Effect of diisocyanate nature on the properties of cyclolinear polyureas containing azacrown ether groups

New cyclolinear polyureas based on a crown-containing diamine—1,10-diaza-18-crown-6—and organic diisocyanates of different natures (aliphatic, aromatic, and alicyclic compounds) and an oligomeric diisocyanate have been synthesized. It has been found that, unlike most polyureas, azacrown-containing polymers are soluble in a wide variety of organic solvents. The calorimetric and mechanical properties of these polymers in dry and equilibrium-swollen states have been studied. It has been shown that the basic characteristics of these cyclolinear systems can be tailored by varying the nature of the diisocyanate used.     

Studies on Enolisation of Some β-Diketones by Spectrophotometric Method

Enolisation of acetoacetanilide (AAAH) acetoacet ortho-toluidide (AATH), 2, 4-acetoacetxylidide (AAXH), acetoacet-ortho-chloroanilide (CAAAH), acetoacetortho-anisidide (OAAAH), benzoyl-acetanilide (BAAH) and benzoyl-meta-nitro-acetanilide (NBAAH) have been studied in different solvents of varying polarities, ranging from chloroform (z=63.2) to methanol (Z=83.6) by ultraviolet spectroscopic methods. The low percentages of enol contents in formamide, dimethylformamide and dimethylsulphoxide, may be due to the formation of charge transfer complexes of these solvents with the diketones. Free energy of tautomerisation has also been calculated. The substituents on the phenyl group attached to the nitrogen have no effect on enolisation.     

Solution behavior of metal sulfonate ionomers. II. Effects of solvents

Previous studies on the dilute-solution behavior of sulfonated ionomers have shown these polymers to exhibit unusual viscosity behavior in mixed solvents of low polarity. These results have been interpreted as arising from specific solvation effects by the solvents with the metal sulfonate groups which persist as ion pairs. The consequences of ion pair interactions and their solvation are exceptional thickening behavior at low polymer levels as compared to unfunctionalized polymers, and anomolous solution viscosities with varying temperature. These studies have now been extended to single-component solvents which traverse a range of polarities. Using the sodium salt of lightly sulfonated polystyrene (S-PS) as a model system, the authors found the solution behavior in low-polarity solvents (tetrahydrofuran) to be consistent with that observed previously for mixed solvents; ion pair interactions predominated. However, in polar solvents such as dimethyl sulfoxide or dimethyl formamide, these polymers behave as classic polyelectrolytes even at sulfonate levels below 2 mol %. The behavior of the S-PS acids is similar to that observed for the metal salts. To a first approximation these two behaviors, ion pair association and polyelectrolyte behavior, are dependent on solvent polarity. In some cases it is possible to induce polyelectrolyte behavior in a S-PS/solvent combination exhibiting ion pair interactions by the addition of very low levels of a polar cosolvent, such as water. These results again demonstrate the selectivity of the solvent-sulfonate interactions.     

Polymer conformation in mixed aqueous-polar organic solvents

The conformation of the common polysaccharide dextran has been investigated in mixed solvents at two different temperatures using viscosity measurements. In particular we considered binary mixtures of water with the polar organic solvents glycerol, formamide, dimethylsulfoxide, or ethanol. The intrinsic viscosity of dextran T500 in the different systems has been determined, and the solvent effects, as manifested in variations of the dextran intrinsic viscosity and coil radius, have been correlated to the surface tension and the fractional solubility parameters of the solvent mixture. The coil dimension changes observed in the different solvent mixtures are consistent with expectations from water-cosolvent-dextran interactions, especially as they pertain to hydrogen bonding.     

Multivariate statistical characterization of the tolerance of argon inductively coupled plasmas to organic solvents

The tolerance of Argon-inductively coupled plasmas to the introduction of organic solvents, defined by Matsunaga's parameter and by “limiting aspiration rate”, has been correlated with their nature by statistical methods. The main physical variables of solvents obtained from the technical literature were used as independent variables to perform principal component analysis (PCA) and factorial discriminant analysis (FDA). Thus the variables which had the greatest influence on heat exchange nebulization and transport processes were determined. Organic solvents were classified into different groups characterized by their tolerance in plasma operation. In the PCA study, the second principal component was the most significative to differentiate between the tolerance of solvents and it showed a high correlation with surface tension, viscosity and heat of vaporization. Scores of the organic solvents belonging to the same class can be adjusted to straight lines and their positions in the plane (expressed as ordinates in the origin) as well as the slope values are characteristics of organic solvent groups. The results of FDA confirms those obtained with PCA. Multivariable regression was applied to obtain predictive equations of the limiting aspiration rate for organic solvents, in terms of their main physical variables.     

