大环疏水效应: 冠醚在DMF+H2O混合物中的焓对作用

利用等温滴定微量热法测定了298.15 K时12-冠-4、15-冠-5、18-冠-6和4,13-二氮杂-18-冠-6四种冠醚在纯水及不同质量分数(w=0-0.3)的N,N-二甲基甲酰胺(DMF)+H₂O混合物中的稀释焓, 根据McMillan-Mayer理论计算得到相应的焓对作用系数(h_xx). 实验发现, h_xx均为较大的正值, 表明在冠醚-冠醚自相互作用中疏水性成分占绝对优势, 主要表现为两种机制: (1) 当疏水-疏水作用发生时, 共球交盖使得水结构形成减少, 对h_xx有正的贡献; (2) 当疏水-亲水作用发生时, 共球交盖使得水结构破坏增加, 对h_xx有正的贡献. 此外, 四种冠醚h_xx的大小关系为: h_xx(18-冠-6)>h_xx(4,13-二氮杂-18-冠-6)≈h_xx(15-冠-5)>h_xx(12-冠-4), 表明冠醚环越大, 疏水-疏水作用越强, 存在显著的大环疏水效应.     

Thermodynamics of Solvation of 18-Crown-6 and Its Alkali-Metal Complexes in Various Solvents

Heats of solution of 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6) in acetonitrile, 1,2-dichloroethane, N,N-dimethylformamide, dimethyl sulfoxide, nitromethane, propylene carbonate, pyridine and water were measured at 25 °C and the enthalpies of the transfer of 18-crown-6 from waterto the aprotic solvents were derived. The thermodynamic quantities, G₁°, H₁° and T S₁°, for the formation of the[M(18-crown-6)]⁺ (M⁺ = Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺) complexeswere determined by titration calorimetry in dimethyl sulfoxide containing0.1 mol dm^-3 (C₂H₅)₄NClO₄ as a constant ionic medium at 25 °C. These thermodynamic quantities suggest that the complexationof 18-crown-6 with the alkali-metal ions mainly reflects the different solvationof 18-crown-6 and also the different degree of solvent structure.     

Gibbs energies of transferring triglycine from water into H2O-DMSO solvent

The Gibbs energies of transferring triglycine (3Gly, glycyl-glycyl-glycine) from water into mixtures of water with dimethyl sulfoxide (χ_DMSO = 0.05, 0.10, and 0.15 mole fractions) at 298.15 K are determined from the interphase distribution. An increased dimethyl sulfoxide (DMSO) concentration in the solvent slightly raises the positive values of Δ_tr G ^○(3Gly), possibly indicating the formation of more stable 3Gly-H₂O solvated complexes than ones of 3Gly-DMSO. It is shown that the change in the Gibbs energy of transfer of 3Gly is determined by the enthalpy component. The relationship of 3Gly and 18-crown-6 ether (18C6) solvation’s contributions to the change in the Gibbs energy of [3Gly18C6] molecular complex formation in H₂O-DMSO solvents is analyzed, and the key role of 3Gly solvation’s contribution to the change in the stability of [3Gly18C6] upon moving from H₂O to mixtures with DMSO is revealed.     

Synthesis of photochromic benzopyrans annulated by 15(18)-crown-5(6) ether

The reaction of hydroxy-substituted benzo-15(18)-crown-5(6) ether or benzo-18-crown-6 ether with β-phenylcinnamaldehyde in the presence of titanium tetraethoxide yielded crown-annulated 2,2-diphenylbenzopyrans. The compounds are photochromic, and the spectral characteristics of their colored form are unusual for this class of chromenes.     

Ion-pair extraction of tetravalent plutonium from hydrochloric acid medium using crown ethers

Ion-pair extraction behaviour of plutonium (IV) from varying concentrations of HCl solution was studied employing crown ethers (benzo-l5-crown-5 (B15C5), 18-crown-6, (18C6), dibenzo-18-crown-6 (DB18C6), dicyclohexano-18-crown-6, (DC18C6), dibenzo-24-crown-8 (DB24C8) and dicyclohexano-24-crown-8 (DCH24C8)) in nitrobenzene as the extractant. Ammonium metavanidate was used as the holding oxidant in the aqueous phase and the conditions necessary for the quantitative extraction of the tetravalent ion were found. The co-extraction of species of the type [HL⁺].[HPu(Cl) ₆ ^– ] and [HL⁺]2·[Pu(Cl) ₆ ^2– ] as ion-pairs (where L represents the crown ether) is suggested.     

