Self-assembly of 5,11,17,23-tetranitro-25,26,27,28-tetramethoxythiacalix[4]arene with neutral molecules and its use for anion recognition

Methylation of 5,11,17,23-tetranitrothiacalix[4]arene with diazomethane leads to the tetramethoxy derivative, which was studied using single-crystal X-ray crystallography. It revealed that this compound, albeit in the 1,3-alternate conformation, can form the inclusion complexes with various solvent molecules possessing acidic methyl groups (ethyl acetate, nitromethane, acetone, acetonitrile) and creates interesting infinite channels filled with solvent molecules. The subsequent transformation of nitro groups into the ureido moieties gave receptors capable of anion recognition even in a highly HB-competitive solvent like DMSO.     

Electron spin resonance studies of spin-labelled polymers—18: Adsorption of spin-labelled poly(vinyl acetate) on silica surfaces

The adsorption of spin-labelled poly(vinyl acetate) from dilute solutions in ethyl acetate, chloroform and toluene onto three silica adsorbents of different surface silanol contents was studied. The adsorption capacities of the three silica samples, which decreased with decreasing surface silanol content, were dependent on the nature of the solvent, being greatest in the poor solvent toluene and least in the good solvent ethyl acetate. The ESR spectra of the polymer adsorbed on the silica of highest silanol content suggested that the polymer had a relatively flat conformation when toluene or chloroform was solvent and a more looped conformation when ethyl acetate was solvent. With the silica of intermediate silanol content, the polymer adsorbed from chloroform solution also had a loopy conformation. The silica of lowest silanol content was prepared by treating the first silica absorbent with trimethylchlorosilane. The line-shapes in the ESR spectrum of the labelled polymer adsorbed on this modified silica indicated a change in mode of adsorption.     

Heterocalixarene Inclusion Chemistry. Structure of a Crystalline Host-Guest Complex Including endo-Calix Ethyl Acetate and exo-Calix Clustering of Water

The X-ray crystal structure of the solvent inclusion compound formed between heterocalix[8]arene 1, ethyl acetate and water (1 : 1 : 4.5) has been studied. The compound crystallized in tetragonal space group I4₁/a, a = b = 21.278(3), c = 31.290(4) Å, V = 14167(4) ų, Z = 8. The host molecule, incorporating benzimidazol-2-one and 2,5-dimethoxy-1,3-phenylene subunits in an alternate cyclic arrangement, forms an almost perfectly closed cavity which encapsulates one solvent ethyl acetate guest molecule. Water molecules being entrapped in the lattice cages in the form of cyclic and linear clusters bind the bulky inclusion complexes via H-bonds in infinite layers. Two symmetry center related benzimidazole-2-one moieties of two hosts from neighbouring layers in the crystal lattice are arranged such that they partially overlap exhibiting stacking interaction.     

Synthesis and investigation of the solution behavior of graft block copolymers of polyimide and poly(methyl methacrylate)

Graft copolymers with a polyimide backbone and poly(methyl methacrylate) side chains are investigated in dilute chloroform and ethyl acetate solutions via the methods of molecular hydrodynamics and optics. Copolymer samples are prepared through the “grafting from” method via atom-transfer radical polymerization with a multicenter polyimide macroinitiator. In solutions of copolymers with low degrees of functionalization Z (40%), supermolecular structures are formed as a result of interactions between the polyimide backbones. In samples with Z → 100%, the backbone is well screened by side chains; therefore, molecular solutions are formed in both solvents. The hydrodynamic and conformational behavior of samples with high functionalization degrees changes after the transition from ethyl acetate to chloroform owing to the different thermodynamic qualities of the solvents with respect to the copolymer components. In both solvents, the backbone tends to avoid contact with a poor solvent. This effect is more pronounced in the case of ethyl acetate. Macromolecules of the studied graft copolymers are characterized by high equilibrium rigidities (>40 nm) that are 10 times higher than the corresponding characteristics of aromatic polyimides.     

Inorganic polarography in organic solvents-IV: polarography of metal oxinate complexes in various solvents

The polarography of 24 metal oxinate complexes extracted into chloroform, IBMK, and ethyl acetate has been investigated, a methanolic solution of lithium chloride being used as base electrolyte. Only 15 complexes gave rise to reduction waves, and interference-free determinations have been developed for indium and thallium(III) in chloroform, and for bismuth, molybdenum and uranium in IBMK. The use of ethyl acetate offered no special advantages, and was the least selective of the three solvents used.     

