An ab initio MO study on the structures and electronic states of hydrogen-bonded O3- HF and SO2-HF complexes

Ab initio molecular orbital (MO) calculations have been carried out for base-hydrogen fluoride (HF) complexes (base = O3 and SO2) in order to elucidate the structures and energetics of the complexes. The ab initio calculations were performed up to the QCISD(T)/6-311++G(d,p) level of theory. In both complexes, hydrogen-bonded structures where the hydrogen of HF orients toward one of the oxygen atoms of bases were obtained as stable forms. The calculations showed that cis and trans isomers exist in both complexes. All calculations for the SO2-HF complex indicated that the cis form is more stable in energy than the trans form. On the other hand, in O3-HF complexes, the stable structures are changed by the ab initio levels of theory used, and the energies of the cis and trans forms are close to each other. From the most sophisticated calculations (QCISD(T)/6-311++G(d,p)//QCISD/6-311+G(d) level), it was predicted that the complex formation energies for cis SO2-HF, trans SO2-HF, cis O3-HF, and trans O3-HF are 6.1, 5.7, 3.4, and 3.6 kcal/mol, respectively, indicating that the binding energy of HF to SO2 is larger than that of O3. The harmonic vibrational frequencies calculated for cis O3-HF and cis SO2-HF complexes were in good agreement with the experimental values measured by Andrews et al. Also, the calculated rotation constants for cis SO2-HF agreed with the experiment.     

Comparative study on camphor enantiomers behavior under the conditions of gas-liquid chromatography and reversed-phase high-performance liquid chromatography systems modified with alpha- and beta-cyclodextrins

The dependence of retention and selectivity parameters of camphor enantiomers on the concentration of alpha- and beta-cyclodextrins were studied under conditions of GLC (matrix solvent: Glycerol, 95 degrees C) and RP-HPLC (matrix solvent: Aqueous methanolic, 20 degrees C). It has been found that beta-cyclodextrin forms complex of 1:1 stoichiometry and does not recognize enantiomers of camphor. In contrast alpha-CD forming complexes of 1:2 stoichiometry appeared to be very efficient chiral selector of (+) and (-)-camphor. Relatively considerable differences have been observed between stability constants determined by GLC and RP-HPLC, what may be explained by the various natures of the matrix solvents and the various temperatures of the measurements. On the contrary, the enantioseparation factor alpha observed at higher concentrations of alpha-cyclodextrin stabilizes on the very similar value alpha+/-(GLC) approximately = alpha-/+(HPLC) approximately = 1.6. Simple theoretical considerations focusing on the differences in the mechanisms of the studied processes have been performed. According to them the enantiomer forming the more stable complex with the cyclodextrin should be eluted from the RP-HPLC column first and GLC column last. This fact has been confirmed experimentally.     

Coordination of rare-earth elements in complexes with monovacant Wells-Dawson polyoxoanions

The alpha-1 and alpha-2 isomers of the monovacant Wells-Dawson heteropolyoxoanion [P(2)W(17)O(61)](10-) are complexants of trivalent rare-earth (RE) ions and serve to stabilize otherwise reactive tetravalent lanthanide (Ln) and actinide (An) ions in aqueous solution. Aspects of the bonding of Ln ions with alpha-1-[P(2)W(17)O(61)](10-) and alpha-2-[P(2)W(17)O(61)](10-) were investigated to address issues of complex formation and stability. We present structural insights about the Ln(III) coordination environment and hydration in two types of stoichiometric complexes, [Ln(alpha-1-P(2)W(17)O(61))](7-) and [Ln(alpha-2-X(2)W(17)O(61))(2)](17-) (for Ln identical with Sm, Eu, Lu; X identical with P, As). The crystal and molecular structures of [(H(2)O)(4)Lu(alpha-1-P(2)W(17)O(61))](7-) (1) and [Lu(alpha-2-P(2)W(17)O(61))(2)](17-) (2) were solved and refined through use of single-crystal X-ray diffraction. The crystallographic results are supported with corresponding insights from XAFS (X-ray absorption fine structure) for a series of nine solid-state complexes as well as from optical luminescence spectroscopy of the Eu(III) analogues in aqueous solution. All the Ln ions are eight-coordinate with oxygen atoms in a square antiprism arrangement. For the 1:1 stoichiometric Ln/alpha-1-[P(2)W(17)O(61)](10-) complexes, the Ln ions are bound to four O atoms of the lacunary polyoxometalate framework in addition to four O atoms from solvent (water) molecules as [(H(2)O)(4)Ln(alpha-1-P(2)W(17)O(61))](7-). This structure (1) is the first of its kind for any metal complex of alpha-1-[P(2)W(17)O(61)](10-), and the data indicate that the general stoichiometry [(H(2)O)(4)Ln(alpha-1-P(2)W(17)O(61))](7-) is maintained throughout the lanthanide series. For the 1:2 stoichiometric Ln/alpha-2-[X(2)W(17)O(61)](10-) complexes, no water molecules are in the Ln-O(8) coordination sphere. The Ln ions are bound to eight O atoms-four from each of two heteropolyanions-as [Ln(alpha-2-X(2)W(17)O(61))(2)](17-). The average Ln-O interatomic distances decrease across the lanthanide series, consistent with the decreasing Ln ionic radius.     

