Determination of copper in medicinal plants used as dietary supplements by atomic absorption spectrometry with direct flame solid analysis

An alternative device for the direct solid analysis (DSA) for copper determination by flame atomic absorption spectrometry (FAAS) is proposed. Copper was directly determined in commercial medicinal plants used as dietary supplements. The determination of copper in solid samples by DSA–FAAS was made by using a conventional air–acetylene flame. Between 0.05 and 1.5 mg of each test, sample was weighed directly into a small polyethylene vial connected to the device used for solid introduction into the flame. Test samples were introduced into the flame as a dry aerosol using a T-quartz cell set between the burner and the optical path. The T-quartz cell has a slit in the superior part by which the solid aerosol passes to the flame. A transient signal, evaluated as integrated absorbance, is produced and it is totally integrated in 2 s. Background signals always presented absorbance values less than 0.1. It was found a characteristic mass of 0.8 ng Cu and absolute limit of detection of 1.2 ng (3 s), or 1.2 μg g⁻¹ if a sample mass of 1 mg was used. Optimized conditions for air flow rate, flame stoichiometry, and so on were established as well. No excessive grinding of the samples was needed and samples with particle of size less than 80 μm were used throughout. No statistical difference between the results from the proposed system and those obtained by sample digestion and determination by conventional FAAS was observed. With the proposed procedure, more than 50 test samples can be analyzed in 1 h and it can be easily adapted to conventional spectrometers for FAAS.     

Uncovering the Stoichiometry of Pyrococcus furiosus RNase P,a Multi‐Subunit Catalytic Ribonucleoprotein Complex,by Surface‐Induced Dissociation and Ion Mobility Mass Spectrometry

We demonstrate that surface‐induced dissociation (SID) coupled with ion mobility mass spectrometry (IM‐MS) is a powerful tool for determining the stoichiometry of a multi‐subunit ribonucleoprotein (RNP) complex assembled in a solution containing Mg²⁺. We investigated Pyrococcus furiosus (Pfu) RNase P, an archaeal RNP that catalyzes tRNA 5′ maturation. Previous step‐wise, Mg²⁺‐dependent reconstitutions of Pfu RNase P with its catalytic RNA subunit and two interacting protein cofactor pairs (RPP21?RPP29 and POP5?RPP30) revealed functional RNP intermediates en route to the RNase P enzyme, but provided no information on subunit stoichiometry. Our native MS studies with the proteins showed RPP21?RPP29 and (POP5?RPP30)₂ complexes, but indicated a 1:1 composition for all subunits when either one or both protein complexes bind the cognate RNA. These results highlight the utility of SID and IM‐MS in resolving conformational heterogeneity and yielding insights on RNP assembly.     

Chemorheology investigation of a glassy epoxy thermoset on tensile plastic flow and fracture morphology

Reproducible and uncharacteristic tensile stress–strain behavior of cured glassy epoxy‐amine networks produces distinctive fracture surfaces. Test specimens exhibiting plastic flow result in mirror‐like fracture surfaces, whereas samples that fail during yield or strain softening regions possess nominal mirror‐mist‐hackle topography. Atomic force microscopy and scanning electron microscopy reveal branched nodule morphologies in the 50‐nm size scale that may be responsible for the unusual tensile properties. Current hypothesis is that plastic flow of the glassy thermoset occurs through the existence and deformation of these nodular nanostructures. The thermal cure profile of the epoxy‐amine thermoset affects the size and formation of the nodular nanostructure. Eliminating vitrification during thermoset polymerization forms a more continuous phase, reduction in size of the nodules, and eliminates the capacity of the material to yield in plastic flow. This maximizes nanostructure connectivity of the glassy epoxy‐amine thermoset and reduces strain to failure significantly. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1333–1344.     

Sustainable Synthesis of Chiral Tetrahydrofurans through the Selective Dehydration of Pentoses

L ‐Arabinose is an abundant resource available as a waste product of the sugar beet industry. Through use of a hydrazone‐based strategy, L ‐arabinose was selectively dehydrated to form a chiral tetrahydrofuran on a multi‐gram scale without the need for protecting groups. This approach was extended to other biomass‐derived reducing sugars and the mechanism of the key cyclization investigated. This methodology was applied to the synthesis of a range of functionalized chiral tetrahydrofurans, as well as a formal synthesis of 3R‐3‐hydroxymuscarine.     

Portable capillary liquid chromatography for pharmaceutical and illicit drug analysis

A newly developed portable capillary liquid chromatograph was investigated for the separation of various pharmaceutical and illicit drug compounds. The system consists of two high‐pressure syringe pumps capable of delivering capillary‐scale flow rates at pressures up to 10 000 psi. Capillary liquid chromatography columns packed with sub‐2 μm particles are housed in cartridges that can be inserted into the system and easily connected through high‐pressure fluidic contact points by simply applying a specific, predetermined torque rather than using standard fittings and less precise sealing protocols. Several over‐the‐counter analgesic drug separations are demonstrated, along with a simple online measurement of tablet dissolution. Twenty illicit drug compounds were also separated across six targeted drug panels. The results described in this study demonstrate the capability of this compact liquid chromatography instrument to address several important drug‐related applications while simplifying system operation, and greatly reducing solvent usage and waste generation essential for onsite analysis.     

