The conductance of electrolytes in acetone-2-propanol and acetone-1,1,1,3,3,3-hexafluoro-2-propanol mixtures at 25°C1

Precise conductance measurements are reported for tetrabutylammonium chloride, bromide, iodie, and perchlorate and lithium chloride in acetone-2-propanol (2-PrOH) and acetone-1,1,1,3,3,3-hexafluoro-2-propanol (HFP) mixtures at 25°C. Densities, viscosities and dielectric constants of the mixtures were determined. The dielectric constant vs mole % acetone curve for the acetone (ε=19.4)-2-propanol (ε=20.5) goes through a minimum at 40% acetone (ε=17.4), while that for acetone-HFP (ε=16.8) goes through a maximum at 50% acetone (ε=26.87). The variations ofK _A with ε in acetone-HFP are in accord with the predictions of electrostatic theory, while those for acetone-2-PrOH show more complex behavior. Ionic association in these mixtures is discussed in terms of an interplay between solvent structure and a multiple-step association process.     

Effects of the 3- and 4-methoxy and acetamide substituents and solvent environment on the electronic properties of N-substituted 1,8-naphthalimide derivatives

The photophysical properties of polar molecules in solution with an intramolecular charge-transfer effect in the excited state depend strongly on the polarity and proticity of the solvents. UV-visible spectra of 1,8-naphthalimide and some N-substituted derivatives in acetic acid, acetonitrile, dichloromethane, and p-dioxane were carried out. Several molecular cluster geometries formed with N-substituted 1,8-naphthalimide derivatives and a large set of random positioning of some solvent molecules in their environment were optimized by a semiempirical method. It provided a complete screening of possible solute-solvent configurations and resulted in a multiple minima hypersurface of the supramolecular systems. With such local minima energies, the main thermodynamic association functions were found. They also provided selected cluster geometries for calculations of vertical electronic transitions with a time-dependent density functional theory (TD-DFT), if the lowest energy structures were considered. Calculated vertical electronic transition energies at the TD-DFT level were compared with experimental data. The experimental absorption UV-visible spectra for the six compounds in the four solvents were performed in our laboratory. Moreover, X-ray photoelectron spectroscospy of the 1,8-naphthalimide was carried out in the ICP-CSIC laboratory. Thermodynamic function values show different association energies between each solvent and the molecules, in correlation with the possibility of hydrogen bond formation and the polarity and dielectric constant of the solvents. The 3- and 4-acetamide 1,8-naphthalimide derivatives have the highest conformer number and the most negative Gibbs free association energy values for a determined solvent. This indicates the importance of the entropic factors.     

Influence des solvants sur la copolymérisation de l'acrylamide avec l'acrylonitrile

The copolymerization of acrylamide with acrylonitrile was investigated in various solvents, which can be put into three groups according to their influence on molecular associations; (1) solvents autoassociated by hydrogen- bonds (acetic acid, methanol, water, dimethylformamide); (2) polar solvents which can associate with the NH group of acrylamide (acetonitrile, dioxane, acetone); (3) inert solvents (toluene, benzene, hexane). The reaction kinetics and the compositions of the copolymers are different for each group of solvents. The composition of copolymers formed in solvents of group 1 vary widely, depend- ing on the solvent. Copolymers formed in all solvents of group 2 have the same composition which is that of copolymers formed in bulk. The amount of acrylamide is highest in copolymers formed in inert solvents of group 3. Such parameters as the degree of conversion, the reaction temperature, the mode of initiation and the extent of dilution only slightly affect the composition of copolymers. Homopolymerizations of acrylamide and acrylonitrile were investigated in all solvent used.The results suggest that the effects of solvents on the copolymerization of acrylamide with acrylonitrile are consequences of the various modes of molecular association of acrylamide. The solvents affect the equilibrium between auto- association of acrylamide and its association with solvent and thereby affect the reactivity of the monomer.     

DCM衍生物双光子吸收截面的溶剂效应

考察了以三苯胺基为给电子基团的4种不同DCM衍生物在有机溶剂中的单光子光物理性质(基态和激发态永久偶极矩差、光学跃迁偶极矩以及跃迁能量等), 并利用双光子诱导荧光法考察了溶剂对其双光子吸收截面(δtpa)的影响. 研究结果表明, DCM衍生物的光学跃迁具有显著的分子内电荷转移特性, 不同末端取代基主要影响其稳态光谱性质, 而分支结构数目主要影响其双光子吸收截面. 研究结果还发现, 双光子吸收截面随分子结构的变化趋势符合双能级模型, 拉电子基团为丙二腈和1,3-茚二酮的DCM衍生物的δtpa随溶剂介电常数的增加呈现不同的变化趋势.     

