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1.
Abstract

Pectic polysaccharides (HP, RP) were extracted from Mongolia hawthorn berries and from rhubarb stalks by hot aqueous oxalic acid treatment. Both polysaccharides contained approximately 78% of galacturonate. HP displayed a low degree of esterification (DE) and arabinose/galactose molar ratio 1.7:1. RP was higher in DE and contained these sugars in a molar ratio 0.5:1. Rhamnose, fucose, xylose, glucose, mannose, 2-O-methylxylose, and 2-O-methylfucose were found in lower amounts. Results from 13C NMR spectroscopy and methylation analysis indicated the presence of branched arabinans, (1?>4)-and (1?>3,6)-linked galactans and hemicelluloses of the xylan and glucan types. The pectins differed in theirmolecular properties. HP exhibited a low molecular weight (M W = 45,000), whereas RP had a broad M W-distribution with M W= 360,000. Independently of these differences, the binding capacity of both pectins towards divalent cations was influenced by the DE only and increased in the order: Ca2+ < Cd2+ < Pb2+ < Cu2+.  相似文献   

2.
The hydrolysis of methyltin(IV) trichloride (CH3SnCl3) has been studied in aqueous NaCl and NaNO3 solutions (0 < I/mol dm−3 ≤ 1), at different temperatures (15 ≤ T/°C ≤ 45) by­potentiometric measurements (H+‐glass electrode). By considering the generic hydrolytic <?tw=97.2%>reaction pCH3Sn3+ + qH2O = (CH3Sn)p(OH)q3pq<?tw>­+ qH+ (logβpq), we have the formation of five species and logβ12 = −3.36, logβ13 = −8.99, logβ14 = −20.27 and logβ25 = −7.61. The first hydrolysis step is measurable only at very low pH values and was not determined: a rough estimate of the hydrolysis constant is logβ11 = −1.5 (± 0.5). The dependence on ionic strength of logβpq is quite different in NaNO3 and NaCl solutions, and the formation at low pH values of the species CH3Sn(OH)Cl+ has been found with logβ = −1.40. Hydrolysis constants strongly depend on temperature and from the relationships logβpq = f(T), ΔH ° values have been calculated. Speciation problems of CH3Sn3+ in aqueous solution are discussed. Copyright © 1999 John Wiley & Sons, Ltd.  相似文献   

3.
The complexation reactions between 7,10,13-triaza-1-thia-4,16-dioxa-20,24-dimethyl-2,3;17,18-dibenzo-cyclooctadecane-6,14-dione ( TTD ) and 7,10,13-triaza-1-sulfoxo-4,16-dioxa-20,24-dimethyl-2,3;17,18-dibenzo-cyclooctadecane-6,14-dione ( TSD ) macrocycles with Ag+, Cd2+, Cu2+, Pb2+, Sr2+, Tl+, and Zn2+ ions have been studied in ethanol and methanol solutions at 25°C. The complexes formed between macrocycles ( TTD ) and ( TSD ) with these metals cations had a stiochiometry of 1:1 and 1:2, respectively. The stability constants of the resulting complexes were determined and found to decrease in the order Cu2+ > Zn2+ > Ag+ > Tl+ > Cd2+ > Pb2+ > Sr2+ with macrocycle ( TTD ) and Tl+ > Zn2+ > Cd2+ > Pb2+ > Cu2+ > Ag+ > Sr2+ with macrocycle ( TSD ).  相似文献   

4.
Abstract

Here, we report on synthesis of some novel derivatives of dibutyltin dichloride/oxide with assorted drugs containing a labile proton of carboxylic acid or alcohol moiety. Ligands used in these reactions are ampicillin trihydrate (ABP), ibuprofen (BPPA), acetylsalicylic acid (ASA), and acetaminophen (APAP). Characterization and structure elucidation of the complexes was achieved by elemental analysis, infrared spectroscopy and multinuclear (1H, 13C, and 119Sn) NMR spectroscopic studies. Their protonation behavior and stability constants were investigated and corresponding thermodynamic parameters were calculated using pH-potentiometric technique. It was suggested on basis of potentiometric studies that the complexes formed are invariably of 1:2 stoichiometry irrespective of ligand-to-metal ratio. The stability constants represented by log β values at 298 K were found to be in the order: ABP > APAP > BPPA > ASA. The free energy of formation of these complexes has a negative value, which shows that formation of the complexes is a spontaneous process. Also, the negative value of standard enthalpy change indicates that reaction of ligands with metal ion is exothermic and this validates the decrease in the value of log β with increasing temperature. Entropy change is positive which seems to be the driving force for complex formation.  相似文献   

