Band 7, Heft 1

Vapor-liquid equilibria (VLE) data for the carbon dioxide + methanol system was measured at 293.15, 298.15, 310.15, and 323.15 K. Phase behavior measurements were made in a high-pressure visual cell with variable volume, based on the static-analytic method. The pressure range under investigation was between 4.8 and 95.1 bar. The Soave-Redlich-Kwong (SRK)-EOS coupled with Huron-Vidal (HV) mixing rules and a reduced UNIQUAC model, was used in a semi-predictive approach, in order to represent the phase behavior (critical curve, isothermal VLE) of the system. The topology of the phase behavior of the carbon dioxide + methanol system is satisfactory predicted with the SRK/HV-residual UNIQUAC model.

The dissociation constants of (4-amino-1-hydroxybutylidene)bisphosphonic (alendronic) acid, (3-(dimethylamino)-1-hydroxypropylidene)bisphosphonic (olpadronic) acid and (3-amino-1-hydroxypropylidene)bisphosphonic (pamidronic) acid were obtained in aqueous solutions (0.10 M KCl) and micellar solutions of cetylpyridinium chloride (0.10 M CPC) at 25.0°C. With the exception of the third dissociation constant of alendronic acid, the dissociation constants of alendronic, olpadronic and pamidronic acids in aqueous solutions matched literature data. The possibility of sodium alendronate determination by acid-base titration by NaOH solution was theoretically grounded on the basis of re-evaluated data of alendronic acid dissociation constants.

The crystal structures of 3-amino-cycloheptanespiro-4′-imidazolidine-2′,5′-dione (I) {systematic name: 3-amino-1,3-diazaspiro[4.6] undecane-2,4-dione} and 3-amino-cyclooctanespiro-4′-imidazolidine-2′,5′-dione (II) {systematic name: 3-amino-1,3-diazaspiro[4.7] dodecane-2,4-dione}, have been determined. In both compounds the polar hydantoin groups cause molecules to aggregate via N-H...O and N-H...N interactions, forming a layer structure, in which the cycloalkane rings project outwards from the central, more polar, region. The observed molecular structure is compared with that calculated by density functional theory methods.

This paper presents the results of determination of selected characteristics (anions, cations, formaldehyde, hydrogen peroxide, phenols, TC, TIC, TOC and metals) in dew samples collected in six different sites in Poland. The influence of local parameters (e.g. wind speed, humidity) was investigated. Discriminant analysis was applied to the study of several dew samples collected from different sampling sites covering six agglomerations in Poland. Discriminant function analysis was used not only for classifying samples into different groups with a better than chance accuracy, but also for detecting the most important variables that discern between the groups of samples considered. In this way it was possible to identify which ions or other physicochemical features are responsible for the similarities or differences observed between different groups of dew samples. A good agreement with their origin and location was observed. It is interesting to note that the classification of all samples was dominated by pH, wind direction, pressure and temperature with a significant contribution of Na+ and Cl− ions.

Layered compounds with CdS particles supported on the ion-exchanger, γ-titanium dihydrogen phosphate, were prepared by the stepwise reaction of the ion-exchanger and cadmium solution, followed by reaction with H2S gas. The CdS content on the ion-exchanger is dependent on the timeframe of the H2S gas flow. The materials obtained were layered, as shown by the X-ray measurements that exhibit both precursor and CdS diffraction peaks. The thermal treatment of the material obtained gives evidence of its stability (≤ 320°C) before the CdS decomposition, which occurs in a single step.

A solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma mass spectromA solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma mass spectrometry (ICP-MS) was developed. The method was based on retention of platinum in a sample on silica gel modified with aminepropyl groups. The retention of platinum(IV) from the sample solution and the recovery of platinum with 1.0 mol L−1 thiourea solution were quantitative. The relative standard deviation (RSD) was calculated as 5% (n = 7) at the 10 ng L−1 level. The enrichment factor was found to be (50-fold) for 250 mL of water sample. Under optimum conditions, the method detection limit (MDL) was found to be 1 ng L−1 for platinum in water matrices. Recoveries of Pt from spike addition to atmospheric water samples were quantitative (80–95%). The present method was used for the determination of platinum in precipitation, throughfall and runoff water samples.