Chemical activation of cytochrome c proteins via crown ether complexation: cold-active synzymes for enantiomer-selective sulfoxide oxidation in methanol

Supramolecular complexation with 18-crown-6 significantly converted catalytically inactive cytochrome c (biological form) to catalytically active synzyme (artificial form). Although a family of cytochrome c proteins does not work as enzymes in nature, crown ether complexation modified their heme coordination structures and functionally activated them to promote the asymmetric oxidation of racemic sulfoxides at low temperature. Horse heart, pigeon breast, and yeast cytochrome c proteins were demonstrated to form supramolecular complexes with 18-crown-6 in methanol, which effectively oxidized (S)-isomers of naphthyl methyl sulfoxide, methyl tolyl sulfoxide, isopropyl phenyl sulfoxide, benzyl methyl sulfoxide, and 4-methylsulfenyl acetophenone at -40 degrees C. Because horse heart and pigeon breast cytochromes c exhibited more efficient and higher enantiomer-selective activities than yeast cytochrome c, a proper combination of cytochrome c and crown ether offers a new class of cold-active synzymes promoting nonbiological asymmetric oxidation.     

Effect of the Composition of Ethanol–DMSO Solvents on the Stability of Silver(I) Complexes with 18-Crown-6

The effect of composition of ethanol–dimethyl sulfoxide (EtOH–DMSO) solvents (χ_DMSO = 0.0–1.0 mole fractions) on the stability of silver(I) complexes with 18-crown-6 ether (18C6) has been studied potentiometrically at 298.15 K. The increasing of DMSO concentrations in mixed solvents are shown to considerably reduce the stability of 18C6 complexes with silver(I) ion ([Ag18C6]⁺). A change in the solvation state of the central ion is suggested to be the key factor in shifting complexing equilibrium.     

Indoor 222Rn concentrations and the corresponding lung cancer risk in Celein region, west of Al Khums, Libya

Paramagnetic products stabilized in both 4,4′(5′)-di-(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6) and its solution in 1-octanol upon low temperature (77 K) X-rays irradiation were studied by ESR spectroscopy. Macrocyclic –O–ĊH–CH₂– radicals and acyclic O = C(H)–ĊH–O– radicals were found as main radiolysis products in neat DtBuCH18C6. Fraction of acyclic radicals resulting from the macrocycle cleavage was about 50%. No radical products resulted from t-Bu and cyclohexyl fragments were observed. It was concluded that the primary events were essentially concerned with ionization of the polyether moiety. Irradiation of frozen DtBuCH18C6 solutions in 1-octanol resulted in formation of radicals both from crown ether and alcohol.     

Extraction of tetrafluoroborate with crown ethers and its application to silicate rock analysis

Summary The extraction behaviour of tetrafluoroborate with crown ethers was studied. A high distribution ratio of tetrafluoroborate is obtained by extraction with dicyclohexano-18-crown-6 (DC18C6) in an organic solvent of high dielectric constant from potassium fluoride solution. The molar ratios of crown ether to KBF₄ in the extracted species are probably 1:1 for DC18C6, dibenzo-18-crown-6 and 18-crown-6, and 2:1 for benzo-15-crown-5 and 15-crown-5. The flow-injection extraction-spectrophotometric determination of tetrafluoroborate with Brilliant Green was worked out. Many rock reference samples were analyzed for boron (1–150 ppm).     

Atmospheric depositional fluxes of cosmogenic <Superscript>32</Superscript>P, <Superscript>33</Superscript>P and <Superscript>7</Superscript>Be in the Sevastopol region

⁹⁰Y was separated from ⁹⁰Sr using an extraction chromatographic resin consisting of 4, 4′(5′)-bis-t-butylcyclohexano-18-crown-6 (DtBuCH₁₈C₆), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) amide (C₂mimNTf₂), and a polymer (Amberlite XAD-7). Ionic liquid was introduced into the column to improve the separation efficiency. The column showed an excellent performance for the separation of Y from Sr. After the separation, the ratio of ⁹⁰Sr/⁹⁰Y was <2.0 × 10^?5; the column was recycled for >18 times. This study provides preliminary results on columns to produce ⁹⁰Y with a high purity in radiopharmaceuticals.     

