Large changes of static electric properties induced by hydrogen bonding: an ab initio study of linear HCN oligomers

We report the partitioning of the interaction-induced static electronic dipole (hyper)polarizabilities for linear hydrogen cyanide complexes into contributions arising from various interaction energy terms. We analyzed the nonadditivities of the studied properties and used these data to predict the electric properties of an infinite chain. The interaction-induced static electric dipole properties and their nonadditivities were analyzed using an approach based on numerical differentiation of the interaction energy components estimated in an external electric field. These were obtained using the hybrid variational-perturbational interaction energy decomposition scheme, augmented with coupled-cluster calculations, with singles, doubles, and noniterative triples. Our results indicate that the interaction-induced dipole moments and polarizabilities are primarily electrostatic in nature; however, the composition of the interaction hyperpolarizabilities is much more complex. The overlap effects substantially quench the contributions due to electrostatic interactions, and therefore, the major components are due to the induction and exchange-induction terms, as well as the intramolecular electron-correlation corrections. A particularly intriguing observation is that the interaction first hyperpolarizability in the studied systems not only is much larger than the corresponding sum of monomer properties, but also has the opposite sign. We show that this effect can be viewed as a direct consequence of hydrogen-bonding interactions that lead to a decrease of the hyperpolarizability of the proton acceptor and an increase of the hyperpolarizability of the proton donor. In the case of the first hyperpolarizability, we also observed the largest nonadditivity of interaction properties (nearly 17%) which further enhances the effects of pairwise interactions.     

Potentials of the D¹0u⁺ (6¹S₀) and F³1u(6³P₂) electronic Rydberg states of Cd₂ from ab initio calculations and laser-induced fluorescence excitation spectra

The method of supersonic free-jet expansion beam combined with techniques of laser spectroscopy was used in an investigation of vibronic and isotopic structures in the D10(u)? (61S?) and F31(u)(63P?) electronic energy Rydberg states of Cd?. Laser-induced fluorescence excitation spectra recorded using the D10(u)? ← X10(g)?(51S?) and F31(u) ← X10(g)? transitions in the region of 206-218 nm provided spectroscopic characteristics of the excited states and allowed constructing of their intratomic potentials. Isotopic structures recorded in the (υ',υ') bands of the D10(u)? ← X10(g)? transition were used in determination of the D10(u)? state vibrational characteristics (ω'(e)x'(e), ω'(e)x'(e)) and υ' assignment. The ν(0,0) recorded directly in the F31(u) ← X10(g)? transition enabled determination of the bottom of the F31(u) state potential well. Valence ab initio calculations of Cd? interatomic potentials were performed with relativistic and spin-orbit effects taken into account. The experimental results were compared with results of the ab initio calculations. A free-jet expansion of Cd? as a source of entangled atoms for a test of Bell's inequality was analyzed.     

Assessment of ion imprinted polymers based on Pd(II) chelate complexes for preconcentration and FAAS determination of palladium

New ion-imprinted polymeric (IIP) materials were synthesized by copolymerization of 4-vinylpyridine (VP) and styrene as functional monomers and divinylbenzene as a cross-linking agent with chelating complexes of Pd(II) in the presence of 2,2-azobisisobutyronitrile as an initiator. The complexes of Pd(II) with ammonium pyrrolidinedithiocarbamate (APDC), N,N′-diethylthiourea (DET), and dimethylglyoxime (DMG) were used for this purpose. Chloroform, ethanol, and cyclohexanol were applied as porogens. The ion-imprinted polymers were tested in a flow mode as sorbents for solid-phase extraction of palladium from aqueous solutions. The conditions of Pd(II) separation on all polymers were optimized. The efficiencies of retention of Pd on different polymers in the presence of high excess of interfering ions were compared. The effect of the used porogen on the analytical performance of the prepared polymers was also investigated. The calculated sorbent capacities for Pd(II) were in the range from 9.25 mg g⁻¹ to 13.3 mg g⁻¹. The sorbent with Pd(II) imprinted as Pd-DMG-VP complex in chloroform was used for preconcentration of trace amounts of Pd. The detection limit for 100 mL of the sample was 5 μg L⁻¹ using flame atomic absorption spectrometry (FAAS). The developed method was applied for the determination of Pd in water samples.     

