H-bonded complexes of aniline with HF/F- and anilide with HF in terms of symmetry-adapted perturbation, atoms in molecules, and natural bond orbitals theories

The hydrogen-bonded isoelectronic complexes of aniline with HF/F- and an ionic form of aniline with HF were investigated by use of computational methods: Symmetry-Adapted Perturbation Theory (SAPT), Atoms in Molecules (AIM), and Natural Bond Orbitals (NBO) approaches. All computations were based on structural models previously generated at the B3LYP/6-311+(d,p) level. The differences between neutral (Ph-NH2...HF)and anionic (Ph-NH2...F- and Ph-NH-...HF) complexes were clearly outlined. The discussed charged complexes serve as Lewis acids and base, HF and F-, respectively. It was found that electrostatic and induction energy terms, obtained as a result of the SAPT method, are most dependent on the type of H-bonding (i.e.,charged or neutral). The electrostatic term is the most distinctive between the neutral and charge-assisted hydrogen bonds in the investigated two-body systems, whereas the latter is more significant in the case of weaker interactions (larger H...B distances). Application of Principal Component Analysis (PCA) to energy components obtained from the SAPT procedure indicated that all of them are relatively well intercorrelated.The above-mentioned terms together with the exchange energy terms are the most important contributions ofthe main principal component, which describes 95% of the total variance. Comparison of AIM parameters in bond critical points for modeled H-bond systems shows a good agreement with those from equilibrium complexes, both experimental and calculated ones. It was found that charged H-bonded complexes exhibit larger fluctuation of electron density and its Laplacian in bond critical points, in line with SAPT analysis. NBO results confirmed the effect of the strength of interaction on property changes both in the region of H-bonding and outside of it. The latter, more distant consequences follow the Bent-Walsh rule for all studied complexes.     

Numerical analysis of the Gran methods. A comparative study

The paper concerns mainly the modified Gran methods, considered as extrapolative standard addition methods. Particularly, the approximation:

     

LC and Principal Component Analysis in the Lipophilicity Study of Seven Angiotensin II-AT1 Receptor Antagonists (Sartans)

Seven sartans have been chromatographed with acetonitrile-buffer and methanol–buffer in different proportions as mobile phases. The retention values, log k or R _M were extrapolated to zero organic modifier content to obtain the log k _w or R _MW values. Calibration equations were obtained for standards of known lipophilicity. A simple method employing a gradient procedure of 10–100% acetonitrile or methanol in 60 min and standards of the extreme lipophilicity was also elaborated. Chromatographic log P values were compared to those calculated by use of different software products. Finally, principal component analysis was performed to explore and visualize similarities and differences among the drugs and among the methods.     

Lanthanide complexes of the heterochiral nonaaza macrocycle: switching the orientation of the helix axis

The La(III), Ce(III), Pr(III), Nd(III), Sm(III), and Eu(III) complexes of the racemic heterochiral nonaaza macrocyclic amine L have been synthesized and characterized by spectroscopic methods. The X-ray crystal structures of the [PrL][Pr(NO(3))(6)].CH(3)OH and the isomorphic [NdL][Nd(NO(3))(6)].CH(3)OH complexes show that all nine nitrogen atoms of the macrocycle coordinate to the Ln(3+) ion, completing its coordination sphere. The macrocycle wraps tightly around the metal ion in double-helical fashion. The structures reveal the RRRRSS/SSSSRR configuration at the stereogenic carbon atoms of the three cyclohexane rings, confirming the heterochiral nature of the parent 3 + 3 macrocycle obtained in the condensation of racemic trans-1,2-diaminocyclohexane and 2,6-diformylpyridine. The NMR spectra of the isolated complexes indicate the presence of low C(1) symmetry [LnL](3+) complexes. The same symmetry is indicated by the X-ray crystal structures of Pr(III) and Nd(III) complexes, which show that for the RRRRSS enantiomer of the macrocycle L, the helix axis passes through the cyclohexane ring of RR chirality and the opposite pyridine ring. The NMR studies of complex formation in solution by the paramagnetic Pr(3+) and Eu(3+) ions indicate that the initially formed [LnL](3+) complexes are of C(2) symmetry. For the RRRRSS enantiomer of the macrocycle L in the C(2)-symmetric species, the helix axis passes through the cyclohexane ring of SS chirality and the opposite pyridine ring. The C(1)-symmetric and C(2)-symmetric forms of the [LnL](3+) complexes constitute a new kind of isomers and the conversion of the kinetic complexation product of C(2) symmetry into the thermodynamic product of C(1) symmetry corresponds to an unprecedented switching of the orientation of the helix axis within the macrocycle framework.     

Extending the coordination chemistry of 1,3,5-triaza-7-phosphaadamantane (PTA) to cobalt centers: first examples of co-PTA complexes and of a metal complex with the PTA oxide ligand

Water-soluble Co (III) and Co (II) complexes with P- or N-coordinated PTA or PTA oxide ligands, respectively, have been prepared and fully characterized, constituting the first examples of cobalt compounds bearing PTA or any ligand with a cage-like PTA core, the latter complex providing also the first PTA oxide coordination to a metal center.     