Catalytic coupling of arenes with <Emphasis Type="Italic">p</Emphasis>-iodonitrobenzene in a system containing ArH,ArI, Pt<Superscript>II</Superscript>, 50% aqueous KOH,and 18-crown-6

The phenanthroline complex, Pt(phen)Cl₂, catalyzes the coupling of aromatic hydrocarbons with p-iodonitrobenzene under phase transfer conditions using 50% aqueous KOH and 18-crown-6. The yield of the asymmetric diaryl products is 10,000–12,000% relative to the catalyst. A mechanism was proposed involving the oxidative addition of ArI to an Ar-Pt^II intermediate species with subsequent reductive elimination of the final product Ar-Ar′ from Ar-Pt^IV-Ar′. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 6, pp. 364–366, November–December, 2007.     

New quaternary ammonium salts and metal complexes of organylheteroacetic acids with diaza-18-crown-6 ether

Quaternary ammonium salts 2(RCH₂COO)⁻·(2H·DACE)⁺ were synthesized in up to 98% yield by the reaction of biologically active organylheteroacetic acids (OHA) RCH₂COOH with diaza-18-crown-6 ether (DACE).     

Effect of the composition of an acetonitrile-dimethyl sulfoxide solvent on stability of the silver(I) complexes with 18-crown-6 ether

The effect of the composition of an acetonitrile-dimethyl sulfoxide (AN-DMSO) mixed solvent on the stability of silver(I) complexes with 18-crown-6 ether (18C6) is studied by potentiometry. An insignificant increase in the stability of [Ag18C6]⁺ (0.34 log units) is observed on going from acetonitrile to dimethyl sulfoxide. The effect of solvation on the shift of complex formation equilibrium is considered.     

Enantioseparation of aspartyl dipeptides by CE: Comparison between 18-crown-6-tetracarboxylic acid and carboxymethyl-β-cyclodextrin as chiral selector

Summary The simultaneous separation of isomeric α-and β-aspartyl peptides as well as their enantiomers by capillary electrophoresis was investigated. Resolution of the enantiomers of the peptides α/β-AspPhe-NH₂ and α/β-AspPhe-OMe was achieved with 18-crown-6-tetracarboxylic acid (18C6H₄) in untreated fused silica capillaries in the acidic pH range. Baseline resolution for the dipeptides was obtained using polyacrylamide (PAA)-coated capillaries. The selectivity of the crown ether is compared with the selectivity of another chiral selector, namely the negatively charged CD derivative carboxymethyl-β-CD (CM-β-CD).     

The effect of properties of water-organic solvent mixtures on the solvation enthalpy of 12-crown-4, 15-crown-5, 18-crown-6 and benzo-15-crown-5 ethers at 298.15 K

Crown ethers are preferential solvated by organic solvents in the mixtures of water with formamide, N-methylformamide, acetonitrile, acetone and propan-1-ol. In these mixed solvents the energetic effect of the preferential solvation depends quantitatively on the structural and energetic properties of mixtures. The energetic properties of the mixtures of water with hydrophobic solvents (N,N-dimethylformamide, dimethylsulfoxide, N,N-dimethylacetamide, hexamethylphosphortriamide) counteract the preferential solvation of the crown ether molecules. The effect of the hydrophobic and acid-base properties of the mixture of water with organic solvent on the solvation of 12-crown-4, 15-crown-5, 18-crown-6 and benzo-15-crown-5 ethers was discussed. The solvation enthalpy of one -CH₂CH₂O- group in water, N,N-dimethylformamide and hexamethylphosphortriamide is equal to −24.21, −16.04 and −15.91 kJ/mol, respectively. The condensed benzene ring with 15-crown-5 ether molecule brings about an increase in the exothermic effect of solvation of the crown ether in the mixtures of water with organic solvent.     