Solution and solid state studies on the binding of isomeric carboranes C2B10H12 by p-Bu(t)-calix[5]arene

p-Bu(t)-calix[5]arene forms crystalline inclusion complexes with o- and m-carboranes in toluene or dichloromethane-hexane, but not with the p-isomer, the extended structures being based on 1 : 1 host-guest supermolecules, with the p-Bu(t)-substituents creating a snug fit for o- and m-carborane; p-carborane forms a highly hexane soluble complex, induced by grinding, which crystallizes as fibres. Solution phase studies showed the presence of a 1 : 1 host-guest stoichiometry with all three isomeric carboranes as determined from Job plots. The association constants for the o- and m-carborane complexes are 6.4 +/- 0.3 M(-1) and 3.8 +/- 0.1 M(-1) respectively, whereas the p-isomer is only weakly associated. Competition experiments involving all three isomers show rapid exchange on the NMR time scale, and no selectivity in solution is evident. Selective association involving the o- and m-isomers in the solid state is therefore remarkable, and it is a manifestation of crystal packing forces which embodies the differences in dipole moments of the carboranes.     

Reactivity of cyclooligophosphanes: synthesis and structural characterisation of cyclo-1,4-(BH3)2(P4Ph4CH2) and cyclo-1,2-(BH3)2(P5Ph5)

The borane complexes cyclo-1,4-(BH3)2(P4Ph4CH2) (3) and cyclo-1,2-(BH3)2(P5Ph5) (4) were prepared by reaction of cyclo-(P4Ph4CH2) and cyclo-(P5Ph5) with BH3(SMe2). Only the 2:1 complexes 3 and 4 were isolated, even when an excess of the borane source was used. In solution, 3 exists as a mixture of the two diastereomers (R(P)*,S(P)*,S(P)*,R(P)*)-(+/-)-3 and (R(P)*,R(P)*,R(P)*,R(P)*)-(+/-)-3. However, in the solid state the (R(P)*,S(P)*,S(P)*,R(P)*)-(+/-) diastereomer is the major stereoisomer. Similarly, while only one isomer of 4 is observed in its X-ray structure, NMR spectroscopic investigations reveal that it forms a complex mixture of isomers in solution. 3 may be deprotonated with tBuLi to give the lithium salt cyclo-1,4-(BH3)2(P4Ph4CHLi) (3 x Li), though this could not be isolated in pure form.     

Contrasting chemistry of cis- and trans-platinum(II) diamine anticancer compounds: hydrolysis studies of picoline complexes

cis-[PtCl2(NH3)(2-picoline)] (AMD473) is currently on clinical trials as an anticancer drug. The trans isomer, AMD443 (1), is also cytotoxic in a variety of cancer cell lines. The X-ray crystal structure of the trans isomer (1) shows that the pyridine ring is tilted by 69 degrees with respect to the platinum square-plane in contrast to the cis isomer in which it is almost perpendicular (103 degrees ). In the 3-picoline (2) and 4-picoline (3) trans isomers, the ring is tilted by 58 degrees /60 degrees (2 molecules/unit cell) and by 56 degrees , respectively. Hydrolysis may be an important step in the intracellular activation and anticancer mechanism of action of these complexes. The first hydrolysis step is relatively fast even at 277 K, with rate constants (determined by 1H,15N NMR) of k1 = 2.6 x 10(-5) s(-1), 12.7 x 10(-5) s(-1), and 5.2 x 10(-5) s(-1) (I = 0.1 M) for formation of the monoaqua complexes of 1-3, respectively. Although the hydrolysis of 3 is slower than 2, it is hydrolyzed to a greater extent. No formation of the diaqua complex was observed for any of the three complexes at 277 K, and it accounts for <3% of the platinum species at 310 K. In general the extent of hydrolysis of the trans complexes is much less than for their cis analogues. The pK(a) values for the monoaqua adducts of 1-3 were determined to be 5.55, 5.35, and 5.39, respectively, suggesting that they would exist largely as the monohydroxo complex at physiological pH. The pKa values for the diaqua adducts were determined to be 4.03 and 7.01 for 1, 3.97 and 6.78 for 2, and 3.94 and 6.88 for 3, the first pK(a) being >1 unit lower than for related cis complexes.     

