Toxicological evaluation in silico and in vivo of secondary metabolites of Cissampelos sympodialis in Mus musculus mice following inhalation

The ethanolic extract of the leaves of Cissampelos sympodialis showed great pharmacological potential, with inflammatory and immunomodulatory activities, however, it showed some toxicological effects. Therefore, this study aims to verify the toxicological potential of alkaloids of the genus Cissampelos through in silico methodologies, to develop a method in LC-MS/MS verifying the presence of alkaloids in the infusion and to evaluate the toxicity of the infusion of the leaves of C. sympodialis when inhaled by Swiss mice. Results in silico showed that alkaloid 93 presented high toxicological potential along with the products of its metabolism. LC-MS/MS results showed that the infusion of the leaves of this plant contained the alkaloids warifteine and methylwarifteine. Finally, the in vivo toxicological analysis of the C. sympodialis infusion showed results, both in biochemistry, organ weights and histological analysis, that the infusion of C. sympodialis leaves presents a low toxicity.     

Salvia officinalis L. essential oils: effect of hydrodistillation time on the chemical composition, antioxidant and antimicrobial activities

Salvia officinalis L. oils were isolated from the plant's commercial dried aerial parts, by hydrodistillation, with different distillation times. The essential oils were analysed by gas chromatography and gas chromatography-mass spectrometry. The antioxidant ability was measured using a free radical scavenging activity assay using 2,2-diphenyl-1-picrylhydrazyl (DPPH), a thiobarbituric acid reactive substances (TBARS) assay, a deoxyribose assay for the scavenging of hydroxyl radical, an assay for site-specific actions and a 5-lipoxygenase assay. Antibacterial activity was determined by the agar diffusion method. 1,8-Cineole, α-pinene and camphor were the dominant components of all the essential oils. The different hydrodistillation times did not affect the oil yield nor the relative amount of the oil components. The time of hydrodistillation influenced the antioxidant activity. With the DPPH method, the oils isolated for 2 and 3 h were stronger free radical scavengers, while with the TBARS method, the highest antioxidant values were obtained in the oils isolated for 30 min, 2 and 3 h. Hydroxyl radical scavenging and lipoxygenase activity assays showed the best results with oils isolated for 1 and 3 h. With the deoxyribose method, sage oils at concentrations <1000 mg L(-1) showed better activity than mannitol. The essential oil of S. officinalis showed very weak antimicrobial activity.     

Changes in chemical composition and collagen structure of dentine tissue after erbium laser irradiation

Erbium laser radiation has a great affinity for the water molecule, which is present in quantity in biological hard tissues. The objective of this work is to identify chemical changes by infrared spectroscopy of irradiated dentine by an Er:YAG-2.94 microm laser. The irradiation was performed with fluences between 0.365 and 1.94 J/cm2. For the infrared analysis a Fourier transform infrared spectrometer was used. After the irradiation were observed: loss of water, alteration of the structure and composition of the collagen, and increase of the OH- radical. These alterations can be identified by a decrease in intensity of the water band between 2800-3800 cm(-1), OH- band at 3575 cm(-1) and bands ascribed to organic matrix between 2800-3400 cm(-1) and 1100-1400 cm(-1).     

Direct tandem mass spectrometry for the simultaneous assay of opioids,cocaine and metabolites in dried urine spots

A micro-analytical method based on spotting urine samples (20 μL) onto blood/urine spot collection cards followed by air-drying and extraction (dried urine spot, DUS) was developed and validated for the screening/confirmation assay of morphine, 6-methylacetylmorphine (6-MAM), codeine, cocaine and benzoylecgonine (BZE). Acetonitrile (3 mL) was found to be a useful solvent for target extraction from DUSs under an orbital-horizontal stirring at 180 rpm for 10 min. Determinations were performed by direct electrospray ionization tandem mass spectrometry (ESI-MS/MS) under positive electrospray ionization conditions, and by using multiple reaction monitoring (MRM) with one precursor ion/product ion transition for the identification and quantification (deuterated analogs of each target as internal standards) of each analyte. The limits of detection of the method were 0.26, 0.94, 1.5, 1.1, and 2.0 ng mL⁻¹, for cocaine, BZE, codeine, morphine and 6-MAM, respectively; whereas, relative standard deviations of intra- and inter-day precision were lower than 8 and 11%, respectively, and intra- and inter-day analytical recoveries ranged from 94 ± 4 to 105 ± 3%. The small volume of urine required (20 μL), combined with the simplicity of the analytical technique makes it a useful procedure for screening/quantifying drugs of abuse. The method was successfully applied to the analysis of urine from polydrug abusers.     