Basicity comparison for di-substituted 4-nitropyridine derivatives in polar non-aqueous media

Acid dissociation, as well as cationic homoconjugation equilibria have been studied potentiometrically in systems involving four di-substituted 4-nitropyridines and conjugate cationic acids in the polar non-aqueous solvents - aprotic protophobic acetonitrile (AN) and propylene carbonate (PC), the amphiprotic methanol (MeOH), and in the aprotic protophilic dimethyl sulfoxide (DMSO). The influence of solvent effect on the obtained acidity constants has been discussed. The acidity constants (expressed as pK_a values) were compared with those previously determined in another polar protophobic aprotic solvent - acetone (AC), and obtained for the unsubstituted pyridine (Py). A comparison of the acid dissociation constants determined in all media studied has proved that the strength of the cationic acids increases on going from acetonitrile through propylene carbonate, acetone, and methanol to dimethyl sulfoxide. Furthermore, the values of acidity constants in the non-aqueous media have shown that in all the solvents studied they change according to the substituent effects. It has been also found that substituted 4-nitropyridine derivatives studied exhibit no tendency towards cationic homoconjugation in acetonitrile, propylene carbonate, and methanol and dimethyl sulfoxide. Moreover, it has been demonstrated that the acid dissociation constants determined by potentiometric titration method in all the solutions investigated correlate well with the calculated energy parameters of the protonation reactions in the gaseous phase.     

A density functional study on dielectric properties of acrylic acid grafted polypropylene

Influence of acrylic acid grafting of isotactic polypropylene on the dielectric properties of the polymer is investigated using density functional theory (DFT) calculations, both in the molecular modeling and three-dimensional (3D) bulk periodic system frameworks. In our molecular modeling calculations, polarizability volume, and polarizability volume per mass which reflects the permittivity of the polymer, as well as the HOMO-LUMO gap, one of the important measures indicating the electrical breakdown voltage strength, were examined for oligomers with various chain lengths and carboxyl mixture ratios. When a polypropylene oligomer is grafted with carboxyl groups (cf. acrylic acid), our calculations show that the increase of the polarizability volume α' of the oligomer is proportional to the increase of its mass m, while the ratio α'/m decreases from the value of a pure polymer when increasing the mixture ratio. The decreasing ratio of α'/m under carboxyl grafting indicates that the material permittivity might also decrease if the mass density of the material remains constant. Furthermore, our calculations show that the HOMO-LUMO gap energy decreases by only about 15% in grafting, but this decrease seems to be independent on the mixture ratio of carboxyl. This indicates that by doping polymers with additives better dielectric properties can be tailored. Finally, using the first-principles molecular DFT results for polarizability volume per mass in connection with the classical Clausius-Mossotti relation, we have estimated static permittivity for acrylic acid grafted polypropylene, assuming the structural density keeping constant under grafting. The computed permittivity values are in a qualitative agreement with the recent experiments, showing increasing tendency of the permittivity as a function of the grafting composition. In order to validate our molecular DFT based approach, we have also carried out extensive three-dimensional bulk periodic first-principles total-energy calculations in the frameworks of the density functional theory and density functional perturbation theory (DFPT) for crystalline acrylic acid grafted polypropylene. Interestingly, the computed electronic and dielectric properties behave very similarly between the simplified molecular DFT modeling and the more realistic 3D bulk periodic DFPT method. In particular, the static permittivity values [ε(r)(0)] from the molecular DFT-Clausius-Mossotti modeling are in excellent agreement with the high-frequency dielectric constant values (ε(∞)) from the DFPT method. This obviously implies that the chain-to-chain interaction to dielectric and electronic properties of acrylic acid polypropylene, to a first approximation, can be neglected, therefore justifying the usage of molecular DFT modeling in our calculations.     

Molecular interactions in polystyrene cosolvent systems

Studied here are miscible binary cosolvents for polystyrene, for which polystyrene is insoluble in either of the individual solvents. Polymer-solvent interactions in solutions of atactic polystyrene in acetone/diethyl ether and in methylcyclopentane (MCP)/acetone binary cosolvents have been investigated using nuclear magnetic resonance (NMR) spectroscopy. Polystyrene ¹³C chemical shifts were measured as a function of miscible binary solvent compositions and temperature. The NMR data were used to calculate “association constants” as a measure of specific interactions of the solvent components with all sites on the polymer. In mixtures of acetone and diethyl ether, ¹³C-NMR indicates a weak interaction between the polystyrene phenyl ring and the diethylether solvent component. In the polystyrene/MCP/acetone system, present NMR data reveal no preferential interactions. Additional NMR measurements were performed on polystyrene in mixtures of CCl₄/acetone. From these results, it is concluded that although preferential polymer-solvent interactions are present in some cosolvent systems, they are not a prerequisite for such behavior.     

