Effect of methanol quality on the ionisation of herbicides,insecticides and fungicides using gradient elution liquid chromatography

This paper explores the changes in the electrospray signal response of 39 structurally different compounds caused by the quality of the methanol, when used as a component in a gradient elution mobile phase. When three batches of LC–MS grade methanol from one manufacturer were evaluated, the largest variation in the electrospray signal responses of the 39 compounds examined was 18%. However, significant enhancement of the electrospray signals of up to 106% were observed among different brands of LC–MS grade methanol from different manufacturers. The effect of methanol quality on signal response was found to be compound dependent. This study also demonstrated that the senescence of the methanol was important. Using an expired batch of LC–MS grade methanol, electrospray signals were suppressed by as much as 95% for all compounds measured using positive mode electrospray. Conversely, the negative mode electrospray signals of compounds such as 4-octyl benzoic acid showed an enhancement of up to 96% when using the same batch of methanol. Linuron was used as a model compound to examine the change in the electrospray response, during gradient elution, when the proportion of an expired batch of methanol was varied. An infusion experiment showed that the linuron signal intensity decreased as the proportion of expired methanol increased in the mobile phase, which was in direct contrast to the increase in linuron signal observed with a non-expired batch of methanol. A series of isocratic experiments also showed that the linuron signal decreased as the proportion of expired methanol increased in the mobile phase. The ion ratios of several of the compounds studied changed significantly when using the expired batch of LC–MS methanol. The change in the ion ratios accentuates the difficulty of identifying compounds from in-source spectral libraries. A protocol is recommended for assessing the quality of methanol for LC–MS applications.     

Synthetic and structural studies on C-ethynyl- and C-bromo-carboranes

A high-yield preparation of the C-monoethynyl para-carborane, 1-Me(3)SiC[triple bond]C-1,12-C2B10H11, from C-monocopper para-carborane and 1-bromo-2-(trimethylsilyl)ethyne, BrC[triple bond]CSiMe(3) is reported. The low-yield preparation of 1,12-(Me3SiC[triple bond]C)2-1,12-C2B10H10 from the C,C'-dicopper para-carborane derivative with 1-bromo-2-(trimethylsilyl)ethyne, BrC[triple bond]CSiMe3, has been re-investigated and other products were identified including the C-monoethynyl-carborane 1-Me3SiC[triple bond]C-1,12-C2B10H11 and two-cage assemblies generated from cage-cage couplings. The contrast in the yields of the monoethynyl and diethynyl products is due to the highly unfavourable coupling process between 1-RC[triple bond]C-12-Cu-1,12-C2B10H10 and the bromoalkyne. The ethynyl group at the cage carbon C(1) strongly influences the chemical reactivity of the cage carbon at C(12)-the first example of the "antipodal effect" affecting the syntheses of para-carborane derivatives. New two-step preparations of 1-ethynyl- and 1,12-bis(ethynyl)-para-carboranes have been developed using a more readily prepared bromoethyne, 1-bromo-3-methyl-1-butyn-3-ol, BrC[triple bond]CCMe2OH. The molecular structures of the two C-monoethynyl-carboranes, 1-RC[triple bond]C-1,12-C2B10H11 (R = H and Me3Si), were experimentally determined using gas-phase electron diffraction (GED). For R = H (R(G) = 0.053) a model with C(5v) symmetry refined to give a C[triple bond]C bond distance of 1.233(5) A. For R = Me3Si (R(G) = 0.048) a model with C(s) symmetry refined to give a C[triple bond]C bond distance of 1.227(5) A. Molecular structures of 1,12-Br2-1,12-C2B10H10, 1-HC[triple bond]C-12-Br-1,12-C2B10H10 and 1,12-(Me(3)SiC[triple bond]C)2-1,12-C2B10H10 were determined by X-ray crystallography. Substituents at the cage carbon atoms on the C2B10 cage skeleton in 1-X-12-Y-1,12-C2B10H10 derivatives invariably lengthen the cage C-B bonds. However, the subtle substituent effects on the tropical B-B bond lengths in these compounds are more complex. The molecular structures of the ethynyl-ortho-carborane, 1-HC[triple bond]C-1,2-C2B10H11 and the ethene, trans-Me3SiBrC=CSiMe3Br are also reported.     

Simultaneous determination of synthetic phosphodiesterase-5 inhibitors found in a dietary supplement and pre-mixed bulk powders for dietary supplements using high-performance liquid chromatography with diode array detection and liquid chromatography-electrospray ionization tandem mass spectrometry

A high-performance liquid chromatography-diode array detection (HPLC-DAD) method and a liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) method were developed to screen for the presence of synthetic phosphodiesterase-5 (PDE-5) inhibitors and their analogues, namely sildenafil, vardenafil, tadalafil, homosildenafil, acetildenafil and hydroxyhomosildenafil. The methods were applied to pre-market samples submitted to the Health Sciences Authority of Singapore (HSA) for testing. One sample was in the form of capsules while six other samples were pre-mixed bulk powder samples for dietary supplements to be repackaged or formulated into the final dosage forms (usually capsules). Identification of PDE-5 inhibitors and their analogues was achieved by comparing individual peak retention times, UV spectra and mass spectra with those of reference standards. The seven samples were found to contain at least one of the following compounds: sildenafil, vardenafil, hydroxyhomosildenafil, homosildenafil and acetildenafil. The five compounds were simultaneously determined by LC-ESI-MS/MS in multiple reactions monitoring (MRM) scan mode. The method has been validated for accuracy, precision, linearity and sensitivity.     

