Hydration of aprotic donor solvents studied by means of FTIR spectroscopy

The paper attempts to explain the mutual influence of nonpolar and electron-donor groups on solute hydration, the problem of big importance for biological aqueous systems. Aprotic organic solvents have been used as model solutes, differing in electron-donating power. Hydration of acetonitrile, acetone, 2-butanone, and triethylamine has been studied by HDO and (partially) H2O spectra. The quantitative version of difference spectra method has been applied to determine solute-affected water spectra. Analysis of the data suggests that solvent-water interaction via the donor center of the solute is averaged between water-water interactions around the solute. Such behavior can be simply explained by the model of solute rotating in a cavity of water structure, which is formed by clathratelike hydrogen-bonded water network. On the basis of the band shape of solute-affected HDO spectra and the corresponding distribution of intermolecular distances, the criterion for hydrophobic type hydration has been proposed. From that point of view, all the studied solutes could be treated as hydrophobic ones. The limiting band position and the corresponding intermolecular distance of affected water, gained with increasing electron-donating power of solutes, has been inferred from the data obtained. These observations are important for interpretation of vibrational spectra of water as well as for volumetric measurements of solutions. The simple model of hydration, proposed to better justify the results, connects the values obtained from the methods providing microscopic and macroscopic characteristics of the system studied.     

A new rigid benzene‐bridged macrotricyclic ligand

A macrotricyclic ligand composed of two benzene rings connected by four 2,2′‐oxydiphenoxide bridges ( 2 ) has been prepared by treating 1,2,4,5‐tetrakis[2‐(2‐hydroxyphenoxy)phenoxymethyl]benzene with 1,2,4,5‐tetrakis(bromomethyl)benzene in acetonitrile in the presence of potassium carbonate. Ligand 2 is of interest because of its similarity to macrocycle 1 which interacts strongly with cesium ions. The proposed more direct route of treating an excess of 2,2′‐oxydiphenol with 1,2,4,5‐tetrakis(bromomethyl)benzene to prepare 2 did not give the desired macrocycle but gave bis(tribenzo‐11‐crown‐3) ( 8 ). An X‐ray crystal structure study of 2 showed that the benzene rings which are linked by the four 2,2′‐oxydiphenoxide bridges are connected in a nonsymmetric pattern. The structure of 8 was also determined using X‐ray diffraction methods, and is reported.     

New syntheses of per-N-alkyl-substituted triaza- and tetraaza-crovm compounds containing an allyloxymethyl substituent

Seven new per-N-alkyl-substituted triaza- and tetraaza-crovm compounds have been prepared using commercially available or easily synthesized per-N-alkyl-substituted oligoethylene and oligopropylene polyamines, tetraazapentaethylene and tetraazaheptaethylene glycols. Five of these new polyaza-crowns have a pendant allyloxymethyl substituent.     

Analysis of Spontaneous Electrochemical Oscillations by the Wavelet Transformation Method

A new way of analyzing current oscillations that accompany anodic metal dissolution is presented. A wavelet transformation is used for separation and spectral analysis of singular courses—elementary components of electrochemical oscillation recordings. A method of obtaining oscillation energy distribution analogous to the spectral power density function is presented. It is shown that the chaotic component (Shil'nikov chaos) can be separated from the deterministic component of the described process.     

Simple Methods for the Synthesis of Cryptands and Supercryptands

The preparation of cryptands, supercryptands and macropolycycliccylindrical compounds is reviewed.     

Synthesis of new dibenzo nitrogen-oxygen donor macrocycles containing two amide groups

Four new nitrogen-oxygen, dibenzo macrocyclic ligands containing two amide groups have been prepared by combining a dibenzo-containing diamidodialdehyde with an appropriate diamine followed by reduction of the intermediate bis Schiff-base. The starting dibenzo-containing diamidodialdehyde was prepared by treating 2 equivalents of salicylaldehyde with a bis(α-chloroamide).     