Electronic and vibrational contributions to first hyperpolarizability of donor-acceptor-substituted azobenzene

In this study we report on the electronic and vibrational (hyper)polarizabilities of donor-acceptor-substituted azobenzene. It is observed that both electronic and vibrational contributions to the electric dipole first hyperpolarizability of investigated photoactive molecule substantially depend on the conformation. The contributions to the nuclear relaxation first hyperpolarizability are found to be quite important in the case of two considered isomers (cis and trans). Although the double-harmonic term is found to be the largest in terms of magnitude, it is shown that the total value of the nuclear relaxation contribution to vibrational first hyperpolarizability is a result of subtle interplay of higher-order contributions. As a part of the study, we also assess the performance of long-range-corrected density functional theory in determining vibrational contributions to electric dipole (hyper)polarizabilities. In most cases, the applied long-range-corrected exchange-correlation potentials amend the drawbacks of their conventional counterparts.     

Thermal denaturation of mixtures of human serum proteins

Differential scanning calorimetry (DSC) has been employed to study the thermal denaturation processes of the main protein fractions of blood serum. These processes have been compared for albumins (nondefatted (HSA) and fatty acid free (HSAf)), α,β-globulins, γ-globulins, and their mixtures in aqueous (pH 6.5) and buffer (pH 7.2) solutions. The results have indicated that α,β-globulins inhibit γ-globulins’ aggregation in buffer solutions. The decrease of stability of HSA and HSAf aqueous solutions has been observed in the presence of γ-globulins. The mixtures of albumins and γ-globulins have revealed the tendency to ready aggregation in water. Moreover, the results have suggested that neither γ-globulins nor albumins severely change the stability of α,β-globulins.     

Application of DLLME to Isolation and Concentration of Non-Steroidal Anti-Inflammatory Drugs in Environmental Water Samples

Dispersive liquid–liquid microextraction (DLLME) coupled with liquid chromatography-tandem mass spectrometry detection was applied for determination of selected anti-inflammatory pharmaceuticals: ibuprofen, ketoprofen, naproxen and diclofenac. Development of DLLME procedure included optimisation of several important parameters such as kind and volume of extracting and dispersive solvents as well as sample pH. Under optimised conditions a two-step extraction with sonication was used. Chloroform was applied as the extracting and acetone as dispersing solvent. Calibration curves ranges were 1–500 μg L^?1 for naproxen and ibuprofen and 0.25–500 μg L^?1 for ketoprofen and diclofenac with correlation coefficients at least 0.997. Limits of quantitation were from 0.5 to 10 ng L^?1. The developed analytical method was employed for determination of ibubrofen, ketoprofen, naproxen and diclofenac in river and tap water samples. The results showed that DLLME is a simple, rapid and sensitive analytical technique for the pre-concentration of trace amounts of pharmaceuticals in environmental water samples.     

Selectivity in normal-phase liquid chromatography with binary mobile phase

A simple theoretical approach to normal-phase liquid chromatography with binary mobile phase is presented. In the model used the driving force for the retention is competitive adsorption of solutes and both solvents. A new expression for the separation factor is proposed and discussed. An influence of different parameters on the selectivity is shown. The theoretical concepts are illustrated by the selected experimental data.     

Influence of solution pH on stability of aluminum oxide suspension in presence of polyacrylic acid

The effect of solution pH and molecular weight of polyacrylic acid (PAA) on its adsorption as well as on stabilization-floculation properties of the colloidal Al₂O₃ and electrolyte solution systems was studied. The measurements showed that at pH = 6, the presence of the polymer of molecular weight 2?000 and 240?000 does not change stability of Al₂O₃ suspension. However at pH =3 and 9 the effect of polyacrylic acid is significant. At pH = 3 it creates destabilization of the suspension while at pH = 9 PAA it improves significantly the stability of Al₂O₃. It was shown that the increase in solution pH affects conformation of adsorbed macromolecules which causes the decrease in PAA adsorbed amount and thickness of polymer adsorption layer. By comparing the values of diffusion layer and surface charges, main effects responsible for the decrease in surface charge and ζ potential of the solid in the presence of the polymer as well as suspension stability were determined.     

Current trends in solid-phase microextraction (SPME) fibre coatings

This critical review presents information on known and innovative approaches to the manufacture of fibre coatings used in solid-phase microextraction (SPME). The properties, advantages and drawbacks of the different types of commercially available SPME fibre coatings are discussed in detail, as are those of novel types of coatings and the methodologies of their preparation. The applications of fibre coatings in the solid-phase microextraction of a broad spectrum of analytes are analysed, with particular emphasis on the sampling of polar analytes from polar matrices (174 references).