Preferential Solvation of Boscalid in Ethanol/Isopropanol + Ethyl Acetate Mixtures from the Inverse Kirkwood–Buff Integrals Method

The preferential solvation parameters (δx _1,3) of Boscalid in solvent mixtures of ethanol (1) + ethyl acetate (2), and isopropanol (1) + ethyl acetate (2) were derived from their available solubility data by means of the inverse Kirkwood–Buff integrals method. The values of δx _1,3 vary non-linearly with the solvent (1) proportion in the two solvent mixtures. For the ethanol (1) + ethyl acetate (2) system, the values of δx _1,3 are negative in ethanol-rich and ethyl acetate-rich mixtures, but positive in intermediate compositions; for the isopropanol (1) + ethyl acetate (2) system, the values of δx _1,3 are positive in ethyl acetate-rich mixtures and in intermediate compositions, but negative in isopropanol-rich mixtures. The δx _1,3 values are positive indicating that Boscalid is preferentially solvated by ethyl acetate. The magnitude of the preferential solvation of Boscalid by ethyl acetate is higher in isopropanol (1) + ethyl acetate (2) mixtures than in ethanol (1) + ethyl acetate (2) mixtures at 298.15, 308.15 and 313.15 K. The ethyl acetate action may be related to the disordered structure of ethanol or isopropanol molecules around the polar moieties of Boscalid, which increases the solvation, with maximum values near x ₁ = 0.40–0.45 for the two solvent mixtures.     

Extraction of cations as salts of fatty acids : Beryllium as Butyrate

The extraction of beryllium has been carried out in the presence of butyric acid. Of the solvents tried, viz., ether, benzene, chloroform, amyl acetate, ethyl acetate and carbon tetrachloride, chloroform is found to be the best, ethyl acetate being the next. 30.7 mg of BeO in solution as chloride is raised to a pH of 9.3 to 9.5 to which 10-15 ml of butyric acid is added. Four extractions with chloroform extract 99% of beryllium.     

Some properties of polyvinyl acetate films cast from methanol,acetone and chloroform as solvent

Polyvinyl acetate was cast into films on a clean mercury surface from its solution in either methanol, acetone or chloroform. Some mechanical properties of the films, exposed at 20 °C and 65% r.h., and 45 and 60 °C in air ovens, were studied. They were found to be highly dependent on the solvent used for film casting and the time of exposure of film at each of the temperatures. The initial modulus, yield stress, tensile strength and work to rupture of the polymer films were greater for those cast from acetone than those cast from chloroform, and for all the films these properties increased with exposure time, with an induction period in some cases. The elongation at break decreased with exposure time from an initial value which was higher for the chloroform-cast than the acetone-cast films. Films cast from methanol were found to be too brittle for testing.The results are interpreted on the basis of interactions between the solvent molecules and those of the polymer. Of the three solvents, chloroform produced polyvinyl acetate films with the most constant mechanical properties over the longest period of exposure which depended on the temperature of exposure, decreasing as the temperature increased. Hence chloroform is recommended for casting films of polyvinyl acetate. Methanol is practically unsuitable while acetone could be used where chloroform is not available.     

Dynamic analyses on induced-fit gaseous guest binding to organic crystals with a quartz-crystal microbalance

The inclusion behavior of gaseous guest molecules in a solid apohost, an orthogonal anthracene-bis(resorcinol)tetraol (1), was investigated with a quartz-crystal microbalance (QCM). Compound 1 forms crystals composed of molecular sheets bound together by an extensive hydrogen-bonded network. An apohost of 1 was cast onto a QCM and the binding of gaseous guest molecules was followed as a function of time by observing the decrease in the oscillation frequency, which is directly related to the increase in mass. Ethyl acetate and methyl ethyl ketone were significantly included into the apohost, whereas benzene and cyclohexane were simply adsorbed onto the surface of the solid; all these guests have similar vapor pressures at 25 degrees C. On the other hand, a host analogue 2, a tetramethoxy derivative of 1, barely included these guest molecules. The inclusion amount and the rate of inclusion of ethyl acetate or methyl ethyl ketone showed a drastic increase above a threshold concentration of guests in the gas phase. Thus, the structure of the apohost changed cooperatively in order to bind guest molecules above the threshold guest concentration. This cooperativity of the binding behavior was kinetically analyzed.     