微波法研制碱土金属氧化物负载型MCM-48碱性介孔材料

以立方相介孔分子筛MCM-48为载体,用微波辐射分散MgO或CaO和醋酸镁溶液浸渍等方法研制碱性介孔材料。MCM-48能经受微波辐射,负载碱性客体之后也保持介相结构。异丙醇分解探针反应表明:载体本身没有碱催化活性,而碱性MCM-48介孔材料的活性随温度升高而提高。本文还对介孔材料在微波分散和碱性催化方面的特点进行分析。     

Dielectric properties for the binary mixture of dimethylsuphoxide and dimethylacetamide with 2-nitrotoluene at microwave frequencies

The dielectric properties of various organic solvents and binary solvent mixtures at different temperatures over the frequency range of 10 MHz–20 GHz, are investigated using the time domain reflectometry technique, at various temperatures from 15 to 45 °C. These solvent mixtures—dimethylacetamide–2-nitrotoluene and dimethylsulphoxide–2-nitrotoluene as well as pure solvents display a Debye type dispersion. Their frequency-dependent dielectric properties can be summarized by the three parameters in the Debye equation: a static permittivity, permittivity at high frequency and a dielectric relaxation time constant. The free energy of activation for dipolar relaxation process and the Kirkwood correlation factor were determined using these fitting parameters, for these solvent systems at various temperatures. By using these dielectric parameters, the excess permittivity and excess inverse relaxation time is obtained. The static permittivity increases with increase in volume percentage of 2-nitrotoluene in dimethylacetamide as well as dimethylsulphoxide whereas the relaxation time decreases for both the systems.     

Electronic absorption spectra of benzoquinone and its hydroxy substituents and effect of solvents on their spectra

The electronic absorption spectra of 1,4-benzoquinone (BQ) and its 2,5-dihydroxy and tetrahydroxy derivatives have been studied in detail. The interpretation of the electronic bands is made on the basis of PPP and CNDO calculations. It is found that the pi --> pi* transitions are well predicted by the PPP method. The predictions of the CNDO method are however superior both in their accuracy as well as ability to predict the n --> pi* transitions. The effect of solvents on the electronic absorption bands have also been investigated in detail. Linear correlations are found between the solvent's dielectric constant and wavelength of the absorption bands. The solvent shifts are explained on the basis of the polarities of the solute and solvent molecules as well as due to hydrogen bonding.     

Anion exchange behaviour of uranium, thorium and lanthanides in organic solvent mixtures

Summary The adsorption behaviour of uranium, thorium, cerium and terbium towards the strongly basic anion exchange resin Dowex-1 in mixtures of various organic solvents with acetone and methanol as the base solvents was investigated. The complexing acid in case of acetone was nitric acid while in the case of methanol, hydrochloric acid was used. Measurements of the distribution coefficients of these elements in such mixtures containing nitric acid as the complexing agent showed that in all cases a linear relationship between the adsorption and the concentration of acetone is existing. Furthermore the relationship between the dielectric constants of the solvent mixtures and the adsorption of above elements was investigated. The results show that the dielectric constant of the solvent mixture cannot be employed for predicting the degree of adsorption.

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Zusammenfassung Das Adsorptionsverhalten von Uran, Thorium, Cer und Terbium gegenüber dem stark basischen Anionenaustauscher Dowex-1 wurde in Mischungen von Aceton oder Methanol mit anderen organischen Lösungsmitteln untersucht. Als Komplexbildner dienten Salpeter- bzw. Salzsäure. Die Messung der Verteilungskoeffizienten in salpetersäurehaltigen Gemischen ergab, daß zwischen der Adsorption und der Acetonkonzentration ein linearer Zusammenhang besteht. Der Zusammenhang zwischen der Adsorption und der Dielektrizitätskonstanten des Lösungsmittelgemisches ist jedoch nicht eindeutig und kann daher nicht zu Aussagen über das Adsorptionsverhalten benutzt werden.