SOLVENT INFLUENCES ON THE SINGLET QUENCHING OF CHLOROPHYLL a BY 2, 5-DIMETHYL-p-BENZOQUINONE

Abstract— The quenching of chlorophyll a excited singlet states by 2.5-dimethyl- p -benzoquinone has been investigated in solvents of varying viscosity and polarity. The observed singlet lifetimes showed little variation in several hydrocarbon solvents. Stern-Volmer constant K depends on the viscosity of the solvent, although cyclic and straight-chain hydrocarbons behave somewhat differently. The decrease of the K values with increase of viscosity suggests that the quenching mechanism is at least partly dynamic, although there is evidence for static quenching as well. The influence of solvent polarity on the K values was found to be insignificant, which is consistent with a very short-lived ion pair intermediate formed by electron-transfer quenching.     

Tautomeric structures, electronic spectra, acid-base properties of some 7-aryl-2,5-diamino-3(4-hydroxyphenyazo)pyrazolo[1,5-a]pyrimidine-6-carbonitriles, and effect of their copper(II) complex solutions on some bacteria and fungi

Infrared and electronic spectra were used to investigate the tautomerism of some azo compounds, in both the solid and solution states. It was found that the compounds exist in azo<==>hydrazone tautomeric equilibrium in solid and in solutions. The different bands displayed in the electronic spectra of the compounds in various organic solvents are assigned to the suitable electronic transitions. The solvatochromic behavior of the compounds was investigated by studying their visible spectra in pure and mixed organic solvents. DeltaG and formation constant, Kf, values of the molecular complexes formed in solution have been determined. Effect of concentration of the compounds in DMF and EtOH solutions has been investigated. The basicity and acidity constants of the different compounds were determined from the spectra of these compounds in aqueous-ethanolic solutions of varying pH values. Some complexes of copper(II) with these compounds in solution were tested as for their antibacterial and antifungal activity.     

Role of hydrogen bonding on the spectroscopic properties of thiazolidinedione derivatives in homogeneous solvents

In this work, three newly synthesized derivatives of thiazolidinediones, with potential for application as drugs in pharmaceutical industry and free radical scavenging activity, have been taken up to investigate their behaviour in different homogeneous solvents. The purpose of this work is to study the solvation characteristics in ground and excited states of the derivatives by monitoring the absorbance and fluorescence band maxima. The steady state and time resolved fluorescence studies in protic and aprotic solvents have been rationalized on the basis of solute–solvent interaction and substituent effect on these photophysical processes have been analyzed. Substituents at different positions of the aryl moiety affect the hydrogen bond formation ability of the probes.     

Solvatochromic behaviours and structure–spectra relationships of 4-carboxyl-2,6-dinitrophenylazohydroxynaphthalenes

Comprehensive electronic absorption spectra of a new dye series, 4-carboxyl-2,6-dinitrophenylazohydroxynaphthalenes have been investigated in solvents of varying polarities. The solvent dependent UV–vis spectral shifts were analysed using some solvent physical parameters such as refractive index, dielectric function, hydrogen bonding acceptor ability, orientation of polarization and others. The observed spectral shifts were correlated with different solute–solvent interaction mechanisms using simple and multiple linear regression analyses. The results of the curve fitting coefficients enabled us to classify the various interactions of solvents with the dyes and relate the solvatochromic behaviours to the substituent effects on the dye molecules. Charge-transfer complexation occurring between one of the congeners and N,N′-dimethylformamide was extensively studied and discovered to be both concentration- and temperature-dependent.The electronic character and the chemical nature of the solvents as well as the chemical nature of the other substituents, apart from the common hydroxyl group, are important factors for the observed solvatochromic properties of the 4-carboxyl-2, 6-dinitrophenylazohydroxynaphthalenes.     