Preferential solvation within hydrophilic nanocavities and its effect on the folding of cholate foldamers

The conformations of three cholate foldamers and one molecular basket were studied by fluorescence and NMR spectroscopy. In nonpolar solvents (e.g., hexane/ethyl acetate or ethyl acetate) mixed with a small amount of a polar solvent (e.g., alcohol or DMSO), the cholate oligomer folded into a helix with the hydrophilic faces of the cholates turned inward. Folding created a hydrophilic nanocavity preferentially solvated by the entrapped polar solvent concentrated from the bulk. This microphase separation of the polar solvent was critical to the folding process. Folding was favored by larger-sized polar solvent molecules, as fewer such molecules could occupy and solvate the nanocavity, thus requiring a smaller extent of phase separation during folding. Folding was also favored by smaller/acyclic nonpolar solvent molecules, probably because they could avoid contact with the OH/NH groups within the nanocavity better than larger/cyclic nonpolar solvent molecules.     

Preparation of Porous Polylactide Microspheres and Their Application in Tissue Engineering

In this study,porous polylactide (PLA) microspheres with different structures were prepared through the multiple emulsion solvent evaporation method.By changing organic solvents (ethyl acetate and chloroform) and adding effervescent salt NH4HCO3 in the inner water phase,microspheres with porous capsular,matrix,microcapsular and multivesicular structures were prepared.The protein encapsulation and release,and the cell growth behavior of porous microspheres were further explored.Under the same inner water phase,microspheres prepared with chloroform had higher protein encapsulation efficiency and less protein release rate as compared with those prepared with ethyl acetate.Cell experiments showed that the relatively rough surface of microspheres prepared with chloroform was more favorable for the cell growth in comparison with the smooth surface of microspheres prepared with ethyl acetate.This study shows a simple and effective method to control the protein release and cell growth behaviors of polymer microspheres by tuning their porous structure.     

Synthesis and Fluorescence Properties of Pyrimidine‐Based Diboron Complexes with Donor–π–Acceptor Structures

Pyrimidine‐based diboron complexes bearing β‐iminoenolate ligands and phenyl groups as bulky substituents on the boron atoms were synthesized as novel fluorescent dyes, and their fluorescence properties were investigated in solution and in the solid state. The diboron complexes with donor–π–acceptor structures showed positive solvatochromism in the fluorescence spectra. The cyano derivative exhibited the most dramatic redshift of the fluorescence maximum F_max with increasing solvent polarity (from 551 nm in n‐hexane to 710 nm in acetonitrile). The diboron complexes showed solid‐state fluorescence in the range of 578–706 nm with fluorescence quantum yields of 0.06–0.28. Additionally, the trifluoromethyl derivative exhibited solvent‐inclusion solid‐state fluorescence. The trifluoromethyl derivative formed toluene‐inclusion and ethyl acetate‐inclusion crystals. The toluene‐inclusion crystal (F_max=668 nm, Φ_f=0.16) showed a blueshifted F_max and higher Φ_f value compared to the original trifluoromethyl derivative (F_max=694 nm, Φ_f=0.08) in the solid state. On the other hand, the F_max (709 nm) and Φ_f (0.04) values of the ethyl acetate‐inclusion crystal were redshifted and lower, respectively.     

Intermolecular association of polymers through functional end-groups: Sulphate and sulphonate end-groups

Intermolecular association of some polystyrene and poly(methyl methacrylate) (PMMA) samples bearing sulphate and/or sulphonate end-groups prepared by using the redox initiator systems K₂S₂O₈ + NaHSO₃, Na₂SO₃ + Cu²⁺, NaHSO₃ + O₂ has been studied for dilute solutions in toluene, chloroform, o-dichlorobenzene, tetrahydrofuran (THF) and ethyl acetate respectively by viscometry and in toluene and THF by osmometry. Significant association of the polymers occurs in toluene, chloroform and o-dichlorobenzene in the dilute solutions used in this work. However, association is significantly reduced in chloroform containing 2% ethanol or in toluene containing 2% methanol. Tetrahydrofuran appears to be the preferred solvent for determining the molecular weights of such polymers, since association is insignificant in this solvent.     