Detection of Bacillus subtilis spores using peptide-functionalized cantilever arrays

We move beyond antibody-antigen binding systems and demonstrate that short peptide ligands can be used to efficiently capture Bacillus subtilis (a simulant of Bacillus anthracis) spores in liquids. On an eight-cantilever array chip, four cantilevers were coated with binding peptide (NHFLPKV-GGGC) and the other four were coated with control peptide (LFNKHVP-GGGC) for reagentless detection of whole B. subtilis spores in liquids. The peptide-ligand-functionalized microcantilever chip was mounted onto a fluid cell filled with a B. subtilis spore suspension for approximately 40 min; a 40 nm net differential deflection was observed. Fifth-mode resonant frequency measurements were also performed before and after dipping microcantilever arrays into a static B. subtilis solution showing a substantial decrease in frequency for binding-peptide-coated microcantilevers as compared to that for control peptide cantilevers. Further confirmation was obtained by subsequent examination of the microcantilever arrays under a dark-field microscope. Applications of this technology will serve as a platform for the detection of pathogenic organisms including biowarfare agents.     

Using cross-metathesis to couple L-phenylalanine to a macrocyclic lactam

Grubbs' second generation ruthenium catalyst was used to couple the amino acid l-phenylalanine to a 17-membered lactam, using cross-metathesis with an E-alkene favored in the process. The best coupling conditions gave the product in 48% yield. The reversibility of the process was also confirmed. Ring-closing metathesis was a key reaction used to form the macrocyclic lactam.     

The electrodeposition of highly reflective lead dioxide coatings

In the presence of a suitable surfactant, such as hexadecyltrimethylammonium chloride or bromide, highly reflective and hard lead dioxide coatings with a black appearance can be electrodeposited from methanesulfonic acid media at room temperature (295 K). The reflective PbO₂ coatings are compact, adherent to the (vitreous carbon or carbon-polymer) substrate and can be formed at current densities of 10 to 100 mA cm^?2 at a thickness up to several hundred microns. The coatings were characterised by measurement of surface optical reflectance, surface roughness, surface microstructure, phase composition and crystallite size. The reflective PbO₂ films were found to mainly consist of the alpha (orthorhombic) phase with feather-like and orientated microstructures. The crystallite size and surface roughness were in the order of tens of nanometres and their optical reflectance was several orders of magnitude higher than matte coatings produced in the absence of additives.     

Structural, spectroscopic, electrochemical and computational studies of C,C′-diaryl-ortho-carboranes, 1-(4-XC6H4)-2-Ph-1,2-C2B10H10 (X = H, F, OMe, NMe2, NH2, OH and O−)

The influence of aryl ring substituents X (F, OMe, NMe₂, NH₂, OH and O⁻) on the physical and electronic structure of the ortho-carborane cage in a series of C,C′-diaryl-ortho-carboranes, 1-(4-XC₆H₄)-2-Ph-1,2-C₂B₁₀H₁₀ has been investigated by crystallographic, spectroscopic [nuclear magnetic resonance (NMR), UV–vis], electrochemical and computational methods. The cage C1–C2 bond lengths in this carborane series show small variations with the electron-donating strength of the substituent X, but there is no evidence of a fully evolved quinoid form within the aryl substituents in the ground state. In the ¹¹B and ¹³C NMR spectra, the ‘antipodal’ shift at B12, and the C1 shift correlates with the Hammett σ _p value of the substituent X. The UV–visible absorption spectra of the cluster compounds show marked differences when compared with the spectra of the analogous substituted benzenes. These spectroscopic differences are attributed to variation in contributions from the cage orbitals to the unoccupied/virtual orbitals involved in the transitions responsible for the observed absorption bands. Electrochemical studies (cyclic and square-wave voltammetry) carried out on the diarylcarborane series reveal that one-electron reduction takes place at the cage in every case with the voltage required for reduction of the cage influenced by the electron-donating strength of the substituent X, affording a series of carborane radicals with formal [2n + 3] electron counts. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synergistic Anti-Inflammatory Activity of Ginger and Turmeric Extracts in Inhibiting Lipopolysaccharide and Interferon-γ-Induced Proinflammatory Mediators

This study aims to investigate the combined anti-inflammatory activity of ginger and turmeric extracts. By comparing the activities of individual and combined extracts in lipopolysaccharide and interferon-γ-induced murine RAW 264.7 cells, we demonstrated that ginger-turmeric combination was optimal at a specific ratio (5:2, w/w) in inhibiting nitric oxide, tumour necrosis factor and interleukin 6 with synergistic interaction (combination index < 1). The synergistic inhibitory effect on TNF was confirmed in human monocyte THP-1 cells. Ginger-turmeric combination (5:2, w/w) also upregulated nuclear factor erythroid 2–related factor 2 activity and heme oxygenase-1 protein expression. Additionally, 6-shogaol, 8-shogaol, 10-shogaol and curcumin were the leading compounds in reducing major proinflammatory mediators and cytokines, and a simplified compound combination of 6-s, 10-s and curcumin showed the greatest potency in reducing LPS-induced NO production. Our study provides scientific evidence in support of the combined use of ginger and turmeric to alleviate inflammatory processes.     

Nasse Bleiproben

Ohne Zusammenfassung