CHARMM additive all-atom force field for carbohydrate derivatives and its utility in polysaccharide and carbohydrate-protein modeling

Monosaccharide derivatives such as xylose, fucose, N-acetylglucosamine (GlcNAc), N-acetylgalactosamine (GlaNAc), glucuronic acid, iduronic acid, and N-acetylneuraminic acid (Neu5Ac) are important components of eukaryotic glycans. The present work details development of force-field parameters for these monosaccharides and their covalent connections to proteins via O-linkages to serine or threonine sidechains and via N-linkages to asparagine sidechains. The force field development protocol was designed to explicitly yield parameters that are compatible with the existing CHARMM additive force field for proteins, nucleic acids, lipids, carbohydrates, and small molecules. Therefore, when combined with previously developed parameters for pyranose and furanose monosaccharides, for glycosidic linkages between monosaccharides, and for proteins, the present set of parameters enables the molecular simulation of a wide variety of biologically-important molecules such as complex carbohydrates and glycoproteins. Parametrization included fitting to quantum mechanical (QM) geometries and conformational energies of model compounds, as well as to QM pair interaction energies and distances of model compounds with water. Parameters were validated in the context of crystals of relevant monosaccharides, as well NMR and/or x-ray crystallographic data on larger systems including oligomeric hyaluronan, sialyl Lewis X, O- and N-linked glycopeptides, and a lectin:sucrose complex. As the validated parameters are an extension of the CHARMM all-atom additive biomolecular force field, they further broaden the types of heterogeneous systems accessible with a consistently-developed force-field model.     

Tissue-Specific stem cell differentiation in an in vitro airway model

The respiratory tract is the primary site of exposure to airborne compounds, with the bronchial epithelium providing one of the first lines of defence. A growing need exists for an accurate in vitro model of the bronchial epithelium. Here, normal human bronchial epithelial (NHBE) cells cultured at an air/liquid interface create a fully differentiated, in-vivo-like model of the human bronchial epithelium. Developmental characterisation includes (i) trans-epithelial electrical resistance, (ii) morphology and (iii) bronchial cell specific stains/markers. It is concluded that the basal/progenitor cells create a pseudo-stratified, mucociliary NHBE model containing basal, serous, Clara, goblet and ciliated cells, reflective of the normal human bronchial epithelium (days 24-33 ALI culture).     

I(-)·(CH3I)2 photoexcitation: the influence of dipole bound states on detachment and fragmentation

We present the results of a photoelectron imaging study of the I(-)·(CH(3)I)(2) cluster anion over excitation wavelengths 355-260 nm. The resulting spectra and photoelectron angular distributions (PADs) suggest extensive electron-molecule interaction following photoexcitation. Fragmentation channels are observed subsequent to excitation between 355 and 330 nm. The origin of these features, which begin 200 meV and peak 70 meV below the X band direct detachment threshold, is described in terms of a predissociative dipole bound state. The nature of the fragments detected and the energetics of the channel opening argue strongly in favor of an asymmetric, head to tail cluster anion geometry posited by Dessent et al. [Acc. Chem. Res. 31, 527 (1998)]. Above the direct detachment threshold, PADs display evidence of phenomena akin to electron-molecule scattering. The fragment anions disappear above the X band threshold but reappear some distance below the second (A) direct detachment band. At these energies there is also rapid variation of the X band PAD, an observation attributed to autodetachment via spin-orbit relaxation of the iodine core of the cluster.     

Circadian variations in biologically closed electrochemical circuits in Aloe vera and Mimosa pudica

The circadian clock regulates a wide range of electrophysiological and developmental processes in plants. This paper presents, for the first time, the direct influence of a circadian clock on biologically closed electrochemical circuits in vivo. Here we show circadian variation of the plant responses to electrical stimulation. The biologically closed electrochemical circuits in the leaves of Aloe vera and Mimosa pudica, which regulate their physiology, were analyzed using the charge stimulation method. The electrostimulation was provided with different timing and different voltages. Resistance between Ag/AgCl electrodes in the leaf of Aloe vera was higher during the day than at night. Discharge of the capacitor in Aloe vera at night was faster than during the day. Discharge of the capacitor in a pulvinus of Mimosa pudica was faster during the day. The biologically closed electrical circuits with voltage gated ion channels in Mimosa pudica are also activated the next day, even in the darkness. These results show that the circadian clock can be maintained endogenously and has electrochemical oscillators, which can activate ion channels in biologically closed electrochemical circuits. We present the equivalent electrical circuits in both plants and their circadian variation to explain the experimental data.     

Determination of operating characteristic, retesting, and testing amount probabilities associated with testing for the presence of Salmonella in foods

The relatively small perceived probability associated with retesting a food for the presence of Salmonella at low levels is often considered as one of the reasons that a confirmatory or check-analysis tends to disagree in practice with the results of an original test. Given a retesting process where a retest is only performed to confirm an original positive Salmonella test, the probability that both the original and retest will test positive for Salmonella has been traditionally determined by some as the product of the probabilities of a positive Salmonella test for the original and retest samples. When examining the probabilities associated with the retesting process, we found that our results disagreed with those based on intuitions apparently held by others concerning how these probabilities should be calculated. For Salmonella testing, operating characteristic values were computed to demonstrate the protections afforded by the Salmonella sampling plans presented in the U.S. Food and Drug Administration's Bacteriological Analytical Manual and to obtain the probability of a positive Salmonella test. The geometric distribution was examined for possible utility in determining the probabilities associated with testing amounts, i.e., the number of Salmonella tests needed to obtain a positive test.