A DFT study on the complexation of La3+ ion with malonamide and diglycolamide ligands

The main goal of this research is to investigate the structural and thermochemical aspects of complexation between La³⁺ with tetrapropyl malonamide (TPMA) and tetrapropyl diglycolamide (TPDGA) ligands via density functional theory (DFT) methods. In this respect, the structural parameters of [La-TPMA]³⁺ and [La-TPDGA]³⁺ complexes have been calculated and compared with the available X-ray crystallographic data. These comparisons revealed that both calculated structural values using B3LYP and M06 are in a reliable agreement with X-ray crystal structure with a near accuracy. In the next step, the more efficiency of diglycolamides in comparison with malonamides in the extraction of La³⁺ have been analyzed by calculating thermochemical properties of the complexation. It should be stated that this issue has been observed in many experimental elucidations. In the next step, the inclusion of solvent effects on thermodynamical properties of complexation has been evaluated via polarized continuum model (PCM) calculations. In this context, enthalpy and Gibbs free energy changes have been determined in the presence of three solvents, chloroform, toluene and n-hexane. Our obtained results demonstrate that using n-hexane as solvent is more favorable thermodynamically than chloroform and toluene that confirms the previously observed experiments. Finally, the bond orders of some selected key bonds in TPMA and TPDGA ligands and their corresponded La³⁺ complexes have been evaluated comparatively to analyze the electronic features of coordination in [La-TPMA]³⁺ and [La-TPDGA]³⁺ complexes.     

Thermodynamic study of complex formation between Ni2+ and Co2+ cations and 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane (kryptofix 5) in binary mixed nonaqueous solutions

Conductometric titrations were performed in pure and binary solvent solutions of ethyl acetate (EtOAc), methyl acetate (MeOAc) and methanol (MeOH) with acetonitrile (AN) at 288, 298, 308, and 318 K to determine the stoichiometry, the complex stability constants and the standard thermodynamic parameters for the complexation of nickel(II) and cobalt(II) cations with 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane (kryptofix 5). The stability constants of the resulting 1:1 complexes formed between the metal cations and the ligand in different solvent mixtures were determined by computer fitting of the conductance-mole ratio data. The results revealed that the stability order of (kryptofix 5)-Ni²⁺ and (kryptofix 5)-Co²⁺ complexes changes with nature and composition of the solvent system. There is a non-linear relationship between the logK _f values of complexes and the mole fraction of acetonitrile in the mixed solvent system. In addition, the conductometric data show that the stoichiometry of the complexes formed between the nickel(II) and cobalt(II) cations with the acyclic ligand changes with the nature of the solvent. The enthalpy and entropy values for the 1: 1 [ML] complexation reactions were evaluated from the temperature dependence of the formation constants. Thermodynamically, in most of systems, the complexation processes of nickel(II) and cobalt(II) cations with kryptofix 5, are both enthalpy and entropy stabilized and the values of these parameters are influenced by the nature and composition of the binary mixed solvent solutions.     

Isothermal titration calorimetry (ITC) study of natural cyclodextrins inclusion complexes with drugs

Isothermal titration calorimetry (ITC) was used to characterize inclusion complex formation of natural cyclodextrins (α- and β-cyclodextrin) with three drugs ((+)brompheniramine, (±)brompheniramine, cyclopentolate) in aqueous solutions. ITC measurements were carried out at 298.15 K on a Microcal OMEGA ultrasensitive titration calorimeter (MicroCal Inc.). The experimental data were analyzed on the basis of the model of a single set of identical sites (ITC tutorial guide). β-CD forms inclusion complexes of stoichiometry 1:1 with the all investigated drugs. In turn, smaller molecule of α-CD forms inclusion complexes of two different stoichiometry: with bigger molecules ((+)brompheniramine and (±)brompheniramine) of a stoichiometry 2:1 and with smaller molecules (cyclopentolate) of a stoichiometry 1:2. Based on the experimental values of equilibrium constant (K) and enthalpy of complex formation (ΔH), the Gibbs energy of complex formation (ΔG), and the entropy of complex formation (ΔS), have been calculated, for all the investigated systems. Obtained results showed that complex formation of β-CD (bigger molecule with wider cavity compared to β-CD) with both (+)brompheniramine, (±)brompheniramine, and cyclopentolate is enthalpy driven while complexes of α-CD with the all investigated drugs are enthalpy-entropy stabilized. This indicated that the difference in the cavity dimensions is reflecting in different driving forces of complex formation and binding modes what resulted in different stoichiometry of the obtained inclusion complexes.     