Ultrafast twisting dynamics in the excited state of auramine

Relaxation dynamics of the excited state of bis-[4-(dimethylamino)-phenyl] methaniminium chloride (Auramine) has been investigated using subpicosecond time-resolved absorption spectroscopic technique in both aprotic and alcoholic solvents. The locally excited (LE) state, formed following photoexcitation of Auramine using 400 nm light, undergoes intramolecular charge transfer (ICT) process, which is accompanied by the twisting of the dimethylanilino groups. Time evolution of the transient absorption-stimulated emission spectra as well as the wavelength dependence of the temporal dynamics investigated in each kind of solvents suggest that the relaxation process proceeds via the formation of at least two transient states (TS I and TS II), which are geometrical conformers and consecutively formed following the decay of the LE state. Twisting of the dimethylaniline groups are nearly barrierless processes, the rates of which show linear correlation both with the macroscopic or shear viscosities as well as the solvation times of the solvents. Time-dependent and fractional viscosity dependence of the relaxation rates of the LE and the TS I states in aprotic solvents suggest the multidimensionality of the reaction coordinate as well as reveal the viscoelastic property of the solvents. However, in normal alcohols, in addition to these two factors, activation energy of the solvent viscosity may be another important factor for the slower twisting dynamics of Auramine in alcohols. To explain the viscosity dependence of the decay time of the TS II state, which undergoes an efficient internal conversion process to the ground state, the possibility of occurrence of different mechanisms, such as, energy gap law, involvement of intramolecular high frequency modes, as well as the phenyl group twisting motion on a potential energy surface having a photochemical funnel, have been discussed. TDDFT method has been applied to obtain the optimized electronic structures of the transient states but it has been possible to obtain only that for the TS II state.     

Effect of the solvent nature on the rheological properties of concentrated solutions of various polymers

The paper compares the viscous, high-elastic and viscoelastic properties of solutions in various solvents of four polymers (polyisobutylene, polystyrene, polymethyl methacrylate and acetyl cellulose) differing in chain rigidity and the intensity of molecular interaction, over a wide range of compositions for the linear region of the mechanical behaviour of these systems. For solutions of polyisobutylene and polystyrene, the effect of the nature of the solvent on the viscosity is determined by the inherent viscosity of the solvent and by the fact that solutions under isothermal conditions are not in corresponding states with respect to their glass transition temperatures. The high-elasticity modulus of polyisobutylene and polystyrene solutions is independent of the nature of the solvent and of temperature. This indicates that the fluctuating network of entanglements is insensitive to the nature of the solvent and that the free volume plays the determining role in the behaviour of these solutions. Solutions of acetyl cellulose and polymethyl methacrylate are characterized by a very strong dependence of the viscosity on the nature of the solvent (which cannot be explained by notions valid for solutions of the first two polymers) and also by a change in the high-elasticity modulus with variation in the nature of the solvent and temperature. This proves that the properties of solutions of polar polymers are determined both by the free volume and the density of the fluctuating network, which changes with the solvent and temperature. The shape of the relaxation spectra of solutions of various polydisperse polymers in solvents of different natures is the same, while the specific properties of the solutions are associated with the position of the spectra on the time scale, which determines the fundamental constants of the solutions, viz. the zero shear viscosity and the initial high-elasticity modulus.     

醋酸纤维素膜及其混合膜渗透气化性能的研究——稀溶液粘度斜率系数的依赖性

研究了醋酸纤维素（CA），乙烯－醋酸乙烯共聚物（EVA），聚乙烯醇缩丁醛（PVB）和聚醋酸乙烯酯（PVAc) 4种高聚物在不同溶剂中的稀溶液粘性行为。同时，从各相应的溶剂中制备了CA均一膜，CA－PVB和CA－PVAc共混膜以及CA－EVA复合膜，并测定了各种膜对甲醇（MeOH），甲基叔丁基醚（MTBE）混合物的渗透气化性能。结果表明，各种膜的渗透通量（J）与其稀溶液粘度斜率系数（b)成反比，即呈现随b值增大J值下降现象。     

A new class of low-molecular-weight amphiphilic gelators

A new powerful class of low-molecular-weight amphiphilic compounds has been synthesized and their structure-property relationships with respect to their gelation ability of organic solvents have been investigated. These compounds are able to gel organic solvents over a broad range of polarity. Especially polar solvents such as valeronitrile and gamma-butyrolactone can be gelled even at concentrations far below 1 wt %. It was found that the gelation ability of these asymmetrically substituted p-phenylendiamines depends on a well-balanced relation of the terminal head group, the units involved in hydrogen bonding (amide or urea groups), and on the length of the alkyl chain. With this class of new gelators it is possible to tailor thermal and mechanical properties in different organic solvents and open various application possibilities.     