Thermodynamic characteristics of alanine-18-crown-6 ether complexes in binary water-acetone solvents

The formation of 18-crown-6 ether (18C6) complexes with D,L-alanine (Ala) in mixed wateracetone solvents with 0.0, 0.08, 0.17, 0.22, and 0.30 mole fractions of acetone (T = 298.15 K) was investigated by means of calorimetry. Thermodynamic characteristics of the reaction of the molecular [Ala18C6] complex formation (Δ_r G°, Δ_r H°, and TΔ_r S°) were calculated on the basis of calorimetric data. Analysis of solvation contributions of reagents into the enthalpy of the [Ala18C6] formation reaction showed that the changes in the reaction energy when the solvent composition is varied are determined by the changes in the solvate state of 18C6.     

The insertion reactions of “crowned” indium(I) trifluoromethanesulfonate into carbon-chlorine bonds

Whereas the soluble reagent indium(I) trifluoromethanesulfonate, InOTf, does not appear to react rapidly with chlorinated solvents, the crown ether ligated compounds [In(18-crown-6)][OTf] and [In(dibenzo-18-crown-6)][OTf] react rapidly with CH₂Cl₂ and CHCl₃ to produce the corresponding C-Cl insertion products. The structural features and the formation of the new indium-containing products are rationalized.     

Production of <Superscript>122</Superscript>Sb for the study of environmental pollution

This article presents, ¹²²Sb (T _1/2 = 2.723 days, I _β- = 97.59%) was produced via the ^natSn(p,xn) nuclear process at the AMIRS (Cyclone-30, IBA, Belgium). The electrodeposition experiments were carried out by potassium stannate trihydrate (K₂Sn(OH)₆) and potassium hydroxide. The optimum conditions of the electrodeposition of tin were as follows: 40 g/L ^natSn, 20 g/L KOH, 115 g/L K₂Sn(OH)₆, DC current density of 5 A/dm² with a bath temperature of 75 °C. The electroplated Tin-target was irradiated with 26.5 MeV protons at current of 180 μA for 20 min. Solvent extraction of no-carrier-added ¹²²Sb from irradiated Tin-natural target hydrochloric solution was investigated using di-n-butyl ether (C₈H₁₈O). Yields of about 3.61 MBq/μAh were experimentally obtained.     

Thermodynamics of complex formation in mixed solvents <Emphasis Type="Italic">K</Emphasis> and Δ<Emphasis Type="Italic">H</Emphasis> for the formation reaction of [Gly18C6] at 298.15 K

The influence of H₂O–EtOH and H₂O–Acetone mixed solvents at various compositions on the thermodynamics of complex formation reaction between crown ether 18-crown-6 (18C6) and glycine (Gly) was studied. The standard thermodynamic parameters of the complex [Gly18C6] (log K°, Δ_r H°, Δ_r S°) were calculated from thermochemical data at 298.15 K obtained by titration calorimetry. The complex stability and its formation enthalpy increase with increasing the non aqueous component concentration in both mixed solvents. The thermodynamic data were discussed on the basis of the solvation thermodynamic approach and the solvation contributions of the reagents and of the complex to the complex stability were analyzed.     

Stability of Complexes of NH4 + with 18-Crown-6, Dicyclohexyl-18-Crown-6, Dibenzo-18-Crown-6 and Dibenzo-24-Crown-8 in Water Saturated Nitrobenzene

From extraction experiments with ²²Na tracer, the exchange extraction constants corresponding to the NH₄ ⁺(aq) + NaL⁺ (nb)NH₄L⁺(nb) + Na⁺ (aq) equilibrium taking place in the two-phase water-nitrobenzene system (L = 18-crown-6, dicyclohexyl-18-crown-6, dibenzo-18-crown-6 and dibenzo-24-crown-8; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Furthermore, the stability constants of the NH₄L⁺ complexes in nitrobenzene saturated with water were calculated; they were found to increase in the order dibenzo-24-crown-8 (DB24C8) < dibenzo-18-crown-6 (DB18C6) < dicyclohexyl-18-crown-6 (DCH18C6) < 18-crown-6 (18C6).