The molecular and ionic solubility of nickel dimethylglyoximate

Values are reported for the solubility product constant and the ionization constant of nickel(II) dimethylglyoximate in aqueous solution. The solubility of nickel dimethylglyoximate in the investigated pH range from 2 to 9 is accounted for by the species Ni⁺² and Ni(HDx)₂; there is no evidence for the existence of a significant amount of NiHDx⁺.The extraction constant

has been calculated from the ionization constants of Ni(HDx)₂ and H₂Dx and the molecular solubilities of the former in water and chloroform.     

The geometry of intermolecular interactions in some crystalline fluorine-containing organic compounds

The propensity of C-F groups to form C-F H-C interactions with C-H groups on other molecules has been analyzed. Crystal structures of molecules containing only carbon, hydrogen, and fluorine, but no oxygen, nitrogen, or other hydrogen-bond-forming elements, were chosen for an initial study in which the intermolecular interactions in crystal-structure determinations of polycyclic aromatic hydrocarbons and their analogous fluoro derivatives were analyzed. It is found that C-F H-C interactions occur, but they are weak, as judged by the intermolecular distances and the angles involved. In a study of crystal structures of molecules containing other elements in addition to carbon, hydrogen, and fluorine, it was found that when an oxygen atom is in a neighboring position on an interacting molecule, a C-O group is more likely than a C-F group to form a linear interaction to the hydrogen atom of a C-H group. Thus, in spite of the high electronegativity of the fluorine atom, a C-F group competes unfavorably with a C-O^–, C-OH, or C=O group to form a hydrogen bond to an O-H, N-H, or C-H group. It is found, however, particularly for polycyclic aromatic hydrocarbons with substituted CF₃ groups that, in the absence of other functional groups that can form stronger interactions, C-F H-C interactions may serve to align molecules and give a different crystal packing from that in the pure hydrocarbon (where fluorine is replaced by hydrogen). Thus, C-F H-X (X = C, N, O) interactions are very weak, much weaker than C=O H-X interactions, but they cannot be ignored in predictions of modes of molecular packing in complexes and in crystals.     

Negative ion laser desorption ionization time-of-flight mass spectrometry of nitrated polycyclic aromatic hydrocarbons

Nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) are widespread environmental pollutants that are generated by incomplete combustion and by atmospheric transformation of polycyclic aromatic hydrocarbons (PAHs). Many nitro-PAH compounds are potent genotoxins and some are direct acting mutagens. Detection of nitro-PAHs in aerosols is complicated by small sample sizes and nitro-PAH abundances that are 1–2 orders of magnitude less than analogous unsubstituted PAHs. Selective detection of several nitro-PAHs by using laser desorption ionization time-of-flight mass spectrometry in negative ion mode has been achieved. Desorption and ionization of nitro-PAHs were effected by using pulsed UV radiation at 266 and 213 ran. Intense molecular anions were observed in addition to fragments identified as CN^? and NO ₂ ^? , which were characteristic indicators of the presence of nitro-PAHs. Selective detection of nitro-PAHs in negative ion mode was demonstrated in the analysis of a diesel particulate sample.     

SOLUBILITIES OF POLYCYCLIC AROMATIC HYDROCARBONS AND DI-REGION THEORY

By using the relationship equation of Partition coefficients with water solubilities for polycyclic aromatic hydrocarbons (PAHs), we have estimated the solubilities of PAHs. In addition the high-performance liquid chromatograph (HPLC) method has been used for the indirect determination of solubilities of PAHs. t3ased on the di-region theory, We have studied the relationship of the solubilities of PAHs with carcinogenicity and introduced the solubility parameter into the di-region theory equation. The calculated carcinogenicity of PAHs from the obtained equation shows little difference from that calculated from Dai Qianhuan's equation.     