Nanostructured hybrid materials containing Al2O3 were synthesized via a sol-gel method through hydrolysis and co-condensation reactions using trimethylsilyl isocyanate (TMSI) as a new silica source in the presence of tetramethoxysilane (TMOS) and three different quantities (10, 20 and 30 wt.%) of aluminum sec-butoxide (Al(OBusec)3 as a modifying agent. The xerogel nanostructured materials are pyrolyzed in nitrogen atmosphere in the temperature range from 400°C to 1100°C. The transformation of the xerogel hybrid networks into Al-Si oxycarbonitride materials has been investigated by XRD, FTIR, SEM, AFM, and 29Si MAS-NMR. To the best of our knowledge, the work reported here is the first synthesis of porous di-urethanesils modified with aluminum and one of the few examples of alumosilica oxycarbonitride materials

Characterization of four amalgam surfaces, with different alteration degrees from Andalusia historical mirrors, has been carried out by grazing-incidence X-ray diffraction (GIXRD), and other spectroscopic techniques (SEM/EDX, XPS, and REELS). The combination of all these techniques allows determining the corrosion state of the amalgams. The results show that the amalgams are composed in all cases of a binary alloy of tin and mercury. As mercury has high vapour pressure at RT, it slowly segregates and eventually evaporates, it leaves finely divided particles of tin that easily can be oxidize, forming tin monoxide (SnO) and tin dioxide (SnO2). In one of the samples, most of the amalgam remains unoxidized, since Hg0.1Sn0.9 and metallic Sn phases are the major components; in two other samples, Hg0.1Sn0.9 and Sn phases are not detected while SnO2 and SnO phases appear. Finally, in the last studied sample, only SnO2 phase is detected. The surface analyses of these samples by XPS show that, for most of them an unique chemical species (Sn4+) is found.

Fullerene black (FB) - a product of electric arc graphite vaporization after extraction of fullerenes - was modified with the di(2-ethylhexyl)phosphoric acid (D2EHPA). The distribution of D2EHPA between FB and aqueous HNO3 solutions has been studied. The effect of HNO3 concentration in the aqueous phase and that of D2EHPA concentration in the sorbent phase on the adsorption of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y nitrates from HNO3 solutions by D2EHPA-modified FB are considered. The stoichiometry of the sorbed complexes has been determined by the slope analysis method. The efficiency of lanthanides’ adsorption increases with an increase in the element atomic number. A considerable synergistic effect has been observed upon the addition of the neutral bidentate tetraphenylmethylenediphosphine dioxide ligand to D2EHPA in the sorbent phase.

Models to predict binding constant (logK) to bovine serum albumin (BSA) should be very useful in the pharmaceutical industry to help speed up the design of new compounds, especially as far as pharmacokinetics is concerned. We present here an extensive list of logK binding constants for thirty-five compounds to BSA determined by florescence quenching from the literature. These data have allowed us the derivation of a quantitative structure-property relationship (QSPR) model to predict binding constants to BSA of compounds on the basis of their structure. A stepwise multiple linear regression (MLR) was performed to build the model. The statistical parameter provided by the MLR model (R = 0.9200, RMS = 0.3305) indicated satisfactory stability and predictive ability for the model. Using florescence quenching spectroscopy, we also experimentally determined the binding constants to BSA for two bioactive components in traditional Chinese medicines. Using the proposed model it was possible to predict the binding constants for each, which were in good agreement with the experimental results. This QSPR approach can contribute to a better understanding of structural factors of the compounds responsible for drug-protein interactions, and be useful in predicting the binding constants of other compounds.

A variety of carbohydrates, in particular polysaccharides can be subjected to chemical modification to obtain derivatives with amphiphilic properties, which enable biochemical or biological reactions at the polymer surface. In the present work, a polydisperse maltodextrin mixture of average molecular weight 3000 was coupled with 1,6-hexamethylenediamine (HMD) via reductive amination reaction. Resulting products were characterized by thermal analysis and positive nanoelectrospray quadrupole time-of-flight (Q-TOF) mass spectrometry (MS) and tandem mass spectrometry (MS/MS). Both thermal analysis and MS screening confirmed the formation of the HMD-polysaccharide coupling products. Moreover, HMD-linked polysaccharide chains containing 2 to 26 glucose building blocks were identified by nanoESI Q-TOF MS. MS/MS fragmentation using collision-induced dissociation (CID) at low ion acceleration energies provided strong evidence for HMD-maltodextrin linkage formation and the set of sequence ions diagnostic for the composition and structure of a HMD-linked chain containing 18 glucose residues.

