Differentiation between o- and p-quinol/quinone functionality with a simple test using cyclic voltammetry

Complexation with boric acid combined with cyclic voltammetry serves to prove theo-quinol/quinone functionality in emmotin H (1) and I (2). Supported by similar investigation of four reference compounds the method is suggested as a quick and reliable test ofo-quinol/quinone functionality and for differentiation fromp-quinol/quinone functionality. Voluminous groups such as 2-isopropanolyl ino-position do not interfere with the complex formation. The test requires quantities of materials in the order of 10 to 100g.     

Optimisation of the quantitative determination of chlormequat by matrix-assisted laser desorption/ionisation mass spectrometry

The plant growth regulator chlormequat, an involatile quaternary ammonium salt, has been quantified by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS). Restrictions for quantitative MALDI-TOFMS analysis, such as irreproducible crystallisation and unsatisfactory laser stability, have been overcome by the application of two synthesised isotopically labelled standards and the optimisation of the measurement protocol. Data acquisition at constant laser power was compared to data acquisition at approximately constant ion abundance of the relevant ions (analyte and internal standards). Data acquisition at constant ion abundance performed better and enabled a high number of consecutive firings to the same sample deposition area. Furthermore an increased sample-to-sample repeatability and a high reproducibility over several weeks without re-calibration have been attained by this method. Linearity over three orders of magnitude (0.05 to 30 ng/microL chlormequat), with a correlation coefficient of 0.9997, was achieved using [13C3]-chlormequat as internal standard. Limit of detection and limit of determination were determined to be in the low pg/microL range for pure standard solutions. Thin-layer chromatography was applied for the removal of high amounts of choline, which is often present in plant tissue extracts and can adversely affect the ionisation and detection of chlormequat by MALDI-TOFMS. The use of two internal standards ([13C3]- and [2H9]-chlormequat) enabled direct quantification and simultaneous control of the recovery.     

Syndiospecific polymerization of styrene. II. Monocyclopentadienyltributoxy titanium/methylaluminoxane catalyst

Syndiospecific polymerization of styrene was catalyzed by monocyclopentadienyltributoxy titanium/methylaluminoxane [CpTi (OBu)₃/MAO]. The atactic and syndiotactic polystyrenes were separated by extracting the former with refluxing 2-butanone. The activity and syndiospecificity of the catalyst were affected by changes in catalyst concentration and composition, polymerization temperature, and monomer concentration. Extremely high activity of 5 × 10⁷ g PS (mol Ti mol S h)^?1 with 99% yield of the syndiotactic product were achieved. The concentration of active species, [C^*], has been determined by radiolabeling. The amount of the syndiospecific and nonspecific catalytic species, [C] and [C] respectively, correspond to 79 and 13% of the CpTi(OBu)₃. The rate constants of propagation for C and C at 45°C are 10.8 and 2.0 (M s)^?1, respectively, the corresponding rate constants for chain transfer to MAO are 6.2 × 10^?4 and 4.3 × 10^?4s^?1. There was no deactivation of the catalytic species during a batch polymerization. The rate constant of chain transfer with monomer is 6.7 × 10^?2 (M s)^?1; the spontaneous β-hydride transfer rate constant is 4.7 × 10^?2 s^?1. The polymerization activity and stereospecificity of the catalyst are highest at 45°C, both decreasing with either higher or lower temperature. The stereoregular polymer have broad MW distributions, M?_w/M?_n = 2.8–5.7, and up to three crystalline modifications. The T_m of the s-PS polymerized at 0–90°C decreased from 261.8 to 241°C indicating thermally activated monomer insertion errors. The styrene polymerization behaviors were essentially insensitive to the dielectric constant of the medium.     

Comprehensive reversed-phase×chiral two-dimensional liquid chromatography coupled to quadrupole-time-of-flight tandem mass spectrometry with post-first dimension flow splitting for untargeted enantioselective amino acid analysis

This work describes a comprehensive achiral × chiral two-dimensional liquid chromatography separation for enantioselective amino acid analysis coupled to electrospray ionization-tandem mass spectrometry detection using data-independent acquisition. Flow splitting after the first and second dimension separation was utilized for volumetric flow reduction and for enabling a multi-detector approach (with ultraviolet, fluorescence, charged aerosol, and MS detection), respectively. Derivatization with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate provided a chromophore, a fluorophore, and an efficient mass tag for efficient ionization in positive electrospray ionization-mass spectrometry. Chiral columns often have limitations in terms of their chemoselectivity, which may be a problem when complex sample mixtures with structurally related compounds need to be separated. It can be alleviated by a reversed-phase×chiral two-dimensional-liquid chromatography setup, in which the first dimension provides the chemoselectivity and a chiral tandem column constituted of quinine-carbamate derived weak anion-exchanger and zwitterionic ion-exchanger in the second dimension separation of D- and L-amino acid enantiomers. The method was used to control the stereointegrity of the therapeutic peptide octreotide. After hydrolysis, all amino acid constituents were detected with the correct configuration and composition. Some options for flow splitting and integration of destructive detectors in the first dimension separation are outlined.     