5.
The speciation of curium(III) with L-threonine and O-phospho-L-threonine was determined by time-resolved laser-induced fluorescence spectroscopy (TRLFS) at trace Cm(III) concentrations (3?×?10?7?M). Curium species of the type MpHqLr were identified in the L-threonine- and O-phospho-L-threonine system. These complexes are characterized by their individual luminescence spectra and luminescence lifetimes. The following formation constants were determined (a) for L-threonine: log?β101?=?6.72?±?0.07, log?β102?=?10.22?±?0.09, and log?β1–22?=?(7.22?±?0.19) at ionic strength I?=?0.5?M and (b) for O-phospho-L-threonine: log?β121?=?18.03?±?0.13 and log?β111?=?14.17?±?0.09 at ionic strength I?=?0.154?M. Possible structures of the identified curium species are discussed on the basis of the luminescence lifetime measurements and the magnitude of the formation constants.  相似文献   

6.
We report results of a microcalorimetry study of the association of inorganic and organic cations with two p-sulfonatocalix[n]arenes (host 1: n = 4; host 2: n = 6) in aqueous solution at 298.15 K. First, we have determined the thermodynamic parameters for the complexation between the host 2 and a series of quaternary ammonium cations. We have evaluated the influence of the pH on the structure and energetics of these organic complexes. We have also reported the association constant and enthalpy of reaction for the complexation of some rare-earth cations (Sm3+, Dy3+, Y3+ and Sc3+ cations) with the two hosts. In all cases we have observed the formation of 1:1 complexes.

Whereas the association is driven by a favourable entropy change for the inorganic cations (ΔH > 0 and TΔS>>0), it is controlled by a favourable enthalpy change for the organic cations (ΔH < < 0 and TΔS < 0 or >0). In acidic solution, the complexes formed between host 2 and tetraalkylammonium cations are weaker than those formed with the cyclic tetramer. In neutral solution this effect is not observed. All the results are in line with a conformational change of host 2 with the pH.  相似文献   

7.
The complexation reactions between Mg2+, Ca2+, Ag+ and Cd2+ metal cations with N-phenylaza-15-crown-5 (Ph-N15C5) were studied in acetonitrile (AN)–methanol (MeOH), methanol (MeOH)–water (H2O) and propanol (PrOH)–water (H2O) binary mixtures at different temperatures using the conductometric method. The conductance data show that the stochiometry of all of the complexes with Mg2+, Ca2+, Ag+ and Cd2+ cations is 1:1 (L:M). The stability of the complexes is sensitive to the solvent composition and a non-linear behaviour was observed for variation of log K f of the complexes versus the composition of the binary mixed solvents. The selectivity order of Ph-N15C5 for the metal cations in neat MeOH is Ag+>Cd2+>Ca2+>Mg2+, but in the case of neat AN is Ca2+>Cd2+>Mg2+>Ag+. The values of thermodynamic parameters (ΔH c o , ΔS c o ) for formation of Ph-N15C5–Mg2+, Ph-N15C5–Ca2+, Ph-N15C5–Ag+ and Ph-N15C5–Cd2+ complexes were obtained from temperature dependence of stability constants and the results show that the thermodynamics of complexation reactions is affected by the nature and composition of the mixed solvents.  相似文献   

8.
The complex formation between Zn2+, Cd2+ and Pb2+ ions with macrocyclic ligand, tetrathia12-crown-4 (12S4) was studied in dimethylsulfoxide (DMSO)–nitrobenzene binary mixtures at different temperatures using conductometric and 1H NMR methods. In all cases, 12S4 found to form 1:1 complexes with these cations. The formation constants of the resulting 1:1 complexes in different solvent mixtures were determined by computer fitting of the resulting molar conductance- and chemical shift-mole ratio data. There is an inverse relationship between the complex stability and the amount of DMSO in the solvent mixtures. The stability of the resulting M2+-12S4 complexes found to decrease in the order Pb2+ > Cd2+ > Zn2+. The values of ?H°, ?S° and ?G° for complexation reactions were evaluated from the temperature dependence of formation constants via van’t Hoff method. The obtained results revealed that, in all cases, the complexes are enthalpy stabilized, but entropy destabilized and the values of ?H° and ?S° are strongly depend on the nature of medium. There is also a linear relationship between all ΔH° and TΔS° values indicating the existence of entropy–enthalpy compensation in complexation of the three cations and ligand in the solvent systems studied.  相似文献   