The present study concerns the electrochemical synthesis of basic copper carbonate nanoparticles by oxidation of metallic copper on the anode in an aqueous bicarbonate solution. This simple and one-step preparation can be considered as green synthesis. The scanning electron microscopy (SEM) analysis indicates that average particle size of the product is in the range of about 70 nm. On the other hand, basic copper carbonate micro-powder has been prepared, by mixing solutions of copper(II) sulphate and sodiu bicarbonate. The SEM analysis showed that the size of particles prepared in the same way is in the range of about 1 µm. In another part of this study, the thermal decomposition of micro and nanoparticles of copper carbonate produced by various methods was studied in air using TG-DTA techniques. The results of thermal study show that the decomposition of both samples occurs in single step. Also, the TG-DTA analysis of the nanoparticles indicates that the main thermal degradation occurs in the temperature range of 245–315°C. However, microparticles of Cu(OH)2 · CuCO3 decomposed endothermally in the temperature range of 230–330°C.

An effective adsorbent for removal of Pb(II) in aqueous solution was synthesized by reaction of nanoscale zero-valent iron (NZVI) and 3-aminopropyltriethoxysilane (APS). The material was characterized using transmission electron microscopy (TEM), infrared spectroscopy (IR) and a thermogravimetric analyzer (TGA). The amino-coated NZVI rapidly removed Pb(II) from aqueous solution and was easily separated by an external magnetic field. The Freundlich equation was used for investigating the adsorption process of APS-NZVI. Compared to untreated NZVI, the APS-coated NZVI exhibited stronger adsorption affinity and better adsorption performance. Therefore, APS-NZVI may be a suitable material for heavy metal remediation and has potential industrial applications.

Seasonal changes in petroleum hydrocarbons in water and streambed sediment from selected oil-related areas of Ondo State, Nigeria have been examined using gravimetric and infrared methods. The highest and lowest total petroleum hydrocarbon concentrations (TPH) in water (sediments in brackets) gravimetrically were 3.49 mg L−1 (199.3) mg kg−1 and 0.003 mg L−1 (81.0) mg kg−1 while the concentrations found by IR were 24.0 mg L−1 (135.0 mg kg−1) and 14.0 mg L−1 (33.0 mg kg−1) respectively. The two seasons were positively correlated (α = 0.01) by both methods. The TPH level was well correlated with the sediment organic carbon (OC) during both seasons. The characteristic carbonyl (C=O) vibrations at 1650 cm−1 and 1700 cm−1 indicate oxidation of the oil residue. The study recommends further investigation into the type of organics present to evaluate their toxicity and appropriate remediation.

The interaction of Procaine hydrochloride (PC) with cationic, anionic and non-ionic surfactants; cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS) and triton X-100, were investigated. The effect of ionic and non-ionic micelles on solubilization of Procaine in aqueous micellar solution of SDS, CTAB and triton X-100 were studied at pH 6.8 and 29°C using absorption spectrophotometry. By using pseudo-phase model, the partition coefficient between the bulk water and micelles, Kx, was calculated. The results showed that the micelles of CTAB enhanced the solubility of Procaine higher than SDS micelles (Kx = 96 and 166 for SDS and CTAB micelles, respectively) but triton X-100 did not enhanced the solubility of drug because of weak interaction with Procaine. From the resulting binding constant for Procaine-ionic surfactants interactions (Kb = 175 and 128 for SDS and CTAB surfactants, respectively), it was concluded that both electrostatic and hydrophobic interactions affect the interaction of surfactants with cationic procaine. Electrostatic interactions have a great role in the binding and consequently distribution of Procaine in micelle/water phases. These interactions for anionic surfactant (SDS) are higher than for cationic surfactant (CTAB). Gibbs free energy of binding and distribution of procaine between the bulk water and studied surfactant micelles were calculated.