Solubility and Dissolution Thermodynamics of Cefmetazole Acid in Four Neat Solvents and Preferential Solvation in Co-Solvent Mixtures of (Methanol,Ethanol or Isopropanol) + Water

The solubilities of cefmetazole acid in methanol, ethanol, isopropanol and water were determined experimentally by using the saturation shake-flask method within the temperature range from (278.15 to 303.15) K under pressure p?=?101.1 kPa. At a fixed temperature, the cefmetazole acid solubility falls in the order methanol?>?ethanol?>?isopropanol?>?water. The apparent dissolution enthalpy, dissolution entropy and Gibbs energy change were calculated. The acquired solubilities were correlated with Apelblat’s equation. The largest value of relative average deviation for mole fraction solubility was 0.45 × 10^?2, and of root-mean-square deviation, 0.747 × 10^?5. The type and extent and direction of solute–solvent interactions were identified using the concept of Linear Solvation Energy Relationship. In addition, the preferential solvation parameters (δx_1,3) of cefmetazole acid in co-solvent mixtures of methanol (1)?+?water (2), ethanol (1)?+?water (2) and isopropanol (1)?+?water (2) were derived via the inverse Kirkwood–Buff integrals method. At 298.15 K, the magnitude of preferential solvation of cefmetazole acid by the co-solvent is highest in methanol mixtures, followed by ethanol mixtures, and finally by isopropanol mixtures.     

Zur Bestimmung der 6 polycyclischen aromatischen Kohlenwasserstoffe nach der Trinkwasser-Verordnung an einer speziellen C18-Umkehrphasen-Trenns?ule

Zusammenfassung Zur Kontrolle des in der Trinkwasser-Verordnung von 1975 festgelegten Wertes von 0,25 g C pro Liter Trinkwasser für 6 polycyclische aromatische Kohlenwasserstoffe (paK) kann ein relativ einfaches flüssigkeitschromatographisches System verwendet werden. Neben einer käuflichen C₁₈-Umkehrphasen-Spezialsäule wird im isokratischen Betrieb Methanol oder Acetonitril als mobile Phase eingesetzt und die UV-Absorption bei 254 nm zur Detektion und quantitativen Messung herangezogen. Zur Gewährleistung der Selektivität sollte die Temperatur der Trennsäule beachtet werden. Die Erfassungsgrenze für die Summe der 6 paK liegt bei 0,007 g pro Liter Wasserprobe — etwa 1/30 des zu prüfenden Grenzwertes.

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Determination of the 6 polycyclic aromatic hydrocarbons according to the drinking water regulation by a special column: dependence of retention upon temperature, detection limit of UV-absorbance, selection of mobile phases

Summary The value of 0.25 g C of six polycyclic aromatic hydrocarbons (PAH) per litre of drinking water according to the drinking water regulation can be controlled with the aid of a relatively simple HPLC-system. A special commercially available C₁₈-reversed phase column is used in an isocratic run with methanol or acetonitrile as the mobile phase and the detection is achieved by a UV-spectrophotometer at 254 nm. The temperature of the column should be observed to ensure the selectivity for the separation of the PAH. The detection limit of the sum of the six PAH is 0.007 g per litre of drinking water — 1/30 of the value to be controlled.

     

Anti-aging and aging factors in life. The role of free radicals

The present review deals with some factors determining the anti-aging as well as the aging process. In order to get a deeper insight in the subject matter, firstly some less known spectroscopic and kinetic data of antioxidant vitamins (C, E, β-carotene) acting as anti-aging factors by electron transfer are briefly discussed. The generation of oxygen transients (OH, ROO, ¹O₂, ozone radicals, etc.) by sunlight, ultrasonic and microwave radiation are causing “oxygen stress” and contribute to early ageing is also reviewed. Particular attention is paid to external environmental aging factors. Their action is based on the incorporation of various pollutants contained in water and air in the human organism. In this respect the polycyclic aromatic hydrocarbons (PAHs) play an essential role by initiating DNA-mutation, leading to an accelerate aging, carcinogenesis and diseases.     