Thermodynamic and geometric study of diasteroisomeric complexes formed by racemic flavanones and three cyclodextrins through NMR

The main purpose of this work was to study the chiral recognition thermodynamics of inclusion complexes formed by flavanones and β-cyclodextrins, and its relation with the inclusion geometries, through NMR experiments. By using the racemic mixtures of (±)-flavanone (FL) and (±)-2′-hydroxyflavanone (2′OHFL), diasteroisomeric complexes were formed employing β-cyclodextrin (βCD), (2-hydroxypropil)-β-cyclodextrin (HPβCD) and heptakis-(2,6-O-dimethyl)-β-cyclodextrin (DMβCD). ¹H NMR experiments of the complexes showed enantiodifferentiation for FL/βCD, FL/HPβCD, FL/DMβCD, 2′OHFL/HPβCD and 2′OHFL/DMβCD complexes, so they were able to be studied by obtaining the stoichiometry (1:1 for each complex), association constants (Ka), Ka ratios, and thermodynamics (ΔH, ΔS and ΔG). The results show that Ka values decrease with increasing temperature and that Ka ratio values removed from 1 not always reflect better enantiodiscrimination by NMR. Thermodynamics (ΔH and ΔG) show an exothermic and spontaneous formation of the complexes. Since the results were established for each couple of diasteroisomeric complexes separately, comparison of thermodynamics between them was possible, concluding that one half of the couples of diasteroisomeric complexes present chiral recognition due to enthalpic phenomena and the other half due to entropic phenomena. Additionally, ROESY experiments were performed to estimate the inclusion geometry of the complexes, which are in good agreement with the thermodynamic and Ka results.     

Cis‐trans Isomerism in Copper(II) Complexes with N‐acyl Thiourea Ligands

The N‐acyl thiourea complexes bis[N,N‐diethyl‐N′‐(p‐nitrobenzoyl)‐thioureato]copper(II) ( 1a,1b ) and bis(N,N‐diphenyl‐N′‐benzoylthioureato)copper(II) ( 2a,2b ) crystallize in each case in two modifications. X‐ray structural analysis shows that 1a and 1b are cis‐trans isomers. This is very unusual for N‐acyl thioureato complexes because with exception of one platinum(II) complex up to now only cis complexes have been found. In contrast X‐ray structural analysis of both forms 2a and 2b of the other complex shows no cis‐trans pair. Both modifications are cis complexes. In solution both isomers of the copper(II) complexes are observable by EPR spectroscopy.     

Synthesis and characterization of iron(II) and ruthenium(II) hydrido hydrazine complexes

Treatment of trans-[MHCl(dmpe)(2)] (M = Fe, Ru) with hydrazine afforded the hydrido hydrazine complexes cis- and trans-[MH(N(2)H(4))(dmpe)(2)](+) which have been characterized by NMR spectroscopy ((1)H, (31)P, and (15)N). Both cis and trans isomers of the Fe complex and the trans isomer of the Ru complex were characterized by X-ray crystallography. Reactions with acid and base afforded a range of N(2)H(x) complexes, including several unstable hydrido hydrazido complexes.     