The mechanism of interaction of hypoglycemic drugs, glimepiride and glipizide with human serum albumin (HSA) has been studied using fluorescence spectroscopy. The results are discussed in terms of the binding parameters, thermodynamics of the binding process, nature of forces involved in the interaction, identification of drug binding site on serum albumin and the fluorescence quenching mechanism involved. The association constants were of the order of 105 and glipizide was found to have much higher affinity for HSA than glimepiride at all temperatures. Thermodynamic parameters for the binding suggested that hydrophobic interactions are primarily involved in the binding of these drugs to HSA. However, glimepiride and glipizide appear to cause temperature-dependent conformational changes in the albumin molecule and, therefore, the nature of interaction varied with temperature. Glimepiride and glipizide bind to both site I and site II on HSA, but the primary interaction occurs at site II. The binding region in site II is different for the two drugs. Stern-Volmer analysis of quenching data indicated that tryptophan residues of HSA are not fully accessible to the drugs and a predominantly dynamic quenching mechanism is involved in the binding. Results can provide useful insight into prediction of competitive displacement of these drugs by other co-administered drugs and excipients, resulting in serious fluctuations of the blood glucose levels in diabetic patients.

Two novel complexes, [La(HL)(H2O)2NO3] · NO3 · H2O and [Gd(HL)(H2O)2NO3] · NO3 · H2O, where HL is a Schiff base derived from o-vanillin and lysine, have been synthesized and characterized by elemental analysis, conductivity measurements, IR, 1H NMR and thermogravimetric analyses (TGA). The Schiff base ligand behaves as a tetradentate, coordinating through azomethine nitrogen, phenolic oxygen and two carboxylic oxygen atoms. The interaction of these complexes with calf thymus DNA (CT-DNA) was also investigated by spectrometric titration and viscometric measurements. The faint hypochromism of the complexes in the absorption spectra, the remarkable reduction of fluorescence intensity of ethidium bromide (EB) bound DNA, together with a small decrease in the viscosity of the DNA suggest that a partial intercalation may be the preferred binding mode between these two complexes and DNA. The antibacterial activity testing revealed that the complexes and their precursor Schiff base show a weak to moderate activity against Bacillus subtilis, Staphylococcus aureus and Escherichia coli.

The synthesis of new 3,7-dibromophenothiazine derivatives bearing bromoalkyl, mercaptoalkyl and alkylthioacetate groups on the N atom at position 10 is reported. The Suzuki coupling reaction of one of these derivatives via the bromine atoms at positions 3 and 7 with bromothiophene derivatives is also discussed.

The degradation efficiency of Th-doped TiO2 / TiO2 photocatalysts were investigated under UV and solar light illumination. The model compound chosen for the study was Oryzalin (OZ). Doping of inner transition metal ion Th was intended to modify the electronic properties of TiO2. The Th-doped TiO2 were synthesized by incorporating 0.02, 0.04, 0.06, and 0.1 atom percentage of Th into the TiO2 lattice by solid-state reaction. The stochiometry of the prepared samples is Ti1−xThxO2, where ‘x’ is the percentage of Th. The samples were characterized by UV-Visible absorption, UV-Visible -Diffused reflectance spectra, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis (EDX) and X-ray Diffraction (XRD). The pore size and surface area of these samples were studied by Brunauer, Emmett and Teller (BET) adsorption method. It was found that metal ion doping at various percentage compositions enables a large shift in the absorption band of the TiO2 towards visible light region. This is due to the formation of various mid band gaps at 2.84 eV, 2.804 eV, 2.66 eV, and 2.55 eV. The extent of degradation of the pesticide was followed by UV-Visible spectroscopy and GC-MS methods. Based on the spectral analysis, the probable degradation reaction mechanism for OZ is proposed. These results indicate that Th-doped TiO2 with the modified electronic properties is a good catalyst under solar light irradiation. But these particles show marginal variation in rates under UV-illumination. All the photodegradation reactions follow the first order kinetics.