     

Molecular mechanism of dielectrically controlled optical resolution (DCR)

We have recently found the first example of dielectrically controlled optical resolution (DCR). By adjusting the dielectric constant of the solvent used in the resolution process, each optical isomer of (R,S)-alpha-amino-epsilon-caprolactam can be selectively obtained using N-tosyl-(S)-phenylalanine as a chiral selector. The molecular mechanism of DCR has been investigated by comparing the molecular and crystal structures of the optical selector, its target substrate and their diastereomeric salts. Strong hydrophobic interactions between the phenyl rings of the optical selector govern the molecular aggregation of the selectors and form a hydrophilic layer in which molecular recognition takes place. The recognition site in the hydrophilic layer can inherently identify both of the isomers. The dielectric constant of the solvent used in the discrimination process controls the intermolecular interaction which determines the isomer to be selected. The molecular mechanism of DCR disclosed in this study strongly suggests that DCR is not a specific but a general phenomenon. This method can be applicable to a large variety of optical resolution processes.     

Polarity of layer-by-layer deposited polyelectrolyte films as determined by pyrene fluorescence.

The polarity of polyelectrolyte (PE) multilayer films is investigated with pyrene as a polarity-sensitive probe. Multilayer films of poly(styrene sulfonate) (PSS) and various polycations were prepared by the layer-by-layer self-assembly technique. Pyrene (PY) molecules were inserted into the films by exposing the multilayers to pyrene solutions. By this method a homogeneous distribution of pyrene molecules at low concentration within the film was obtained. The ratio of the fluorescence intensities of the first (I) to the third (III) vibronic band (Py-value) of the pyrene emission spectrum is employed here to determine the polarity of the PE films. PSS and poly(allylamine hydrochloride) (PAH) multilayer films yielded a pyrene value close to the solvent polarity of acetone, while multilayers of PSS and poly(diallyldimethylammonium chloride) (PDADMAC) displayed a value higher than the one corresponding to water. The pyrene values of the polyelectrolyte films were independent from the solvent employed for probe dissolving. Although no direct relationship between solvent polarity and dielectric constant (epsilon) is available, an estimate of the static dielectric constant of the films can be provided by comparing the Py-values of the films with those of various solvents. Changes in the humidity conditions of the film environment in a closed cell did not affect the film polarity. However, a drastic and irreversible reduction of polarity could be induced by actively drying the samples by a nitrogen flow.     

Copolymerization and interaction of acrylonitrile and indene

The donor–acceptor interaction of acrylonitrile (AN) with indene (In) has been investigated by means of ultraviolet spectroscopy and dielectric polarization measurements. The latter method yielded a value of 0.5 for the association constant of the charge-transfer-complex (CTC) and a 4.02 D for its dipole moment. The copolymerization of the two monomers was characterized by a tendency towards alternation when conducted in the bulk. This might be due to the participation of a weak CTC in the process of copolymerization. However, this tendency disappeared in polar solvents such as DMF.     

Temperature Dependent Dielectric Relaxation in Solvent Mixtures at Microwave Frequencies

By the use of time domain reflectometry method, dielectric measurements were carried out on dimethylformamide‐2‐nitrotoluene solvent mixtures in the frequency range 10 MHz‐20 GHz, at various temperatures from 15 °C to 45 °C. These solvent mixtures as well as pure solvents display a Debye type dispersion. Their frequency dependent dielectric properties can be summarized by the three parameters in the Debye equation: a static permittivity, permittivity at high frequency and a dielectric relaxation time constant. The free energy of activation for dipolar relaxation process and the Kirkwood correlation factor were determined using these fitting parameters for these solvent mixtures at various concentrations and temperatures. By using these dielectric parameters, the excess permittivity and excess inverse relaxation time is obtained. The excess permittivity is found to be positive for all concentrations and temperatures whereas the excess inverse relaxation time is negative.     

Design and synthesis of nematic liquid crystals with negative dielectric anisotropy

Axially fluorinated cyclohexane derivatives are a promising new type of liquid crystals with negative dielectric anisotropy. Up to now, the technical application of these materials in LCDs was impeded by their strong tendency to form smectic B mesophases. We present a convenient synthetic pathway leading to new homologues carrying alkenyl side chains which induce nematic phases.     