Remarkable interplay of redox states and conformational changes in a sterically crowded, cross-conjugated tetrathiafulvalene vinylog

Derivatives of 9-[2-(1,3-dithiol-2-ylidene)ethylidene]thioxanthene have been synthesized using Horner-Wadsworth-Emmons reactions of (1,3-dithiol-2-yl)phosphonate reagents with thioxanthen-9-ylidene-acetaldehyde (5). Further reactions lead to the sterically crowded cross-conjugated "vinylogous tetrathiafulvalene" derivative 9-[2,3-bis-(4,5-dimethyl-1,3-dithiol-2-ylidene)-propylidene]thioxanthene (10). X-ray crystallography, solution electrochemistry, optical spectroscopy, spectroelectrochemistry, and simultaneous electrochemistry and electron paramagnetic resonance spectroscopy, combined with theoretical calculations performed at the B3LYP/6-31G(d) level, elucidate the interplay of the electronic and structural properties in these molecules. For compound 10, multistage redox behavior is observed: the overall electrochemical process can be represented by 10-->10(.+)-->10(2+)-->10(4+) with good reversibility for the 10-->10(.+)-->10(2+) transformations. At the tetracation stage there is the maximum gain in aromaticity at the dithiolium and thioxanthenium rings. Theory predicts that for 10, 10(.+), and 10(2+) the trans isomers are more stable than the cis isomers (by ca. 2-18 kJ mol(-1)), whereas for 10(4+) the cis isomer becomes more stable than the trans isomer (by ca. 25 kJ mol(-1)) [trans and cis refer to the arrangement of the two dithiole moieties with respect to the central ==C(R)--C(H)== fragment]. These data explain the detection in cyclic voltammograms of both trans and cis isomers of 10 and 10(.+) during the reduction of 10(4+) at fast scan rates (>100 mV s(-1)) when the cis-trans isomerization is not completed within the timescale of the experiment. The X-ray structure of the charge-transfer complex (CTC) of 10 with 2,4,5,7-tetranitrofluorene-9-dicyanomethylenefluorene (DTeF) [stoichiometry: 10(.+)(DTeF)(2) (.-)2 PhCl] reveals a twisted conformation of 10(.+) (driven by the bulky thioxanthene moiety) and provides a very rare example of segregated stacking of a fluorene acceptor in a CTC.     

Ab initio studies of CIO, reactions: prediction of the rate constants of CIO + NO for the forward and reverse processes.

The mechanisms for ClO+NO and its reverse reactions were investigated by means of ab initio molecular orbital and statistical theory calculations. The species involved were optimized at the B3LYP/6-311 +G(3df) level, and their energies were refined at the CCSD(T)/6-311+ G(3df)//B3LYP/6-311 + G(3df) level. Five isomers and the transition states among them were located. The relative stability of these isomers is ClNO2 > cis-ClONO > trans-ClONO > cis-OClNO>trans-OClNO. The heats of formation of the three most-stable isomers were predicted using isodesmic reactions by different methods. The predicted bimolecular reaction rate constant shows that, below 100 atm, the formation of Cl+NO2 is dominant and pressure-independent. The total rate constant can be expressed as: k(ClO+NO)= 1.43 x 10(-9)T(-083)exp(92/ T) cm3 molecule(-1)s(-1) in the temperature range of 200-1000 K, in close agreement with experimental data. For the reverse reaction, Cl+NO2-->ClNO2 and ClONO (cis and trans isomers), the sum of the predicted rate constants for the formation of the three isomers and their relative yields also reproduce the experimental data well. The predicted total third-order rate constants in the temperature range of 200-1000 K can be represented by: k0(He) = 4.89 x 10(-6)T(-5.85) exp(-796/T) cm6 molecule(-1)s(-1) and k0(N2) =5.72 x 10(-15)T(-5.80) exp(-814/T) cm6 molecule(-1)s(-1). The predicted high- and low-pressure limit decomposition rates of CINO2 in Ar in the temperature range 400-1500 K can be expressed, respectively, by: k-(ClNO2) = 7.25 x 10(19)T(-1.89) exp(-16875/T) s(-1) and kd(ClNO2) = 2.51 x 10(38)T(-6.8) exp(-18409/T) cm3 molecule(-1) s(-1). The value of k0(ClNO2) is also in reasonable agreement with available experimental data.     