Electronic spectra, solvatochromic behavior and acid-base properties of some azo cinnoline compounds

The electronic spectra of three azo cinnoline derivatives have been studied in pure and mixed organic solvents of different characteristics as well as the effect of concentration of the compounds in the different solvents. The different bands observed have been assigned to the proper electronic transition. The longer wavelength band displayed by the para nitro cinnoline derivative in dimethylformamide (DMF) solution is assigned to an intermolecular CT transition. The solvated H-bonding complexes formed between DMF and the para nitro derivative were investigated. DeltaG and K(f) values of these complexes have been determined. The acidity constants of the para nitro compound were determined from the spectra in aquous-methanolic solution of varying pH values. The effect of temperature on the longer wavelength visible band of p-NO(2) has been investigated.     

Solubility profiles of poly(ethylene glycol)/solvent systems, I: Qualitative comparison of solubility parameter approaches

Solubility of systems involving four different molecular weights of poly(ethylene glycol) (PEG) in tetrahydrofuran (THF), chloroform, dimethylsulfoxide (DMSO), methanol and water have been investigated by different algorithmic approaches as the mathematical application of the “like dissolves like” principle. In this study, the solubility parameters and their components for PEG and solvents have been evaluated by using of atomic group contribution methods; Small, van Krevelen-Hoftyzer (VKH), Hoy and Breitkreutz methods, respectively. Then their 2-dimensional graphs (Bagley, Henry and Hoernschemeyer diagrams) and 3-dimensional graph (Hansen diagram) have been drawn by creating the solubility profiles of the polymer in selected solvents. The dissolving capability of these solvents has been discussed. In addition the solubility parameters have been calculated by use of the van der Waals volume in the selected molecule or repeating unit of the polymer instead of the molar volume which is used in atomic group contribution methods (Askadskii approach). Surface tensions of the polymer and solvent systems have been calculated with this method and solubility criteria of PEG have been explained after a serial calculation steps. In addition, influence of molecular weight of PEG on solubility has been also analyzed. As a consequence of algorithmic calculations, THF has been determined as the best solvent whereas water is found to be the weakest solvent for polymer/solvent systems.     

Solvent Role of Ionic Liquids in Fundamental Chemical Reaction Dynamics Analyzed by Time-Resolved Spectroscopy

Ionic liquids (ILs), which are used as solvents for chemical reactions, are different from conventional organic solvents owing to their designability. Physicochemical parameters of the ILs, such as polarity and viscosity, that affect chemical equilibria and reaction kinetics can be tuned by changing the combination of anions and cations or by varying the lengths of the alkyl chains present in the cations. We were interested in knowing how these physicochemical parameters affect fundamental chemical reactions in ILs. Therefore, in this personal account, we investigate our recent work on two different photochemical reactions in ILs, namely excited-state intramolecular proton transfer of hydroxyflavone and photodissociation of aminodisulfide, using time-resolved spectroscopic techniques. Interestingly, the roles of the ILs in these chemical reactions are quite different. The effect of the cationic species of the ILs (i. e., the head groups and number of alkyl carbons) on the solvation environment upon photoexcitation and reaction rate are discussed.     