Homoaromaticity and homoconjugation in the quinacenes: Biquinacene,triquinacene, and hexaquinacene

A thermodynamic criterion for aromatic and conjugative interactions is proposed. Enthalpies of stepwise hydrogenation of, for example, three double bonds are compensated for strain energy changes during hydrogenation. Strain energies are calculated by molecular mechanics. If the compensated values show a monotonic increase from bond 3 to bond 1, the molecule is conjugatively stabilized. If the initial rise is sharp followed by a constant H _h for bonds 2 and 1 and the molecule is cyclic, stabilization is aromatic. If the compensated H _h decreases, the interaction is destabilizing. By this set of criteria, biquinacene is unstabilized, triquinacene is homoaromatically stabilized, hexaquinacene is homoconjugatively stabilized, and cis,cis,cis-1,4,7-cyclononatriene is homoaromatically destabilized. New experimental data are presented for the biquinacenes (bicycloocta-1,7-diene and its hydrogenation products) and the hexaquinacenes.     

Mutual Solubilities of Water and Alkanes

Summary.  The evaluation of mutual solubility data for systems water with n-alkanes, isoalkanes, and cycloalkanes along the three phase line is reported and a formula for the prediction of solubility of alkanes in water is developed. Then a cubic equation of state with an added term, which accounts for hydrogen bonding is used for correlation of liquid–liquid equilibrium data and for prediction of solubility of water in hydrocarbons using alkane in water solubility data. Comparison of the predicted and experimental solubilities is performed using all accessible experimental data. With this approach it is possible to predict the solubilities of water in alkanes with good accuracy over the temperature range up to about 20 K below critical temperature. Solubility of alkanes in water can also be calculated using experimental data for solubility of water in alkanes but results of these calculations are more sensitive to experimental errors of the data. Corresponding author: E-mail: macz@ichf.edu.pl Received August 5, 2002; accepted (revised) September 13, 2002 Published online March 13, 2003 RID="a" ID="a" Dedicated to Prof. Dr. H. Gamsj?ger on the occasion of his 70^th birthday anniversary     

Uranyl ion luminescence quenching with benzene derivatives and related compounds. Linear free energy relationship

Irradiation of uranyl ion with light of wavelength =345 nm to singlet state, through vibrational relaxation populates the lowest excited triplet state from where it emits luminescence emission at 486, 506, 535 nm. Elongation and weakening of uranium-oxygen multiple bonds is evident from the lower stretching frequency (701.15 cm^–1) in the excited state relative to the ground state (942.5 cm^–1). Series of aromatic molecules including benzene derivatives, aromatic hydrocarbons and heterocyclic molecules very efficiently quench uranyl ion luminescence through nonradiative donor-acceptor complex formation. Increasing inductive effect, resonance phenomena and extension of aromatic -electron cloud determine the order of Stern-Volmer constant to measure their quenching action.     

Determination of chlorinated polycyclic aromatic hydrocarbons in water by solid‐phase extraction coupled with gas chromatography and mass spectrometry

Given the potential risks of chlorinated polycyclic aromatic hydrocarbons, the analysis of their presence in water is very urgent. We have developed a novel procedure for determining chlorinated polycyclic aromatic hydrocarbons in water based on solid‐phase extraction coupled with gas chromatography and mass spectrometry. The extraction parameters of solid‐phase extraction were optimized in detail. Under the optimal conditions, the proposed method showed wide linear ranges (1.0–1000 ng/L) with correlation coefficients ranging from 0.9952 to 0.9998. The limits of detection and the limits of quantification were in the range of 0.015–0.591 and 0.045–1.502 ng/L, respectively. Recoveries ranged from 82.5 to 102.6% with relative standard deviations below 9.2%. The obtained method was applied successfully to the determination of chlorinated polycyclic aromatic hydrocarbons in real water samples. Most of the chlorinated polycyclic aromatic hydrocarbons were detected and 1‐monochloropyrene was predominant in the studied water samples. This is the first report of chlorinated polycyclic aromatic hydrocarbons in water samples in China. The toxic equivalency quotients of chlorinated polycyclic aromatic hydrocarbons in the studied tap water were 9.95 ng the toxic equivalency quotient m^?3. 9,10‐Dichloroanthracene and 1‐monochloropyrene accounted for the majority of the total toxic equivalency quotients of chlorinated polycyclic aromatic hydrocarbons in tap water.     