Transesterification and amide cis-trans isomerization in Zn and Cd complexes of the chelating amino acid ligand Boc-Asp(Dpa)-OBzl

The amino acid derivative Boc-Asp-OBzl (Boc=N-butyloxycarbonyl; Asp=aspartic acid; Bzl=benzyl) was functionalized by coupling its carboxylate side chain to dipicolylamine. This yielded the tridentate nitrogen donor ligand Boc-Asp(Dpa)-OBzl (-OBzl). The compound -OBzl contains three different carbonyl groups: a tertiary amide linkage between Asp and Dpa, a C-terminal benzyl ester function, and an N-terminal urethane protecting group. NMR spectra were used to compare the reactivity of these moieties. The Boc protecting group gives rise to two isomers, (E, 9%) and (Z, 91%). Coordination of Cd(NO3)2 and Zn(NO3)2 yielded the complexes and. These compounds have significantly reduced barriers to rotation about the tertiary amide C-N bond compared with the free ligand (-OBzl:18.5 kcal mol-1 in CDBr3;: 12.9 kcal mol-1 in (CD3)2CO;: 13.8 kcal mol-1 in (CD3)2CO). Both complexes readily undergo transesterification in methanol or CD3OD. Experimental pseudo-first order rate constants were determined in CD3OD and (CD3)2CO:CD3OD (3:1;). It was found that the zinc complex (k=(2.28+/-0.02)x10(-4) s-1) is significantly more reactive than the cadmium complex (k=(1.41+/-0.03)x10(-6) s-1). In order to study their tertiary amide cis-trans isomerization, the cadmium complex [(-OCH3)Cd(NO3)2] was synthesized, and the zinc complex [(-OCD3)Zn(NO3)2] was generated in situ in (CD3)2CO:CD3OD (3:1). The barriers to rotation were determined (:14.1 kcal mol-1 in CD3OD;: 13.4 kcal mol-1 in (CD3)2CO:CD3OD (3:1)). Our results show that the stronger Lewis-acid zinc(II) is significantly more active than cadmium(II) in the acceleration of the transesterification. This is in marked contrast to the tertiary amide bond rotation which is comparably fast with both metal ions.     

Complexation behavior of alpha-, beta-, and gamma-cyclodextrin in modulating and constructing polymer networks

A systematic study of the host-guest complexation by alpha-, beta-, and gamma-cyclodextrin (CD) in either the free state or as substituents of poly(acrylic acid) (PAA) with the hydrophobic n-octadecyl groups, C18, substituted onto PAA (HMPAA) and its effect on polymer aggregation and network formation is reported. Free alpha-CD, beta-CD, and gamma-CD mask hydrophobic associations between the C18 substituent of HMPAA in aqueous solution and form host-guest complexes with a 1:1 or CD:C18 substituent stoichiometry at 0.5 wt % polymer concentration. For alpha-CD this host-guest stoichiometry changes to 2:1 or 2alpha-CD:C18 at > or =1 wt % polymer concentrations but not for beta-CD and gamma-CD. Shear-thickening occurs when gamma-CD complexes C18 HMPAA substituents. Upon addition of sodium dodecyl sulfate, SDS (SDS:CD = 1:1), the hydrophobic associations between C18 diminished by alpha-CD masking were fully restored, were only partly restored in the case of beta-CD, and not restored for gamma-CD. When alpha- and beta-CD substituted PAA (alpha-CDPAA and beta-CDPAA) were mixed with HMPAA polymer, networks formed. As for free beta-CD, the beta-CD substituents of beta-CDPAA also formed 1:1 or beta-CD:C18 stoichiometry host-guest complexes with the C18 substituents of HMPAA. The alpha-CD substituents of alpha-CDPAA also formed 1:1 or alpha-CD:C18 stoichiometry host-guest complexes with some indication of the formation of 2:1 or 2alpha-CD:C18 stoichiometry host-guest complexes at polymer concentrations > or =1 wt %. The polymer networks formed by beta-CDPAA with HMPAA are less viscous than those formed by alpha-CDPAA, for which shear-thickening occurs at polymer concentrations > or =2 wt %. It is evident that the difference in CD annular size and its match with the C18 of HMPAA control the diversity of the interactions of alpha-CD, beta-CD, gamma-CD, alpha-CDPAA, and beta-CDPAA with HMPAA.     

