Antiphytopathogenic activity of Psoralea glandulosa (Fabaceae) against Botrytis cinerea and Phytophthora cinnamomi

The resinous exudate, three meroterpenes, namely bakuchiol (1), 3-hydroxybakuchiol (2), 12-hydroxyisobakuchiol (3), and one furanocoumarin, psoralen (4), were isolated from the leaves of culen (Psoralea glandulosa). In addition to these, two semi-synthetic derivatives, bakuchiol acetate (5) and bakuchiol methyl eter (6), were obtained from 1, and were subsequently evaluated in vitro for the inhibitory effect of resin and compounds on the mycelial growth of Botrytis cinerea Pers.: Fr. and Phytophthora cinnamomi Rands. The resinous exudate inhibited the mycelial growth of both the pathogens, while bakuchiol (1) exhibited an inhibitory effect on the mycelial growth of B. cinerea up to 94% at a concentration of 150 mg/L and psoralen (4) reduced the mycelial growth of P. cinnamomi up to 80% at a concentration of 150 mg/L. These compounds have the ability of blocking the development of mycelial growth and may be used as a potential biopesticide in the agricultural sector once the in vivo test results have been validated.     

Study of the distribution of actinides in human tissues using synchrotron radiation micro X-ray fluorescence spectrometry

This study aims at evaluating the capabilities of synchrotron radiation micro X-ray fluorescence spectrometry (SR micro-XRF) for qualitative and semi-quantitative elemental mapping of the distribution of actinides in human tissues originating from individuals with documented occupational exposure. The investigated lymph node tissues were provided by the United States Transuranium and Uranium Registries (USTUR) and were analyzed following appropriate sample pre-treatment. Semi-quantitative results were obtained via calibration by external standards and demonstrated that the uranium concentration level in the detected actinide hot spots reaches more than 100 μg/g. For the plutonium hot spots, concentration levels up to 31 μg/g were found. As illustrated by this case study on these unique samples, SR micro-XRF has a high potential for this type of elemental bio-imaging owing to its high sensitivity, high spatial resolution, and non-destructive character.

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Graphical Abstract SR micro-XRF study of the distribution of actinitides in human tissues. Left Location of the U-contaminated tissue sample in the human body. Middle U distribution derived from the high resolution SR micro-XRF scan on the tissue sample, indication of five U hot spots. Right Detail of the point measurement spectrum of U hot spot 3, intense U-L_α fluorescence peak located at 13.6 keV.

     

Extreme red shifted SERS nanotags

Surfaced enhanced Raman scattering (SERS) nanotags operating with 1280 nm excitation were constructed from reporter molecules selected from a library of 14 chalcogenopyrylium dyes containing phenyl, 2-thienyl, and 2-selenophenyl substituents and a surface of hollow gold nanoshells (HGNs). These 1280 SERS nanotags are unique as they have multiple chalcogen atoms available which allow them to adsorb strongly onto the gold surface of the HGN thus producing exceptional SERS signals at this long excitation wavelength. Picomolar limits of detection (LOD) were observed and individual reporters of the library were identified by principal component analysis and classified according to their unique structure and SERS spectra.     

Characterization of sugarcane bagasse by autofluorescence microscopy

The spatial distribution of chemical compounds in sugarcane bagasse is an important issue in its use as a raw material for second generation ethanol production from cellulose hydrolysis. Lignocellulosic materials including whole bagasse, fiber, pith, and respective samples obtained after chemical bleaching were investigated using confocal fluorescence microscopy and spectroscopy with one and two-photon excitation. Autofluorescence from unbleached samples revealed that emission from fiber walls containing the lignin fraction was longitudinally oriented. After bleaching treatment, the oriented emission was partially disrupted. Autofluorescence from bleached samples with a residual lignin content of about 1 % was ascribed to improved dispersion of remaining fluorophores throughout the samples inducing a concomitant reduction of fluorescence self-quenching in the samples. The combination of autofluorescence images with spectral emission and lifetime measurements provides a tool for microscopic characterization of natural bagasse samples. Moreover, the technique allows monitoring bleaching processes related to lignin removal.     

Quantification of myo‐inositol, 1,5‐anhydro‐ D‐sorbitol,and D‐chiro‐inositol using high‐performance liquid chromatography with electrochemical detection in very small volume clinical samples