9.
The equilibrium constants and thermodynamic parameters for complex formation of 18-Crown-6 (18C6) with Tl+, Pb2+, Hg2+, and Zn2+ metal cations have been determined by conductivity measurements in methanol (MeOH)-water (H2O) binary solutions. 18-Crown-6 forms 1:1 complexes with Hg2+ and Zn2+ cations, but in the case of Tl+ and Pb2+ cations, in addition to 1:1 stoichiometry, 1:2 (ML2) complexes are formed in some binary solvents. The thermodynamic parameters (ΔH c0 and ΔS c0), which were obtained from the temperature dependences of equilibrium constants, show that in most cases the complexes are enthalpy destabilized but entropy stabilized. Non-linear behavior is observed between the equilibrium constants (log K f ) of complexes and the composition of the mixed solvent. The selectivity of the ligand for these metal cations is sensitive to the solvent composition, and, in some cases, the selectivity order is reversed in certain compositions of the mixed solvent. The results also show that the mechanism of complexation reactions and the stoichiometry of complexes of some metal cations change with the nature and even with the composition of the mixed solvent. The article was submitted by the authors in English.  相似文献   

10.
The complexation processes between Fe3+, Y3+, Cd2+, Sn4+, Ce3+ and Au3+ metal cations with macrocyclic ligand, 4′-nitrobenzo-15-crown-5 (4′NB15C5), were studied in acetonitrile (AN), methanol (MeOH) and nitromethane (NM) solvents at different temperatures using conductometric method. The conductance data show that the stoichiometry of the complexes formed between this macrocyclic ligand and Cd2+, Au3+ cations is 1: 1 (ML), but in the case of Fe3+, Y3+ and Ce3+ metal cations, 2: 1 (M2: L) and 2: 2 [M2: L2] complexes are formed in nitromethane solutions. The results show, that the selectivity of 4’NB15C5 for the studied metal cations in methanol solutions at 15°C is: Sn4+ > Cd2+ > Y3+ > Fe3+ ∼ Ce3+ > Au3+, but in the case of acetonitrile, the stability order was found to be: Y3+ > Au3+ > Fe3+ > Cd2+. The values of stability constants of the 1: 1 [M: L] complexes were determined from conductometric data using a GENPLOT computer program. The values of thermodynamic parameter (ΔH c o and ΔH c o) for formation of the complexes were obtained from temperature dependence of the stability constants, using the van’t Hoff plots. The results show that the values of standard enthalpy (ΔH c o) and standard entropy (ΔH c o) change with the nature of the non aqueous solvents.  相似文献   

11.
12.
The protonation and complex formation equilibria of two biodegradable aminopolycarboxylate chelants {dl-2-(2-carboxymethyl)nitrilotriacetic acid (GLDA) and 3-hydroxy-2,2??-iminodisuccinic acid (HIDS)} with Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+ ions were investigated using the potentiometric method at a constant ionic strength of I?=?0.10?mol·dm?3 (KCl) in aqueous solutions at 25?±?0.1?°C. The stability constants of the proton?Cchelant and metal?Cchelant species for each metal ion were determined, and the concentration distributions of various complex species in solution were evaluated for each ion. The stability constants (log10 K ML) of the complexes containing Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+ ions followed the identical order of log10 K CuL?>?log10 K NiL?>?log10 K PbL?>?log10 K ZnL?>?log10 K CdL for either GLDA (13.03?>?12.74?>?11.60?>?11.52?>?10.31) or HIDS (12.63?>?11.30?>?10.21?>?9.76?>?7.58). In each case, the constants obtained for metal?CGLDA complexes were larger than the corresponding constants for metal?CHIDS complexes. The conditional stability constants (log10 $ K_{\text{ML}}^{'} $ ) of the metal?Cchelant complexes containing GLDA and HIDS were calculated in terms of pH, and compared with the stability constants for EDTA and other biodegradable chelants.  相似文献   