Synthesis, characterization and electronic spectra of cefadroxil complexes of d-block elements

Cefadroxil (CD) is an essential pharmaceutical drug used in curing many diseases. Due to its popular use in many pharmaceutical forms, attention is paid in this research to the synthesis and stereochemistry of new iron, cobalt, nickel, copper, and zinc complexes of this drug both in solution and the solid states. The spectra of these complexes in solution and the study of their stoichiometry refer to the formation of 1:1 and 1:2 ratios of metal (M) to ligand (L). The calculated stability constants (Kf) of these complexes (1.5x10(7) to 5x10(13)) and the change in free energy of formation (deltaGf=2.5-12.5 kcal mol(-1) degree(-1)) are indicative of their high stability. The stereo chemical structure of the solid complexes was studied on the basis of their analytical, spectroscopic, magnetic, and thermal data. Infrared spectra proved the presence of M-N and M-O bonds. Magnetic susceptibility and solid reflectance spectral measurements were used to infer the structure. The prepared complexes were found to have the general formulae [ML(OH)x(H2O)y](H2O)z-M: Fe(II), x=0, y=2, z=1; M: Fe(III) and Co(III), x=1, y=2, z=1; M: Co(II) and Zn(II), x=0, y=1, z=0; M: Ni(II) and Cu(II), x=1, y=0, z=1; L: CD. Octahedral and tetrahedral structures were proposed for these complexes depending upon the magnetic and reflectance data and were confirmed by detailed mass and thermal analyses comparative studies.     

Fluorescence enhancement of coumarin-6-sulfonyl chloride amino acid derivatives in cyclodextrin media.

Coumarin-6-sulfonyl (6-CS) amino acid derivatives form inclusion complexes with a- and /-cyclodextrins (CD) in aqueous solution. The stoichiometry of the inclusion complex and the equilibrium constant were investigated. Using a fluorescence technique and alanine-beta-CD as a model, a 1:2 guest-host complex was established, and K = 4.7 x 10(5) mol(-2) l(2) was obtained. Fluorescence enhancement was observed for all derivatives studied, with glycine exhibiting a greater enhancement, and tyrosine showing the least. The stability of the inclusion complex was found to depend on the respective sizes of the guest-host complex and their interaction.     

First pseudorotaxane-like [3]complexes based on cryptands and paraquat: self-assembly and crystal structures

A new cryptand, bis(1,3,5-phenylene)tri(1,4,7,10-tetraoxadecyl) (3a), has been synthesized in good yield from bis(5-hydroxy-1,3-phenylene)-26-crown-8 (2a) and tri(ethylene glycol) ditosylate using pseudo-high dilution conditions. 3a forms a strong 1:1 complex with paraquat (1) in acetone solution with a high apparent association constant, 1.4 x 10(4) M(-)(1). A stoichiometry of 1:1 was also observed by mass spectrometry in the gaseous state. However, in the solid state, as determined by X-ray crystallography, the two complexes of 3a and the previously reported homologous cryptand, bis(1,3,5-phenylene)tri(1,4,7,10,13-pentaoxatridecyl) (3b), with paraquat (1) have 2:1 stoichiometry. A unique feature of these trimolecular pseudorotaxane-like complexes is that the guest occupies parts of the cavities of two cryptand molecules. For the first time it was found that in cryptand-based complexes, different stoichiometries are possible for the same host-guest pair.     

Richness of isomerism in labile octahedral Werner-type cobalt(II) complexes demonstrated by 19F NMR spectroscopy: structure and stability

The cobalt(II) complexes [CoL2(R2-Py)2] (1-4) where HLA = 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, R2-Py = 4-methylpyridine (1), HLB = 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione, R2-Py = 4-methylpyridine (2), 4-phenylpyridine (3) and S-(-)-1-(4-pyridyl)ethanol (4) were prepared by two-step reactions. X-ray structure analysis of [CoLA2(CH3-Py)2] revealed the {trans(N)-trans(CF3)-trans} configuration for the complex obtained by crystallization from ethanol. A dynamic equilibrium between the five possible stereoisomers was observed for each complex 1-4 in solution by 19F NMR spectroscopy. The criteria used for full NMR assignment (180-265 K) include comparison of integral ratios, cis(N) and trans(N) differentiation in presence of the chiral amine [S-(-)-1-(4-pyridyl)ethanol], effect of solvent polarity on the relative stabilities of the five isomers and observation of trans influences in a mixture of complexes. Thermodynamic parameters for the equilibria between the isomers of 2 in CD2Cl2 (DeltaHi,j, DeltaSi,j and Ki,j) were obtained from signal integrals. The two trans(N) isomers are slightly more stable than the three cis(N) isomers at low temperature [DeltaGdegreesi,j (max) = 2.8 kJ mol(-1) at 179.8 K], but this stability difference almost vanishes with increasing temperature [DeltaGdegreesi,j (max) = 1.0 kJ mol(-1) at 265.0 K]. The values found for DeltaHdegreesi,j are relatively small and largely entropy compensated.     