Enamels in stained glass windows: Preparation, chemical composition, microstructure and causes of deterioration

Stained glass windows incorporating dark blue and purple enamel paint layers are in some cases subject to severe degradation while others from the same period survived the ravages of time. A series of dark blue, green–blue and purple enamel glass paints from the same region (Northwestern Europe) and from the same period (16–early 20th centuries) has been studied by means of a combination of microscopic X-ray fluorescence analysis, electron probe micro analysis and transmission electron microscopy with the aim of better understanding the causes of the degradation. The chemical composition of the enamels diverges from the average chemical composition of window glass. Some of the compositions appear to be unstable, for example those with a high concentration of K₂O and a low content of CaO and PbO. In other cases, the deterioration of the paint layers was caused by the less than optimal vitrification of the enamel during the firing process. Recipes and chemical compositions indicate that glassmakers of the 16–17th century had full control over the color of the enamel glass paints they made. They mainly used three types of coloring agents, based on Co (dark blue), Mn (purple) and Cu (light-blue or green–blue) as coloring elements. Blue–purple enamel paints were obtained by mixing two different coloring agents. The coloring agent for red–purple enamel, introduced during the 19th century, was colloidal gold embedded in grains of lead glass.     

Changes of surface chemical structure and composition of phenolphthalein poly(ether sulfone) in different radiations

To understand the different action mechanisms of space irradiation on polymers, phenolphthalein poly(ether sulfone) (PES‐C) blocks were irradiated by electrons and atomic oxygen. The changes in surface chemical structure and composition of PES‐C in different radiations were studied by attenuated total‐reflection FTIR (FTIR‐ATR) and XPS. It was found that PES‐C was prone to be influenced by space irradiation. Electron and atomic oxygen irradiation can destroy the molecular chain of PES‐C and result in changes of surface chemical composition of the polymer. But due to the different nature of the radiation sources, electron irradiation induced the carbonization of the polymer surface, while atomic oxygen irradiation resulted in the oxidation of the polymer surface. Besides this, the sulfone structure was reduced or oxidized depending on the nature of the radiation sources. So, different radiation sources might influence the surface chemical structure and composition of polymers differently. Copyright © 2008 John Wiley & Sons, Ltd.     

Photodegradation of polyimides. III. The effect of chemical composition,radiation source,atmosphere, and processing

Polymide films made from diarylanhydrides with oxygen, carbonyl, and hexafluoroisopropylidene 6F bridging groups are photolabile when irradiated with unfiltered light from a medium-pressure mercury lamp. The presence of oxygen is necessary to the photolytic degradation process, which results in the ultimate oxidative ablation of thin polyimide films. Films based on the 6F dianhydride containing a hexafluoroisopropylidene hinge group are the most unstable. However, photolysis of 6F dianhydride based polyimides in an inert atmosphere with either the unfiltered medium pressure mercury lamp or an electron beam results in no detectable changes even after long exposure times.     

The chemical composition of mixed wastes: Analysis of the photolysis products of organic ligands

A survey of the literature regarding the composition of mixed wastes originating from the clean ups of spills of radioactive solutions shows that (1) the mixtures obtained in studies of the X-ray and -ray radiolysis, and of the UV-photolysis of organics in aqueous solutions have very similar composition provided the photolysis is carried out with UV beams with wavelengths below 242 nm; (2) the composition of the organic fraction of mixed wastes containing initially EDTA, NTA, and/or citric acid is complex. The mass recoveries are between 20 and 60%; and (3) the UV-photolysis of complexing agents gives much more complex mixtures at high pH than at low pH, because carbonyl compounds are formed, and these compounds undergo complex series of reactions in strongly alkaline solutions. The mixed wastes considered have a high pH due to the necessity of complexing strongly the heavy metals involved in spills. These results are confirmed by an investigation of the properties of the products of the UV-irradiation of EDTA, citric acid and some of their binary mixtures. The products of the esterification by BF₃/BuOH are only partly soluble in methylene chloride. Much better yields are obtained by using BF₃/BuOH as the reagent.¹³C NMR illustrates the composition of the mixture, without requiring a separation and is useful to follow the fate of compounds during their methylene chloride extraction after esterification.     

Diblock copolymers as emulsifying agents in polymer blends: Influence of molecular weight,architecture, and chemical composition