Aminolysis of N3P3CI6 by an oxodiamine, bis-(2-ortho-aminophenoxyethyl) ether, has been carried out under various experimental conditions and new products with different architectures have been obtained. The reaction in diethyl ether when using a Na2CO3-water interface process gives the mono-BINO as major product. Reaction on Al2O3/KOH leads to the spirocyclic compound, while, when the reaction is carried out in toluene in the presence of NEt3, a mixture of mono- and di-BINO products are obtained. These new products have been characterized by IR, 1H and 31P NMR spectroscopy.

TiO2, Fe2O3, CuO, ZnO, ZnS, Nb2O5, MoO3, CdO, CdS, Sb2O3, CeO2, HgO, Pb2O3, PbO2 and Bi2O3 microparticles exhibit band gap excitation with UV-A light but they are selective to photodegrade phenols. While TiO2 anatase and ZnO photocatalyze the degradation of phenol, o-aminophenol, m-aminophenol, p-aminophenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-nitrophenol, p-nitrophenol, o-cresol, m-cresol, p-cresol, catechol, resorcinol and quinol, MoO3 does not photodegrade any of the fifteen phenols. Fe2O3, CuO, ZnS, Nb2O5, CdO, CdS, Sb2O3, CeO2, HgO, Pb2O3, PbO2 and Bi2O3 are selective in photodegrading the fifteen phenols; however, the phenols get adsorbed over all sixteen particulate semiconductors.

In this report, we described the synthesis and characterization of a variety of diaminotriarylmethane derivatives with dimethylamino functional groups. These compounds were synthesized by the tandem regio-selective electrophilic aromatic substitution reaction of N,N-dimethylaniline with aryl aldehydes to form the corresponding diaminotriarylmethane compounds. In our strategy, Bi(NO3)3 was used as a catalyst under solvent free conditions to afford the desired products in good to excellent yields.

A simple and selective method for penicillin V potassium (PVK) determination by chemiluminescence (CL) was developed. Oxidation of PVK by alkaline hydrogen peroxide produces CL, which is greatly enhanced by N, N-dimethyl formamide (DMF) and N-cetyl-N,N,N-trimethylammonium bromide (CTMAB). Optimum conditions were established using luminometry. There is a linear relationship between the chemiluminescent peak height and the amount of PVK within the range 0.5–129.5 mg L−1, with a detection limit of 0.2 mg L−1. The coefficient of variation was 1.2% for 40 mg L−1 PVK solution (n = 7). The method is very simple, has high sensitivity and good selectivity, and is usable for process control. It was successfully utilized for the determination of PVK in pharmaceuticals and spiked human urine.

A cloud point extraction procedure for the preconcentration of copper, nickel, iron and zinc ions in various samples has been described. Analyte ions in aqueous phase are complexed with 3-((indolin-3-yl)(phenyl)methyl)indoline (IYPMI) and following centrifugation quantitatively extracted to the aqueous phase rich in Triton X-114. The surfactant-rich phase was dissolved in 2.0 mol L−1 HNO3 in methanol prior to metal content determination by flame atomic absorption spectrometry (FAAS). The effects of some parameters including, the concentrations of IYPMI, Triton X-114 and HNO3, bath temperature, centrifuge rate and time were investigated on the recoveries of analyte ions. At optimum conditions, the detection limits of (3 SDb m−1) of 1.6, 2.8, 2.1 and 1.1 ng mL−1 for Cu2+, Fe3+, Ni2+ and Zn2+ along with preconcentration factors of 30 and enrichment factor of 48, 39, 34 and 52 for Cu2+, Ni2+, Fe3+ and Zn2+ respectively, were obtained. The proposed cloud point extraction has been successfully applied for the determination of metal ions in real samples with complicated matrix such as biological, soil and blood samples with high efficiency.

Nanosized NiO2 particles with an average diameter of 15 nm are prepared by treating of Ni(NO3)2 · 6H2O with an aqueous solution of KClO in the presence of Triton® X-100. This black fine powder of nickel peroxide was characterized by XRD diffraction, energy dispersive spectroscopy (EDS) and scanning electron microscopy (SEM). The as-prepared NiO2 can be easily transformed to nanosized NiO merely by washing it with acetone. The obtained NiO has an average diameter of 40 nm and was characterized by the same means used for NiO2. The nanoparticles of NiO2 and NiO were obtained in high yields and purities.