under the experimental conditions used, this implies that the alphaH formation only occurs if the compartmentalized radical cation is able to migrate from its host micelle to another micelle, either via the surrounding bulk or by fusion of two micelles followed by mixing of their contents before micellar fission. The formation yield of the radical cation depends on the charge density of the mixed micelle; a lower charge density, that is, an increased amount of nonionic surfactant, lowers the yield. The yield of the coupling product alphaH, however, does not follow the same trend. A maximum yield of alphaH is found at intermediate nonionic surfactant molar ratios. This behavior is understood in terms of the Poisson-Boltzmann simulation results and by comparing charge-density changes as a function of molar fraction with the changes in counterion activity. The alphaH yield is a result of the balance between an increased possibility of radical cation bulk migration and a lowered electrostatic stabilization of the radical. 相似文献
Transition metal ions are notorious for their fluorescence quenching abilities. In this paper, we discuss the design strategies
for the development of efficientoff-on fluorescence signalling systems for the transition metal ions. It is shown that even simplefluorophore-spacer-receptor systems can display excellentoff-on fluorescence signalling towards the quenching metal ions when the fluorophore component is chosen judiciously. 相似文献
A linear free energy relationship was found betweenvmax, the energy of the absorption maximum of chloride, bromide, or iodide ion in various solvents, and the solvatochromic parameter which is a measure of the hydrogen bond donor ability of the solvent. The relationships are: for chloride,vmax=6.99+50.16 kK; for bromide,vmax=5.52+45.20 kK; for iodide,vmax=5.02+40.33 kK. The correlation ofvmax for iodide ion with gave a larger correlation coefficient and smaller standard deviation than a correlation with the ET(30) parameter of Dimroth. From the values ofvmax for iodide ion and the solvated electron in liquid ammonia at 25°C, these correlations indicate a preliminary value of 0.00 for the parameter of liquid ammonia. This had not been reported before and is lower than expected from a general knowledge of the physical and chemical properties of liquid ammonia but is consistent with a more detailed consideration and recent gas phase measurements of hydrogen bond donor strength. 相似文献