13.
The structures of new butadienyl dyes of the benzothiazole series containing the dithia-15-crown-5 (2a) or dithia-18-crown-6 (2b) fragments were established by X-ray diffraction. Complexation of dyes 2a,b with Hg2+, Pb2+, Cd2+, Ag+, Zn2+, and alkaline-earth cations in aqueous-acetonitrile solutions was studied by spectrophotometry. At a high percentage of water in solutions (P w ≈ 50%), these dyes have a very low ability to bind Pb2+ cations (logK < 2) and virtually do not bind Cd2+, Zn2+, and alkaline-earth cations. At the same time, these dyes form stable 1: 1 complexes with Hg2+ and Ag+ cations at all P w. The stability constants of complexes with the Ag+ cation increase with increasing P w because the free energy of hydration of this cation is much lower than the free energy of solvation in acetonitrile. In the P w range from 0 to 75%, the stability constants of the complexes of dyes 2a,b with the Hg2+ cation are larger than those of the corresponding complexes with the Ag+ cation by more than four orders of magnitude. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 90–96, January, 2006.  相似文献   

14.
Three novel thiaazacrown ethers 1, 2 and 3 were synthesized in a simple way and in high yield. The complex formation between Ag+, Cu2+, Zn2+, Pb2+, Hg2+ and Cd2+ metal cations with thiaazacrown ethers 1, 2 and 3 have been studied in acetonitrile:chloroform (1:1) binary solvent system using conductometric technique. The conductance data show that the stochiometry of the complexes with Ag+, Cu2+ and Zn2+ cations is 1:1 (L:M), but in the case of Pb2+ and Hg2+ cations, a 1:2 (L:M) complex is formed in solutions. The formation constants of the resulting 1:1 complexes were determined from the molar conductance-mole ratio data at 25 °C. It was found that the stability constants of 1-Ag2+, 2-Ag+ and 3-Ag+ complexes are higher than those of their corresponding Zn2+ and Cu2+ complexes and found to vary in order 2 for Ag+.  相似文献   

15.
The synthesis and structural characterization of a tetrazine-based catecholamide (CAM) ligand, N,N′-bis(N″-(aminoethyl)-2,3-bis(hydroxy)benzamide)-1,2,4,5-tetrazine-3,6-diamine (5), were investigated. All compounds were characterized by 1H NMR spectroscopy, 13C NMR spectroscopy, and FTIR spectroscopy. The protonation equilibria of 5 and complexation capacities (log βpqr) of Cd2+, Co2+, and Cu2+ complexes of 5 were evaluated through potentiometric titration and spectrophotometric titration, respectively. Species independent pM value (=?log [M]free) was used to compare metal affinities with the final sequence Cu2+ > Cd2+ > Co2+. Results show that 5 has potential for heavy metal removal.  相似文献   

16.
The complex formation between Cu2+, Zn2+, Tl+ and Cd2+ metal cations with macrocyclic ligand, dibenzo- 18-crown-6 (DB18C6) was studied in dimethylsulfoxide (DMSO)–ethylacetate (EtOAc) binary systems at different temperatures using conductometric method. In all cases, DB18C6 forms 1:1 complexes with these metal cations. The stability constants of the complexes were obtained from fitting of molar conductivity curves using a computer program, Genplot. The non-linear behaviour which was observed for variations of log K f of the complexes versus the composition of the mixed solvent was discussed in terms of changing the chemical and physical properties of the constituent solvents when they mix with one another and, therefore, changing the solvation capacities of the metal cations, crown ether molecules and even the resulting complexes with changing the mixed solvent composition. The results show that the selectivity order of DB18C6 for the metal cations in pure ethylacetate and pure dimethylsulfoxide is: Tl+ > Cu2+ > Zn2+ > Cd2+ but the selectivity order is changed with the composition of the mixed solvents. The values of enthalpy changes (ΔH°C) for complexation reactions were obtained from the slope of the van’t Hoff plots and the changes in standard enthalpy (ΔS°C) were calculated from the relationship: ΔG°C,298.15H°C − 298.15 ΔS°C. The obtained results show that in most cases, the complexes are enthalpy stabilized, but entropy destabilized and the values of ΔH°C and ΔS°C depend strongly on the nature of the medium.  相似文献   

