Simultaneous determination of alkylphenol ethoxylates and their biotransformation products by liquid chromatography/electrospray ionisation tandem mass spectrometry

Reversed-phase LC-MS/MS is used to determine major estrogenic alkylphenol ethoxylates (APEOs) and their biotransformation products. It allows the simultaneous analysis of eight APEOs, alkylphenoxy carboxylates (APECs) and alkylphenols (APs) in sewage treatment plant (STP) effluents in the same extract after solid-phase enrichment on polymeric Oasis HLB. As precursor ions, [APEO + NH4]+, [APEC - H]- and [AP - H]- were monitored. Instrumental limits of detection (LOD) were 2-600 pg, corresponding to sample concentrations of 0.04-12 ng l(-1), without correction for overall method recoveries. Matrix-induced signal suppression during electrospray ionisation (ESI) and extraction as well as overall method recoveries were assessed and the suitability of deuterated surrogates as internal standards was evaluated.     

Darstellung von polyfluororganotrichlorsilanen

The following substances could be prepared by Grignard reactions or by conversions with trichlorosilane: C₆F₅CH₂CHCH₂, C₆F₅(CH₂)₃SiCl₃, CF₃(CF₂)₉CH₂CHCH₂, CF₃(CF₂)₇(CH₂)₂SiCl₃, CF₃(CF₂)₁₁(CH₂)₃CHCH₂ und CF₃(CF₂)₁₁(CH₂)₅SiCl₃.They were characterized by spectroscopical and microanalytical methods.     

Characterization of H2 binding sites in prototypical metal-organic frameworks by inelastic neutron scattering

The hindered rotor transitions of H(2) adsorbed in the chemically related and prototypical porous metal-organic frameworks IRMOF-1, IRMOF-8, IRMOF-11, and MOF-177 were studied by inelastic neutron scattering to gain information on the specifics of H(2) binding in this class of adsorbents. Remarkably sharp and complex spectra of these materials signify a diversity of well-defined binding sites. Similarities in the spectral features as a function of H(2) loading and correlations with recent crystallographic studies were used to assign transitions ranging in rotational barrier from <0.04 to 0.6 kcal/mol as corresponding to localized adsorption sites on the organic and inorganic components of these frameworks. We find that binding of H(2) at the inorganic cluster sites is affected by the nature of the organic link and is strongest in IRMOF-11 in accord with our adsorption isotherm data. The sites on the organic link have lower binding energies, but a much greater capacity for increases in H(2) loading, which demonstrates their importance for hydrogen uptake by these materials.     

Chemical Composition of Tagetes patula Flowers Essential Oil and Hepato-Therapeutic Effect against Carbon Tetrachloride-Induced Toxicity (In-Vivo)

The liver is a crucial organ among body organs due to its wide functions, in particular, detoxification and metabolism. Exposure to detrimental chemicals or viral infections may provoke liver dysfunction and ultimately induce liver tissue damage. Finding natural substances for liver disease treatment to overcome the conventional treatments’ side effects has attracted the attention of researchers worldwide. Our current work was conducted to investigate the hepato-therapeutic activities of essential oil (EO) isolated from Tagetes patula flowers. EO was extracted using the hydro-distillation (HD) technique and its chemical composition was identified by GC/MS. Then, the hepatic treatment potential of extracted EO was evaluated in vivo against CCL₄ in rats. HD of T. patula flowers yielded highly chemical constituents of EO along with significant antioxidant potential. A coherent molecular network was fashioned via the Global Natural Products Social Molecular Networking (GNPS) to visualize the essential components and revealed that the sesquiterpene (E)-β-caryophyllene was the most predominant volatile constituent which accounted for 24.1%. The treatment of CCL₄ led to significant induced oxidative stress markers malonaldehyde, total protein, and non-protein sulfhydryl, as well as elevated serum aminotransferase, gamma-glutamyl transferase, alkaline phosphatase, and bilirubin. In addition, it disrupted the level of lipid profile. The post-treatment using T. patula EO succeeded in relieving all toxic effects of CCl₄ and recuperating the histopathological signs induced by CCL₄. Silymarin was used as a standard hepatoprotective agent. The obtained results demonstrated that the extracted EO exerted high protective activities against the toxicity of CCL₄. Moreover, the T. patula flowers EO can be used as a natural remedy to relieve many contemporary liver diseases related to oxidative stress.     

Revisiting the S-Au(111) interaction: static or dynamic?