Identification and determination of triterpenoids in Hieracium pilosella L

Fractions of triterpenoids have been isolated from herb, inflorescences, and rhizomes with roots of Hieracium pilosella by typical extraction with petroleum ether. The fraction from inflorescences was investigated using GC-MS techniques. The occurrence of alpha- and beta-amyrin, taraxerol, taraxasterol, and fern-7en-3beta-ol has been observed. Quantitative analysis was also performed and taraxasterol is distinctly predominant in this triterpenoid fraction. Thin-layer chromatography on silica gel was performed on all the investigated fractions and additionally revealed the occurrence of lupeol and psi-taraxasterol in vestigial quantities. All of the triterpenoid components are reported for the first time in the investigated plant.     

Improving the universal response of evaporative light scattering detection by mobile phase compensation

Mobile phase compensation, first reported for the charged aerosol detector (CAD), was used as a suitable method to overcome problems related to the mobile phase-dependent response of the evaporative light scattering detector (ELSD). Mobile phase compensation was effectively performed both in the flow injection- and in gradient modes. Without compensation, the response factors of the ELSD for six sulfonamide drugs differed by a factor of two when varying the mobile phase composition between 10 and 90% acetonitrile. This change could be effectively eliminated using the technique of mobile phase compensation, where a secondary pump with a reversed gradient was used to provide the detector with a constant composition of the mobile phase. For identical experimental conditions, the ELSD showed a nearly constant, albeit somewhat reduced, response with compensation. This indicates that under such conditions, the ELSD behaved as a concentration-sensitive detector. The analysis of sulfonamides drugs at 0.05% level using gradient UPLC-ELSD separation with mobile phase compensation is demonstrated.     

Determination of polydimethylsiloxane-air partition coefficients using headspace sorptive extraction

Polydimethylsiloxane-air partition coefficients (K(PDMS-A)) were determined using direct headspace analysis and headspace sorptive extraction (HSSE) with polydimethylsiloxane-coated (PDMS) stir bars. The partition coefficients were investigated for three compounds, p-dichlorobenzene (PDCB), naphthalene and camphor, all of which sublimate at room temperature and find use as moth repellents. In order to determine the K(PDMS-A) values of these compounds, the air concentration and the concentration present on PDMS, both at equilibrium, were measured. The results indicate that PDMS-air partition coefficients are proportional to octanol-air partition coefficients. Thus, the latter could be used to estimate the extraction efficiency of PDMS for these compounds in air. Alternatively, octanol-air partition coefficients for organic compounds could be estimated from the PDMS-air partition coefficient values. As expected, the PDMS-air (or octanol-air) partition coefficient increased with decreasing temperature. Importantly, the partition coefficients determined at saturated vapor pressures were lower than the values determined at lower analyte concentrations, with the differences being greater for compounds with larger partition coefficients. Consequently, caution should be exercised when applying K(PDMS-A) values determined at high analyte concentrations to measurements at lower concentrations, especially when the partition coefficients are large.     

Dioxadiazuliporphyrin: a near-IR redox switchable chromophore

The synthesis of dioxadiazuliporphyrinogen 7 and its oxidized forms: dioxadiazuliporphyrin 8 and dication 8(2+), is reported. These compounds were characterized in solution using UV-vis and 1H and 13C NMR spectroscopic means and in the solid state via single-crystal X-ray diffraction analysis. Dioxadiazuliporphyrin is a nonaromatic porphyrinoid, readily and reversibly oxidizable to its cation radical and to the aromatic carbaporphyrinoid dication, which can be viewed as a 21,23-dicarba-22,24-dioxaporphyrin with two fused tropylium rings. Further insight into the geometric and magnetic manifestations of aromaticity and antiaromaticity in the case of the redox couple 8, 8(2+) is obtained using density functional calculations and nucleus-independent chemical shifts.     

Photobleaching of melanosomes from retinal pigment epithelium: II. Effects on the response of living cells to photic stress

Melanosomes of the retinal pigment epithelium (RPE) are long lived organelles that may undergo photobleaching with aging, which can diminish the antioxidant efficiency of melanin. Here, isolated porcine RPE melanosomes were experimentally photobleached with visible light to simulate aging and compared with untreated granules or control particles (black latex beads) for their effects on the survival of photically stressed ARPE-19 cultures. Particles were delivered to cultures for uptake by phagocytosis then cells were exposed to violet light and analyzed by a new live cell imaging method to identify the time of apoptotic blebbing as a dynamic measure of reduced cell survival. Results indicated that untreated melanosomes did not decrease photic injury to ARPE-19 cells when compared with cells lacking particles or with cells containing control particles, as might be expected if melanin performed an antioxidant function. Instead cells with untreated melanosomes showed reduced survival indicated by an earlier onset of blebbing and a lower fraction of surviving cells after photic stress. Cell survival was reduced even further in stressed cells containing melanosomes that were photobleached, and survival decreased with increasing photobleaching time. Photobleaching of RPE melanosomes therefore makes cells containing them more sensitive to light-induced cytotoxicity. This observation raises the possibility that aged melanosomes increase RPE cell photic stress in situ, perhaps contributing to reduced tissue function and to degeneration of the adjacent retina that the RPE supports. How melanosomes (photobleached or not) interact with their local subcellular environment to modify RPE cell survival is poorly understood and is likely determined by the physicochemical state of the granule and its constituent melanin. The live cell imaging method introduced here, which permitted detection of a graded effect of photobleaching, provides a sensitive bioassay for probing the effects of melanosome modifications.