Counter-current chromatographic estimation of hydrophobicity of Z-(cis) and E-(trans) enalapril and kinetics of cis/trans isomerization

The kinetics of Z-(cis)/E-(trans) isomerization of enalapril was investigated by reversed phase high-performance liquid chromatography (RP-HPLC) using a monolith ODS column under a series of different temperature and pH conditions. At a neutral pH 7, the rate (k(obs)) of Z-(cis)/E-(trans) isomerization of enalapril at 4 degrees C (9.4 x 10(-3)min(-1)) is much lower than at 23 degrees C (1.8 x 10(-1)min(-1)), while the fractional concentration of Z-(cis) isomer is always higher than that of E-(trans) isomer in the pH range 2-7. The fractional concentration of the E-(trans) isomer becomes a maximum (about 40%) in the pH range 3-6, where enalapril exists as a zwitterion. The hydrophobicity (logP(O/W)) of both isomers was estimated by high-speed counter-current chromatography (HSCCC). Normal phase HSCCC separation using a tert-butyl methyl ether-acetonitrile-20mM potassium phosphate buffer (pH 5) two-phase solvent system (2:2:3, v/v/v) at 4 degrees C was effective in partially separating the isomers, and the partition coefficient (K) of each isomer was directly calculated from the retention volume (V(R)). The logP(O/W) values of Z-(cis) and E-(trans) isomers were -0.46 and -0.65, respectively.     

Inclusion complexes of a bichromophoric diester containing anthracene and naphthalene groups with alpha- and beta-cyclodextrins: thermodynamics and molecular mechanics

Fluorescence and molecular mechanics have been used to study the inclusion complexes of the (9-anthryl)-COO-(CH2)2-OOC-(2-naphthyl) bichromophoric compound with alpha- and beta-cyclodextrins. Emission spectra upon excitation of the naphthalene group denote the presence of non-radiative energy transfer from naphthalene to anthracene, which is influenced by the type of CD. Naphthalene emission also shows two peaks whose ratio of intensities R is sensitive to the medium polarity. The stoichiometry, the formation constants and the changes of enthalpy and entropy upon inclusion of complexes formed were obtained from the change of R with CD concentration and temperature. Both complexes, in agreement with Job's plots, show 1:1 stoichiometry. Quenching, fluorescence depolarization and the analysis of R when all the guests are complexed permit us to explain the possible location of CDs in the complexes formed. Molecular mechanics calculations were also employed to study the formation of 1:1 complexes with both alpha- and betaCDs. The study was mainly performed in the presence of water as a solvent. Results seem to explain the stoichiometries and geometry for both complexes.     

Detection and Removal of Metal Ion based on a Fluorescent Sensor Composed of a Photoresponsive Rhodamine Derivative by Host–Gust Interaction

Although a variety of chemosensors as probes have been exploited for the detection of metal ions with high sensitivity and selectivity, the formed probe–metal complex was hardly suitable for separation, removal, and further recovery. This paper presents a method to detect and remove metal ions from aqueous solutions simultaneously by a fluorescence chemosensor and functional magnetic nanoparticles. A novel probe SRhB ‐Azo was synthesized based on rhodamine B (RhB ), maleic anhydride (MAH ), and azobenzene (Azo). SRhB ‐Azo showed high selectivity and sensitivity to Hg ions in aqueous solutions. Job's experiment showed the formation of a 1:2 stoichiometry complex between Hg²⁺ and SRhB ‐Azo. Moreover, β‐cyclodextrin (β‐CD )‐modified magnetic nanoparticles (CD‐MNPs ) were fabricated and used as host materials to form the inclusion complex CD–MNP and SRhB ‐Azo–Hg²⁺. Then, the SRhB ‐Azo‐Hg²⁺ complex could be removed by an external magnet, and subsequently recovered by UV ‐irradiation‐induced trans/cis isomerization of the Azo groups. The CD‐MNP s could be reused for nearly four times. Thus, the SRhB ‐Azo probe and CD‐MNP system has great potential application in sewage treatment.