Solution properties of ion-containing polymers in polar solvents

The placement of ionic groups within the molecular structure of a polymer produces marked modification in physical properties. A large number of studies have been performed on these ion-containing polymers, but few have focused on the effects of anion–cation interactions (i.e., counterion binding or ionization) on hydrodynamic volume, especially as the molecular structure of the solvent and nature of counterion are varied. In this study changes in hydrodynamic volume are followed through reduced viscosity measurements as a function of the abovementioned molecular parameters. The dilute solution properties of various polyelectrolytes that contain sulfonate and carboxylate groups were investigated as a function of the counterion structure, charge density, molecular weight, and solvent structure. The polymeric materials were selected because of their specific chemical structure and physical properties. In the first instance a (2-acrylamide-2 methylpropanesulfonic acid)-acrylamide-sodium vinyl sulfonate terpolymer was synthesized and subsequently neutralized with a series of bases. Viscometric measurements on these materials indicate that the nature of the cation affects the ability of the polyelectrolyte to expand its hydrodynamic volume at low polymer levels. The magnitude of the molecular expansion is shown to be due in part to the ability of the counterion to dissociate from the backbone chain, which, in turn, is directly related to the solvent structure. The changes in solution behaviour of these inomers lend support for the existence of ion pairs (i.e., site binding) and ionized moieties on the polymer chains. Measurements performed in a variety of solvent systems further confirm this interpretation. In addition, and acrylamide-sodium vinyl sulfonate copolymer was partially hydrolyzed with sodium hydroxide to study the effect of varying the charge density at a constant degree of polymerization and counterion structure. The results show that the charge density has a significant effect on the magnitude of the reduced viscosity and dilute solution behaviour. These observations, made in aqueous and nonaqueous solvents, are related to the interrelation of hydrodynamic volume, counterion concentration, and site binding. Again the controlling factor is the degree of site binding of the counterion onto the polymer backbone. Finally, we observe that the increased hydrodynamic volume affects viscosity behavior beyond the polyelectrolyte effect regime. If the average charge density on the macromolecule is relative high and/or the molecular weight is large (≥ 10⁶) sufficient intermolecular interactions will occur to produce rapid changes in reduced viscosity.     

Photophysics of benzazole derived push–pull butadienes: A highly sensitive fluorescence probes

Two new homologues of 1,4-diphenylbutadiene, namely, 1-(2-benzazolyl)-4-(p-dimethylaminophenyl)buta-1,3-diene have been synthesized and their absorption and fluorescence properties have been investigated in different organic solvents. The absorption spectra are less sensitive to the solvent polarity than the corresponding fluorescence spectra, which show dual emission and high solvatochromic effect in polar solvents. Using an efficient solvatochromic method, a large excited state dipole moment parallel to the smaller ground state dipole moment was calculated. Other properties of the lowest excited state such as the planar ICT B_u nature, fluorescence quantum yield and the basicity of the two nitrogen atoms (of the benzoxazole or benzothiazole ring as well as the amino group) were studied by spectroscopic techniques and semiempirical AM1 quantum chemical calculations. The findings have been presented and discussed along with the promising fluorescence probing and pH-sensing properties of these two dienes. The main spectroscopic properties of the two derivatives have been also compared.     

树形聚醚的合成及其应用

树形聚合物高度支化,与线形结构的聚合物相比具有较低的粘度及良好的溶解性,而且其单分子尺寸通常在纳米尺度,在多方面具有广阔的应用前景。树形聚合物通常分为3种,即树枝状聚合物、超支化聚合物和树枝化聚合物。作为树形聚合物的主要一类,树形聚醚由于其良好的化学、物理稳定性,良好的水及有机溶剂的溶解性,以及生物相容性等诸多优点,其合成及应用研究得到了广泛重视。本文对不同种类树形聚醚的合成及其应用作一详尽的综述,包括树枝状聚醚、树枝化聚醚及超支化聚醚3种主要类型,同时报道了作者等在该领域的最新研究进展,并对该领域的研究进行了相应的展望。     

Thin-layer chromatography of metal chelates : Part II. An extended theory and its testing on metal dithizonates and metal diethyldithiocarbamates

The model of thin-layer chromatography suggested earlier has been developed so that it describes solute behaviour more thoroughly. Equations have been derived which describe particular cases such as development by a single solvent, or by a mixture of two solvents of different polarity, or by a mixed solvent of constant composition at varying humidity. Experimental verification was provided by a study of the t.l.c. behaviour of metal dithizonates and diethyldi-thiocarbamates on Silufol. A comparison of the mobilities of these metal chelates, as well as of those of 8-hydroxyquinoline, salicylaldoxime and benzoylacetone, with their extraction constants showed a mutual correlation between these properties.