X-ray structural investigation of gossypol and its derivatives. IX. Semiclathrates of gossypol with esters of acetic acid

Inclusion compounds of gossypol with a number of acetic acid esters have been obtained and have been identified by derivatography and NMR spectroscopy. An x-ray structural investigation of the structures of crystalline complexes of gossypol with ethyl acetate and butyl acetate has shown that these complexes are isostructural semiclathrates. On the basis of the structures of these two semiclathrates of gossypol, it has been concluded that esters and ketone with chain lengths of from five to seven atoms form inclusion compounds isomorphous with the semiclathrates of ethyl and butyl acetates. If the chain length is shorter or longer than that given, inclusion compounds with a different crystal structure are formed.A. S. Sadykov Institute of Bioorganic Chemistry, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 669–675, September–October, 1988.     

Solvent‐Dependent Self‐Discrimination of Bis(2‐hydroxyphenyl)diamides

Solvent‐dependent, self‐discrimination of diamides is described. Mixing a solution of (R)‐ 1 a and (S)‐ 1 a , which are valine‐derived, bis(2‐hydroxyphenyl)diamide‐bearing, multiple hydrogen‐bonding modules, in dichloromethane immediately led to the formation of a thick suspension comprising a 1:1 heterochiral aggregate of 1 a . The solubility of heterochiral 1 a was substantially lower in halogenated solvents than in ethyl acetate. A perusal of racemic crystal structures obtained from chloroform and ethyl acetate revealed a significant difference in the crystal‐packing pattern, which is likely to be the basis for the pronounced difference in solubility. Specific self‐discrimination of 1 a in an ensemble of eight structurally related molecules showcased the specific aggregation through the hydrogen‐bonding network of the bis(2‐hydroxyphenyl)diamide framework. The low solubility of heterochiral 1 a in halogenated solvent was exploited to achieve high stereoselectivity in a catalytic asymmetric reaction by using a low enantiomeric excess sample of 1 a .     

Simultaneous Analysis of Lipid-Soluble Constituents of Erxian Decoction by GC–MS

Erxian Decoction (EXD), a traditional Chinese medicine formula mainly composed of six Chinese herbs, was originally developed for menopausal syndromes and had been practiced since the 1950s in China. Previous studies only focused on the water-soluble compounds involved in EXD by LC or TLC. This study analyzed the whole profile of the volatile constituents contained in EXD to supplement its quality evaluation method. Several EXD samples were extracted with chloroform and ethyl acetate, respectively, to get the lipid-soluble chloroform and ethyl acetate fractions and compared their gas chromatographic profiles by GC–MS. The EXD samples were hydrolyzed with hydrochloric acid in a water-bath at 100 °C, neutralized with 40% NaOH, and finally extracted with ethyl acetate and chloroform for the quantification of the total sarsasapogenins contained in EXD. A total of 56 compounds belonging to a variety of natural product categories such as aromatic phenols, terpenes, fatty acids, ketones, esters, and aldehydes, etc. were identified from the chloroform and ethyl acetate extracts by using the online EI–MS characterization. The GC–MS method showed a linear response for sarsasapogenin quantification with r = 0.994. The intra-day and inter-day variations of precision and accuracy of the assay were less than 5%. This developed GC–MS method could thus be successfully applied for the identification of lipid-soluble constituents derived from EXD, and also for the accurate quantification of the total sarsasapogenins contained in the acid hydrolyzed EXD samples.     

Separation of zinc(II), cadmium(II) and mercury by solvent extraction using thiocarbohydrazide and the complexing agent

The extraction behaviour is reported of zinc(II), cadmium(II) and mercury(II) complexes of thiocarbohydrazide in benzene, chloroform, carbon tetrachloride, di-isopropyl ether, ethyl acetate, amyl acetate, and amyl alcohol. The separation of the three elements has been achieved by the use of various masking agents, as well as by making use of the effect ofpH on their extractability. This work was carried out under CSIR (India) Scheme No. 1 (450/69 GAU. II.