17.
The synthesis and complexive abilities of 5,11,17-tris(tert-butyl)-23 amino-25,26,27,28-tetra-propoxycalix[4]arene towards alkali cations Li+, Na+, K+, Rb+, Cs+ and alkali earth cations Mg2+, Ca2+, Sr2+ and Ba2+ in methanol-chloroform mixture have been evaluated at 25°C, using UV-Vis spectrophotometric techniques. The results showed that the ligand is capable to complex with all the cations by 1: 1 metal to ligand ratios. The selectivity presented considering the calculated formation constants are in the order Li+ > Na+ > K+ > Rb+ > Cs+ and Mg2+ > Ca2+ > Sr2+ > Ba2+ with the ligand.  相似文献   

18.
The complexation reaction between Zn2+, Pb2+, Cd2+ and Tl+ cations by 5,7‐diiodo‐8‐hydroxyquinoline (IQN) was studied in the Dimethylformamide /Acetonitril (DMF‐AN) binary system using square wave polarography technique. The stoichiometry and stability of the complexes were determined by monitoring the shifts in half‐wave or peak potential of the polarographic waves of metal ions against the ligand concentration. The stoichiometry of the complexes was found to be 1:1. The results obtained show that there is an inverse relationship between the formation constant of the complexes and the donor number of solvent base on the Guttmann donocity scale. In all cases the formation constants increased with increasing amounts of AN in these binary systems. The selectivity order for IQN complexes with the cations is Zn2+ > Pb2+ > Cd2+ > Tl+.  相似文献   

19.
The redox properties of the tri-heteropolytungstosilicates of transition elements KnSiZ(H2O)W11O39 (Z ? Mn2+, Fe3+, Co2+, Ni2+, Zn2+, Cd2+). In solution have been studied with polarography and cyclic voltammetry as well as with ultraviolet spectroscopy and X-ray photoelectron spectroscopy. The order of the polarographic half-wave potentials (E1/2) of these heteropolyanions is as follows: Z?Ni2+>Co2+>Zn2+>Fe2+>Mn2+. We have found that the E1/2 of heteropolyanions could be correlated linearly with both the electronegativities X of the transition elements and the logarithm of the rate constants (log ke) of reaction of transition metal ions with hydrated electrons. The reduction mechanism and effects of transition elements on the redox properties of the heteropolyanions have been discussed.  相似文献   

20.
The complexation reactions between La3+, Y3+ and Ce3+ cations with the macrocyclic ligand, kryptofix 21, were studied in methanol-acetonitrile (MeOH-AN) and methanol-methylacetate (MeOHMeOAc) binary mixed solvent solutions at different temperatures using the conductometric method. The conductance data show that in most solvent systems, the kryptofix 21 forms a 1: 1 [M: L] complex with La3+, Y3+ and Ce3+ metal cations, but in the case of Y3+ cation in pure methylacetate, in addition of formation of a 1: 1 [ML] complex, 1: 2 [ML2] and 1: 3 [ML3] complexes are formed in solution. In the case of Ce3+cation, a 1: 1 [ML] and also a 1: 2 [ML2] complexes are formed in this solvent system at all studied temperatures. The electrical conductance data in acetonitrile, show that a 1: 1 [ML] and also a 1: 2 [ML2] complexes are formed between the ligand and La3+ and Ce3+ metal cations at different temperatures. The stability constants of the 1: 1 [ML] complexes were determined using the conductometric data and a computer program, GENPLOT. A non-monotonic relationship was observed between logK f of the 1: 1 complexes with the composition of the binary solvent solutions which was discussed in term of solvent-solvent interactions and also preferential solvation of the metal cations and the ligand in solutions. The selectivity order of the ligand for the metal cations in MeOH–AN and MeOH–MeOAc binary solvent solutions, at 25°C was found to be: Y3+ > La3+ > Ce3+ and La3+ > Y3+ > Ce3+, respectively. The values of the standard thermodynamic quantities (ΔH c ° and ΔS c ° ) for formation of the 1: 1 complexes were obtained from temperature dependence of the stability constans of the complexes and the results show that the thermodynamics of the complexation reactions between kryptofix 21 and La3+, Y3+ and Ce3+ cations, is affected by the nature and composition of the mixed solvents systems.  相似文献   

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