The Au-S interaction is probably the most intensively studied interaction of Au surfaces with nonmetals, as, for example, it plays an important role in Au ore formation(1) and controls the structure and dynamics of thiol-based self-assembled monolayers (SAMs). Various S-induced surface structures on Au(111) were recently reported for different conditions and predominantly interpreted in terms of a static Au surface. Here, we demonstrate that the Au(111) surface exhibits a very dynamic character upon interaction with adsorbed sulfur: large-scale surface restructuring and incorporation of Au atoms into a growing 2D AuS phase were observed in situ. These results provide new insight into the Au-S surface chemistry.     

Mass spectrometric characterization of lipid-modified peptides for the analysis of acylated proteins

The analysis of acylated proteins by mass spectrometry (MS) has largely been overshadowed in proteomics by the analysis of glycosylated and phosphorylated proteins; however, lipid modifications on proteins are proving to be of increasing importance in biomedical research. In order to identify the marker ions and/or neutral loss fragments that are produced upon collision-induced dissociation, providing a means to identify the common lipid modifications on proteins, peptides containing an N-terminally myristoylated glycine, a palmitoylated cysteine and a farnesylated cysteine were chemically synthesized. Matrix-assisted laser desorption/ionization time-of-flight time-of-flight (MALDI-TOF-TOF), electrospray ionization quadrupole time-of-flight (ESI Q-TOF), and electrospray ionization hybrid triple-quadrupole/linear ion trap (ESI QqQ(LIT)) mass spectrometers were used for the analysis. The peptide containing the N-terminally myristoylated glycine, upon CID, produced the characteristic fragments a1 (240.4 Th) and b1 (268.4 Th) ions as well as a low-intensity neutral loss of 210 Da (C14H26O). The peptides containing a farnesylated cysteine residue fragmented to produce a marker ion at a m/z of 205 Th (C15H25) as well as other intense farnesyl fragment ions, and a neutral loss of 204 Da (C15H24). The peptides containing a palmitoylated cysteine moiety generated neutral losses of 238 Da (C16H30O) and 272 Da (C16H32OS); however, no marker ions were produced. The neutral losses were more prominent in the MALDI-TOF-TOF spectra, whereas the marker ions were more abundant in the ESI QqQ(LIT) and Q-TOF mass spectra.     

Structure of a surfactant-templated silicate framework in the absence of 3d crystallinity

The structure of a novel molecularly ordered two-dimensional (2D) silicate framework in a surfactant-templated mesophase has been established by using a combination of solid-state nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction, and quantum chemical and empirical force-field modeling. These materials are unusual in their combination of headgroup-directed 2D crystalline framework ordering, zeolite-like ring structures within the layers, and long-range mesoscopic organization without three-dimensional (3D) atomic periodicity. The absence of registry between the silicate sheets, resulting from the liquidlike disorder of the alkyl surfactant chains, has presented significant challenges to the determination of framework structures in these and similar materials lacking 3D crystalline order. Double-quantum (29)Si NMR correlation experiments establish the interactions and connectivities between distinct intra-sheet silicon sites from which the structure of the molecularly ordered inorganic framework is determined.     

Cosmetic Formulations with Melaleuca alternifolia Essential Oil for the Improvement of Photoaged Skin: A Double-Blind,Randomized, Placebo-Controlled Clinical Study

This aim of this study was to evaluate the penetration depth, antioxidant capacity and the clinical efficacy of Melaleuca alternifolia pure essential oil and in a nanoemulsion to prevent skin photoaging. For this, 2% of pure essential oil or 2% of this essential oil in a nanoemulsion were vehiculated in a formulation. The skin penetration was evaluated using confocal Raman microspectroscopy. The radical protection factor was evaluated using electron paramagnetic resonance spectroscopy. For a clinical study, 40 male participants, aged 18–28 years, were enrolled, being divided into three groups: vehicle formulation, M. alternifolia pure essential oil and M. alternifolia Nanoemulsion. All the participants also received a sunscreen SPF 50 to use during the day. Before and after 90 days of study, skin hydrolipidics and morphological characteristics were performed by skin imaging and biophysical techniques. The nanoemulsion presented a lower antioxidant capacity and a higher penetration through the stratum corneum, reaching the viable epidermis, improving the stratum granulosum morphology. The groups presented an increase in the papillary depth, improving in the dermis echogenicity and the collagen fibers. Melaleuca alternifolia essential provides the potential to improve photoaged skin, being the application of nanoemulsion able to reach deeper skin layers.