Inositol is a six‐carbon sugar alcohol and is one of nine biologically significant isomers of hexahydroxycyclohexane. Myo‐inositol is the primary biologically active form and is present in higher concentrations in the fetus and newborn than in adults. It is currently being examined for the prevention of retinopathy of prematurity in newborn preterm infants. A robust method for quantifying myo‐inositol (MI), D ‐chiro‐inositol (DCI) and 1,5‐anhydro‐ D ‐sorbitol (ADS) in very small‐volume (25 μL) urine, blood serum and/or plasma samples was developed. Using a multiple‐column, multiple mobile phase liquid chromatographic system with electrochemical detection, the method was validated with respect to (a) selectivity, (b) accuracy/recovery, (c) precision/reproducibility, (d) sensitivity, (e) stability and (f) ruggedness. The standard curve was linear and ranged from 0.5 to 30 mg/L for each of the three analytes. Above‐mentioned performance measures were within acceptable limits described in the Food and Drug Administration's Guidance for Industry: Bioanalytical Method Validation. The method was validated using blood serum and plasma collected using four common anticoagulants, and also by quantifying the accuracy and sensitivity of MI measured in simulated urine samples recovered from preterm infant diaper systems. The method performs satisfactorily measuring the three most common inositol isomers on 25 μL clinical samples of serum, plasma, milk, and/or urine. Similar performance is seen testing larger volume samples of infant formulas and infant formula ingredients. MI, ADS and DCI may be accurately tested in urine samples collected from five different preterm infant diapers if the urine volume is greater than 2–5 mL. Copyright © 2015 John Wiley & Sons, Ltd.     

Analysis of trifluoroacetic acid and other short-chain perfluorinated acids (C2-C4) in precipitation by liquid chromatography-tandem mass spectrometry: comparison to patterns of long-chain perfluorinated acids (C5-C18)

This paper provides analytical chemical information on selected new molecular entities (NMEs) which are drugs that have recently been approved by the FDA. These are the antiretroviral drugs, atazanavir, indinavir and emtricitabine, the antibacterial gemifloxacin, rosuvastatine which is a cholesterol-lowing drug, the anti-cancer drug gefitinib and aprepitant for neurological disorders. Electrospray ionisation-quadrupole ion trap mass spectrometry (ESI-MSⁿ) was employed to generate tandem mass spectrometric (MS²) data of the drugs studied and structural assignments of product ions were supported by quadrupole time-of-flight mass spectrometry (QToF-MS/MS). These fragmentation studies were then utilised in the development and validation of a specific and sensitive liquid chromatographic method (LC–ESI-MS²) to identify and determine these drugs at therapeutic concentration levels in serum after a single protein precipitation procedure with acetonitrile. In addition, this method was compared to the application of gas liquid chromatography-flame ionisation detection (GLC-FID) and differential pulse polarography (DPP) for the analysis of these NMEs in serum.     

Investigation of the hybrid molecular probe for intracellular studies

Monitoring gene expression in vivo is essential to the advancement of biological studies, medical diagnostics, and drug discovery. Adding to major efforts in developing molecular probes for mRNA monitoring, we have recently developed an alternative tool, the hybrid molecular probe (HMP). To optimize the probe, a series of experiments were performed to study the properties of HMP hybridization kinetics and stability. The results demonstrated the potential of the HMP as a prospective tool for use in both hybridization studies and in vitro and in vivo analyses. The HMP has shown no tendency to produce false positive signals, which is a major concern for living cell studies. Moreover, HMP has shown the ability to detect the mRNA expression of different genes inside single cells from both basal and stimulated genes. As an effective alternative to conventional molecular probes, the proven sensitivity, simplicity, and stability of HMPs show promise for their use in monitoring mRNA expression in living cells. Figure Hybrid molecular probe (HMP). HMPs consist of two single strands of DNA (green) and a polyethylene glycol (PEG, purple) linker that is used to tether these two sequences together. When a target (orange strand) containing the complementary sequences to both probes at adjacent positions is added, each strand binds to its corresponding target sequence, thus bringing the two fluorophores into close proximity, which allows energy transfer to occur     

A DFT‐Based Investigation of Hydrogen Abstraction Reactions from Methylated Polycyclic Aromatic Hydrocarbons

The growth of polycyclic aromatic hydrocarbons (PAHs) is in many areas of combustion and pyrolysis of hydrocarbons an inconvenient side effect that warrants an extensive investigation of the underlying reaction mechanism, which is known to be a cascade of radical reactions. Herein, the focus lies on one of the key reaction classes within the coke formation process: hydrogen abstraction reactions induced by a methyl radical from methylated benzenoid species. It has been shown previously that hydrogen abstractions determine the global PAH formation rate. In particular, the influence of the polyaromatic environment on the thermodynamic and kinetic properties is the subject of a thorough exploration. Reaction enthalpies at 298 K, reaction barriers at 0 K, rate constants, and kinetic parameters (within the temperature interval 700–1100 K) are calculated by using B3LYP/6‐31+G(d,p) geometries and BMK/6‐311+G(3df,2p) single‐point energies. This level of theory has been validated with available experimental data for the abstraction at toluene. The enhanced stability of the product benzylic radicals and its influence on the reaction enthalpies is highlighted. Corrections for tunneling effects and hindered (or free) rotations of the methyl group are taken into account. The largest spreading in thermochemical and kinetic data is observed in the series of linear acenes, and a normal reactivity–enthalpy relationship is obtained. The abstraction of a methyl hydrogen atom at one of the center rings of large methylated acenes is largely preferred. Geometrical and electronic aspects lie at the basis of this striking feature. Comparison with hydrogen abstractions leading to arylic radicals is also made.