Metal Phosphorous Trichalcogenides (MPCh3): From Synthesis to Contemporary Energy Challenges

Owing to their unique physical and chemical properties, layered two‐dimensional (2D) materials have been established as the most significant topic in materials science for the current decade. This includes layers comprising mono‐element (graphene, phosphorene), di‐element (metal dichalcogenides), and even multi‐element. A distinctive class of 2D layered materials is the metal phosphorous trichalcogenides (MPCh₃, Ch=S, Se), first synthesized in the late 1800s. Having an unusual intercalation behavior, MPCh₃ were intensively studied in the 1970s for their magnetic properties and as secondary electrodes in lithium batteries, but fell from scrutiny until very recently, being 2D nanomaterials. Based on their synthesis and most significant properties, the present surge of reports related to water‐splitting catalysis and energy storage are discussed in detail. This Minireview is intended as a baseline for the anticipated new wave of researchers who aim to explore these 2D layered materials for their electrochemical energy applications.     

Mass spectral studies of perfluorooctane sulfonate derivatives separated by high-resolution gas chromatography

The mass spectral characteristics of perfluorooctane sulfonate (PFOS, C(8)F(17)SO(3)-) isomers present in technical PFOS were obtained using high-resolution gas chromatography (HRGC) combined with mass spectrometry (MS). To make PFOS amenable to HRGC separation, a simple derivatization procedure was developed. The method involved the conversion of PFOS into the iso-propyl ester using iso-propanol as the derivatization reagent under acidic conditions. Mass spectra were generated employing electron ionization (EI) and negative chemical ionization (NCI). Interpretation of fragment ions was possible due to the use of deuterium-labeled iso-propanol as derivatization reagent, which induced mass shifts in the electron ionization (EI) and negative chemical ionization (NCI) mass spectra. HRMS allowed the accurate mass measurement of important EI fragments and confirmed the derivatization reaction as well as the proposed fragmentation pathway involving rearrangement. Moreover, the high resolution provided by HRGC enabled the separation of eleven PFOS isomers present in the technical product. This is an improvement over the previously reported high-performance liquid chromatography (HPLC) separation. A complete identification of all isomers was not possible due to lack of pure reference materials. Finally, the developed derivatization procedure was successfully applied to perfluoroalkyl carboxylates (PFCA) and corresponding fragmentation involving rearrangement of the derivatized PFCA was observed. The described qualitative derivatization offers a promising alternative technique for the separation and identification of isomers of perfluoroalkyl sulfonates and carboxylates by HRGC/MS.     

Vanadocene(IV) dicyanide complexes: the evidence super-hyperfine coupling for compounds with 13CN ligands

An EPR study of the vanadocene complexes (C(5)H(5))2V(CN)2 and (CH(3)C(5)H(4))2V(CN)2 was carried out. Such compounds show strong super-hyperfine coupling (|a(iso)(13C)| approximately 1.27 mT) when 13C labeled cyanide is used for their preparation. Super-hyperfine splitting was observed in the isotropic spectra of solution samples as well as in the anisotropic spectra of frozen solutions. Such studies were supplemented with structural characterization of the parent compounds. Molecular structure of the complex (CH(3)C(5)H(4))2V(CN)2 was determined by single-crystal X-ray diffraction analysis. Both compounds were characterized by infrared and Raman spectroscopy.     

Estrogen-induced cholestasis results in a dramatic increase of b-series gangliosides in the rat liver

Hepatic ganglioside composition was investigated in normal and cholestatic Wistar rats. Cholestasis was induced by 17alpha-ethinylestradiol (EE; 5 mg/kg body weight s.c. for 18 days). As compared with controls, the EE administration resulted in severe cholestasis, as indicated by biochemical as well as morphological signs. Gangliosides isolated from the liver tissue were separated by TLC, with resorcinol-HCl detection and densitometric evaluation. As compared with controls, the total hepatic lipid sialic acid content in cholestatic rats was increased almost 2-fold (44.3 +/- 15.2 vs 79.1 +/- 9.0 nmol/g wet weight of liver tissue, p < 0.01). This increase was primarily due to the increase of ganglioside GD1a (3.6 +/- 1.0 vs 11.8 +/- 3.0 nmol/g wet weight of liver tissue, p = 0.001), as well as to the enormous up-regulation of b-series gangliosides GD3 (0.08 +/- 0.03 vs 2.0 +/- 1.2 nmol/g wet weight of liver tissue, p = 0.002), GD1b (0.1 +/- 0.06 vs 5.4 +/- 1.6 nmol/g wet weight of liver tissue, p = 0.002) and GT1b (0.06 +/- 0.03 vs 6.4 +/- 2.6 nmol/g wet weight of liver tissue, p = 0.002). As the majority of gangliosides are concentrated in cell membranes, our findings suggest that dramatic increase of b-series gangliosides might contribute to the protection of hepatocytes against the deleterious effects of cholestasis.     

ChemInform Abstract: Structural Properties and Singular Phase Transitions of Metallic Pr0.50Sr0.50CoO3 Cobaltite.

Two successive magnetic transitions of Pr_0.50Sr_0.50CoO₃ contrast with the single ferromagnetic transition in other Ln_0.50Sr_0.50CoO₃ compounds.