π-hole bonding: A new retention mechanism for the solid phase extraction of polycyclic aromatic hydrocarbons from the hexane extracts of soil samples

In this work, the perfluorobenzene-bonded silica sorbent was tested to adsorb polycyclic aromatic hydrocarbons in hexane. In the comparison experiments, the perfluorobenzene-bonded sorbent's performance was better than octadecyl silica sorbent and phenyl-bonded silica sorbents, which indicated that the π-hole···π bonds between perfluorobenzene and the polycyclic aromatic hydrocarbons were stronger than π···π interactions and hydrophobic interactions in hexane. Then the perfluorobenzene-bonded silica sorbent was applied to solid-phase extraction of 15 polycyclic aromatic hydrocarbons from the hexane extracts of soil samples directly without the solvent replacement, which simplified the soil pretreatment process. And the results showed that under the optimal conditions, the proposed method for the determination of polycyclic aromatic hydrocarbons in the environment soil presented good recoveries and stabilities for the 10 heavier polycyclic aromatic hydrocarbons with the recoveries ranging from 75.1% to 104.6% and the relative standard deviations being in the range of 1.4%–5.8%. The limits of detection of the method varied from 0.1 to 2 ng/g. This work reveals the great application potential of the π-hole bond as a new retention mechanism in the field of solid-phase extraction.     

Molecular Structure of 5-Methylchrysene-7,8-dihydro-7,8-trans-(e,e)-diol

The crystal structure of the weak carcinogen 5-methylchrysene-7,8-dihydro-7,8-trans-(e,e)-diol is reported. This molecule contains a distorted bay region as a result of the presence of the 5-methyl group as found in 5-methylchrysene and 5,6- and 5, 12-dimethylchrysene. One torsion angle in this bay region is 20. The two hydroxyl groups of this molecule form hydrogen bonds throughout the crystal along theb direction. This is similar to the packing in other crystal structures of dihydrodiols of polycyclic aromatic hydrocarbons, each hydroxyl group both receiving and donating one hydrogen bond.     

多环芳烃水中溶解度的理论计算

建立了计算多环芳烃水中溶解度的数学表达式，用量子化学方法计算了7个多环芳烃的水中溶解度，计算结果与实验测定结果相符合．多环芳烃处于水体内体系状态能量愈高，其溶解度愈小，多环芳烃中的碳氢基团越多，溶解度越小．此时体系中的溶质呈单分子态，而不是聚集态．     

Solubilities of the cyclodextrins in the presence of transition metal salts

The solubilities of -, -, and -cyclodextrin have been measured in the presence of the first row transition metals: Cr³⁺, Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺; chlorides, nitrates and sulphates (in this case Fe²⁺), and, for companson, with CaCl₂, the corresponding Group IIa salt. Where possible the measurements are reported as a function of the activity of the salts. In general, for the transition metals the sulphates all show a linear decrease in solubility with increasing salt activity: for the nitrates the solubility increases and then reaches a limiting value; and for the chlorides a small decrease in solubility is observed at low activity followed by an increase in solubility at higher salt activity. Circular dichroism measurements confirm that there is no direct complexation at non-basic pH.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August 1995.     

Hydroxyundecanethiol-Modified Steel Fibers for the Selective Solid-Phase Microextraction of Polycyclic Aromatic Hydrocarbons from River and Wastewater