ASSESSMENT OF DIELECTRIC ENRICHMENT AROUND TWO FLUOROPHORES IN BINARY SOLVENTS

Abstract We investigated dielectric enrichment, or the preferential interaction between a probe and a polar solvent, using two different fluorophores in binary solvents that will not form strong hydrogen bonds with the probe. The first probe, 6-propionyl( N,N -dimethylamino)naphthalene (PRODAN), undergoes a large change in dipole moment in the excited state. We found that its emission energy varies linearly with the dielectric parameter f(D) [f(D) = 2(D - 1)/(2D + 1)] in acetone/benzene and acetonekyclohexane mixtures. The emission of the second probe, N-acetyl tryptophanamide (NATA), also varies linearly with f (D) in ethylether/acetonitrile solvents. This lack of preferential solvation was further investigated by studies of NATA in acetonitrile/methanol mixtures where hydrogen bonding is possible. We found that NATA-methanol interactions are not energetic enough to give rise to significant preferential solvation. Since preferential solvation does not occur even for weakly hydrogen bonding solvents it is thus highly unlikely that dielectric enrichment, which takes place in the absence of specific interactions, occurs with any frequency. We postulate that previous reports of dielectric enrichment were due to a lack of consideration of changes in f (D) of the solvent.     

Ruthenium‐Catalyzed Asymmetric Hydrogenation of 3‐Oxoglutaric Acid Derivatives: A Study of Unconventional Solvent and Substituent Effects

A series of 3‐oxoglutaric acid derivatives have been hydrogenated in different solvents in the presence of [RuCl(benzene)(S)‐SunPhos]Cl (SunPhos=(2,2,2′,2′‐tetramethyl‐[4,4′‐bibenzo[d][1,3]dioxole]‐5,5′‐diyl)bis(diphenylphosphine)). Unlike simple β‐keto acid derivatives, these advanced analogues can be readily hydrogenated in uncommon solvents such as THF, CH₂Cl₂, acetone, and dioxane with high enantioselectivities. Two possible catalytic cycles have been proposed to explain the different reactivities of these 1,3,5‐tricarbonyl substrates in the tested solvents. The C‐2 and C‐4 substituents had notable but irregular influence on the reactivity and enantioselectivity of the reactions. More pronounced solvent effects were observed: the ee values increased from around 20 % in EtOH or THF to 90 % in acetone. Inversion of the product configuration was observed when the solvent was changed from EtOH to THF or acetone, and a mixed solvent system can lead to better enantioselectivity than a single solvent.     

Liquid water confined in carbon nanochannels at high temperatures

Structure, hydrogen bonding, electrostatics, dielectric, and dynamical properties of liquid water confined in flat graphene nanochannels are investigated by molecular dynamics simulations. A wide range of temperatures (between 20 and 360 degrees C) have been considered. Molecular structure suffers substantial changes when the system is heated, with a significant loss of structure and hydrogen bonding. In such case, the interface between adsorbed and bulk-like water has a marked tendency to disappear, and the two preferential orientations of water nearby the graphite layers at room temperature are essentially merging above the boiling point. The general trend for the static dielectric constant is its reduction at high temperature states, as compared to ambient conditions. Similarly, residence times of water molecules in adsorbed and bulk-like regions are significantly influenced by temperature, as well. Finally, we observed relevant changes in water diffusion and spectroscopy along the range of temperatures analyzed.     

The Extraction of Polycyclic Aromatic Hydrocarbons from Atmospheric Particulate Matter Samples by Accelerated Solvent Extraction (ASE)

Abstract

The Accelerated solvent extraction (ASE) of PAHs (23 2- to 6-ring species) spiked onto glass fibre filters (GFFs) was studied as a function of variable extraction solvents, pressure, temperature and extraction times. Acceptable recoveries (85% ± 15%) were obtained for certain combinations of conditions and a tentative method (1500 psi, 150°C, 70:30 hexane:acetone mixture, 7 min heat-up time, 5 min static extraction time, 60% flush volume, 2 static cycles was selected for further testing. However, this method did not prove as effective as the traditional Soxhlet method of extraction when these parameters were used to extract native PAHs from ambient atmospheric particulate matter collected on a GFF by Integrated Atmospheric Deposition Network (IADN) sampling protocols. The extraction recovery study for spiked GFFs was repeated using slightly different extraction conditions: 2000 psi, 100°C, 70:30 hexane:acetone, 5 min heat-up time, 5 min static extraction time, 150% flush volume, 3 static cycles. When this method was applied to the extraction of native PAHs from ambient atmospheric particulate matter collected on GFFs, the results showed equivalent or better recoveries to that of the Soxhlet method. The total time of extraction was 25 min requiring only 30 mL of solvent. This ASE method is presently used to quantitatively determine PAHs in IADN particle-phase samples.