Preparation of crown compounds containing allyloxymethyl or butenyl groups for attachment to silica gel or containing long chain lipophilic groups for use in liquid membrane systems

Several new macrocyclic polyether ligands have been prepared for use in the separation of metal ions from aqueous solutions. Four of the crown ethers reported contain 1,2,4-triazole or 4-pyridone protonionizable subcyclic units and lipophilic groups. The remaining crown ethers are not proton-ionizable but contain alkene groups and were prepared for attachment to silica gel. The crowns were prepared by reacting the appropriate glycols with the appropriate ditosylates or dichloride in the case of the 1,2,4-triazole subcyclic unit. The crowns with proton-ionizable and lipophilic substituents were tested in liquid membrane transport systems and some of the crowns with alloxymethyl or butenyl substituents were attached to silica gel. The log K values for the interaction of these silica gel-bound macrocycles with certain metal ions were nearly the same (± 10%) as those for the association of the unbound macrocycles with the same metal ions.     

Hydration of simple amides. FTIR spectra of HDO and theoretical studies

The hydration of formamide (F), N-methylformamide (NMF), N,N-dimethylformamide (DMF), acetamide (A), N-methylacetamide (NMA), and N,N-dimethylacetamide (DMA) has been studied in aqueous solutions by means of FTIR spectra of HDO isotopically diluted in H2O. The difference spectra procedure has been applied to remove the contribution of bulk water and thus to separate the spectra of solute-affected HDO. To facilitate the interpretation of obtained spectral results, DFT calculations of aqueous amide clusters were performed. Molecular dynamics (MD) simulation for the cis and trans forms of NMA was also carried out for the SPC model of water. Infrared spectra reveal that only two to three water molecules from the surrounding of the amides are statistically affected, from among ca. 30 molecules present in the first hydration sphere. The structural-energetic characteristic of these solute-affected water molecules differs only slightly from that in the bulk and corresponds to the clathrate-like hydrogen-bonded cage typical for hydrophobic hydration, with the possible exception of F. MD simulations confirm such organization of water molecules in the first hydration sphere of NMA and indicate a practical lack of orientation and energetic effects beyond this sphere. The geometry of hydrogen-bonded water molecules in the first hydration sphere is very similar to that in the bulk phase, but MD simulations have affirmed subtle differences recognized by the spectral method and enabled their understanding. The spectral data and simulations results are highly compatible. In the case of F, NMF, and A, there is a visible spectral effect of water interactions with N-H groups, which have destabilizing influence on the amides hydration shell. There is no spectral sign of such interaction for NMA as the solute. The energetic stability of water H-bonds in the amide hydration sphere and in the bulk fulfills the order: NMA > DMA > A > NMF > bulk > DMF > F. Microscopic parameters of water organization around the amides obtained from the spectra, which have been used in the hydration model based on volumetric data, confirm the more hydrophobic character of the first three amides in this sequence. The increased stability of the hydration sphere of NMA relative to DMA and of NMF relative to DMF seems to have its origin in different geometries, and so the stability, of water cages containing the amides.     

The Design of Ion Selective Macrocycles and the Solid-Phase Extraction of Ions Using Molecular Recognition Technology: A Synopsis

Abstract

We have combined organic synthesis and the study of cation complexation properties of the crown ethers in an effort to design and prepare macrocyclic ligands that will selectively bind specific cations.^1–3 The bis-phenol-containing diazacrown ethers allow a great number of possibilities for designing ion selectivity into macro-cyclic ligands. In these cases, the macrocyclic ligand can be varied as can the type and position of attachment of the phenolic group. Any of these variations can have profound effects on complexation properties. For example, ligand 1 (see Figure 1), where two 5-chloro-8-hydroxy-quinoline (CHQ) groups are attached through their positions 7, is selective for Mg²⁺ over other alkali and alkaline earth metal ions (see Table I).⁴ On the other hand, ligand 2, where the two CHQ groups are attached through their positions 2, exhibits remarkable selectivity for K⁺ and Ba²⁺ over all other metal ions studied. The chemical shifts of the CHQ protons in the ¹H NMR spectra of K⁺- and Ba²⁺- complexes with 2 shift significantly upfield in relation to the free ligand. These shifts are indicative of an overlap of the two CHQ substituents. Indeed, the crystal structure of the Ba²⁺-2 complex shows that Ba²⁺ is in the center of a pseudo-cryptand with the diazacrown forming two arms and the two overlapping CHQ groups forming the third.^4,5 This pseudo-cryptand formation accounts for the fact that the K⁺-2 and Ba²⁺-2 complexes are so stable in comparison to complexes of 2 with the other alkali and alkaline earth cations.