A novel organic–inorganic composite-coated fiber was developed for selective solid-phase microextraction (SPME) by direct electrodeposition of zinc oxide microparticles on a pretreated stainless steel wire followed by self-assembly of hydroxyundecanethiol with zinc–sulfur bonds. The performance of the hydroxyundecyl-modified zinc oxide-coated steel fiber was then assessed for SPME of polar aromatic compounds coupled to high-performance liquid chromatography with ultraviolet detection. Excellent extraction and selectivity were obtained for polycyclic aromatic hydrocarbons. The extraction and desorption times, temperature, stirring rate, and ionic strength were optimized. The limits of detection were from 0.034 to 0.132?µg?L^?1. The relative standard deviations were from 3.4 to 4.9% for a single fiber and from 5.1 to 6.4% for multiple fibers. The recovery of polycyclic aromatic hydrocarbons in environmental water fortified at 5.0 and 50?µg?L^?1 was from 83.1 to 103% with relative standard deviations below 8.4%. This fiber was shown to withstand at least 200 extraction and desorption cycles. The method was used for the preconcentration and determination of polycyclic aromatic hydrocarbons in environmental water.     

Solubility of pentane, 2-methylbutane,and cyclopentane in liquid nitrogen at 77.4 K

The solubilities of pentane, 2-methylbutane (isopentane) and cyclopentane were measured in liquid nitrogen at 77.4 K by the filtration method. The solubilities of the C₅ hydrocarbons in liquid nitrogen at 77.4 K vary from 1.8×10^–8 mole fraction for cyclopentane, to 3.0×10^–8 mole fraction for pentane and 3.2×10^–7 mole fraction for 2-metylbutane. Correlations between the solubilities of alkanes, alkenes and cyclic hydrocarbons in liquid nitrogen, and some properties of solutes [normal boiling point T _b , enthalpy of vaporization at normal boiling point H _b and the mean of the enthalpy of vaporization and the enthalpy of melting [(H _b +H _m )/2] are presented.     

Recent advances in metal-organic frameworks for adsorption of common aromatic pollutants

This review (with 85 refs.) summarizes the recent literature on the adsorption of common aromatic pollutants by using modified metal-organic frameworks (MOFs). Four kinds of aromatic pollutants are discussed, namely benzene homologues, polycyclic aromatic hydrocarbons (PAHs), organic dyes and their intermediates, and pharmaceuticals and personal care products (PPCPs). MOFs are shown to be excellent adsorbents that can be employed to both the elimination of pollutants and to their extraction and quantitation. Adsorption mechanisms and interactions between aromatic pollutants and MOFs are discussed. Finally, the actual challenges of existence and the perspective routes towards future improvements in the field are addressed.

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Graphical abstract Recent advance on adsorption of common aromatic pollutants including benzene series, polycyclic aromatic hydrocarbons, organic dyes and their intermediates, pharmaceuticals and personal care products by metal-organic frameworks.

     

Magnetic solid phase extraction of N- and S-containing polycyclic aromatic hydrocarbons at ppb levels by using a zerovalent iron nanoscale material modified with a metal organic framework of type Fe@MOF-5, and their determination by HPLC

Metal organic frameworks of type MOF-5 exhibit good adsorption capacity for many organic compounds. The authors have used nanoscale silica-coated zerovalent iron and MOF-5 to prepare, by co-precipitation, a novel magnetic nanomaterial of type Fe@MOF-5. Its morphology and structure were characterized by transmission electron microscopy and X-ray diffraction. The nanomaterial is shown to be well suited for magnetic solid phase extraction for five kinds of N- and S-containing polycyclic aromatic hydrocarbons prior to quantitation by HPLC. The limits of detection are in the 25 to 33 ng?L^?1 concentration range. Four real water samples were used to validate the method, and the recoveries of spiked samples with concentrations of 5 and 10 ppb were found to be in the range between 92.6 and 97.3% (n = 3). The Fe@MOF-5 sorbent obviously has excellent adsorption capability for such compounds, can be fairly easily synthesized, displays sensitivity, simplicity, ease of operation, and can be prepared at low costs. In our perception, it has a large potential in terms of monitoring such environmental pollutants.

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Graphical abstract A metal organic framework of type Fe@MOF-5 is found to exhibit good adsorption capacity for N- and S-containing polycyclic aromatic hydrocarbons. A sensitive magnetic solid phase extraction method with Fe@MOF-5 was developed for the determination of N- and S-containing polycyclic aromatic hydrocarbons from the water samples.