Interfacial agents used in the compatibilization of immiscible polymer blends often consist of block copolymers containing at least one segment compatible with each of the two phases of the blend. This work examines the influence of the molecular weight, architecture, and chemical composition of the interfacial agent on its ability to emulsify a polymer blend. The system chosen is a blend containing 80% polystyrene and 20% ethylene-propylene rubber, compatibilized by diblock copolymers of poly(styrene-hydrogenated butadiene). The emulsification curve, which relates the dispersed phase particle size to the concentration of interfacial agent added to the system, was used as a tool to characterize the efficacy of the different interfacial agents. The observed behavior is similar to that of classical emulsions: a rapid drop in phase size at low concentrations of interfacial modifier, followed by a levelling off to an equilibrium diameter value once a “critical” concentration has been reached. For systems compatibilized by symmetrical diblocks (i.e., containing approximately 50% styrene by weight), the volume average particle diameter decreased from 2.7 μm for the unmodified system to about 0.4 μm once interfacial saturation is reached. The critical concentration for emulsification decreased with increasing interfacial agent molecular weight, due to the higher interfacial area occupied by longer molecules; however, this parameter did not affect the equilibrium particle diameter. The asymmetrical diblock copolymer (30% styrene) was found to be less effective than the symmetrical ones over the entire range of concentrations studied (5 to 35% modifier, based on the volume of the minor phase). Asymmetrical diblock copolymers would tend to form micelles, whereas symmetrical copolymers are less constrained at the interface. No significant difference was observed between the emulsifying capability of tapered and pure diblocks of similar composition and molecular weight. © 1996 John Wiley & Sons, Inc.     

Structure, chemical composition, and reactivity correlations during the in situ oxidation of 2-propanol

Unraveling the complex interaction between catalysts and reactants under operando conditions is a key step toward gaining fundamental insight in catalysis. We report the evolution of the structure and chemical composition of size-selected micellar Pt nanoparticles (～1 nm) supported on nanocrystalline γ-Al(2)O(3) during the catalytic oxidation of 2-propanol using X-ray absorption fine-structure spectroscopy. Platinum oxides were found to be the active species for the partial oxidation of 2-propanol (<140 °C), while the complete oxidation (>140 °C) is initially catalyzed by oxygen-covered metallic Pt nanoparticles, which were found to regrow a thin surface oxide layer above 200 °C. The intermediate reaction regime, where the partial and complete oxidation pathways coexist, is characterized by the decomposition of the Pt oxide species due to the production of reducing intermediates and the blocking of O(2) adsorption sites on the nanoparticle surface. The high catalytic activity and low onset reaction temperature displayed by our small Pt particles for the oxidation of 2-propanol is attributed to the large amount of edge and corner sites available, which facilitate the formation of reactive surface oxides. Our findings highlight the decisive role of the nanoparticle structure and chemical state in oxidation catalytic reactions.     

Hydrogel microspheres: influence of chemical composition on surface morphology, local elastic properties, and bulk mechanical characteristics

Hydrogel microspheres, beads, and capsules of uniform size, differing in their chemical composition, have been prepared by electrostatic complex formation of sodium alginate with divalent cations and polycations. These have served as model spheres to study the influence of the chemical composition on both surface characteristics and bulk mechanical properties. Resistance to compression experiments yielding the compression work clearly identified differences as a function of the composition, with forces at maximal compression in the range of 34-455 mN. The suitability and informative value of atomic force microscopy have been confirmed for the case where surface characterization is performed in a liquid environment equivalent to physiological conditions. Surface imaging and mechanical response to indentation revealed different average surface roughness and Young's moduli for all hydrogel types ranging from 0.9 to 14.4 nm and from 0.4 to 440 kPa, respectively. The hydrogels exhibited pure elastic behavior. Despite a relatively high standard deviation, resulting from both surface and batch heterogeneity, nonoverlapping ranges of Young's moduli were reproducibly identified for the selected model spheres. The findings indicate the reliability of contact mode atomic force microscopy to quantify local surface properties, which may have an impact on the biocompatibility of alginate-based hydrogel materials of different composition and conditions of preparation. Moreover, it seems that local elastic properties and bulk mechanical characteristics are subject to analogous composition influences.     

The Thai medicinal plant Gynura pseudochina var. hispida: chemical composition and in vitro NF-kappaB inhibitory activity

Gynura pseudochina (L.) var. hispida Thv. (Asteraceae) has been used in traditional medicine in Thailand for the treatment of conditions associated with chronic and acute inflammation. In continuation of our search for bioactive natural products from Thai medicinal plants, G. pseudochina var. hispida showed potential in vitro NF-kappaB (Nuclear Factor kappa B) inhibitory activity and, therefore, was chosen for bio-assay-guided isolation of active compounds. Bioassay-guided fractionation of the methanol extract of the leaves of G. pseudochina var. hispida led to the isolation and identification, by spectroscopic and mass spectrometric methods, of four compounds previously not reported from this poorly studied species: Quercetin 3- rutinoside (1), 3,5-di-caffeoylquinic acid (2), 4,5-di-caffeoylquinic acid (3), and 5-monocaffeoylquinic acid (4). This paper discusses the current knowledge of these active components as NF-kappaB inhibitors, which lends some support to the use of this plant in traditional medicine. Potential risks associated with pyrrolizidine alkaloids will, however, have to be investigated further.     

Effect of container material, storage time and temperature on determinations of cadmium levels in human urine

The effect of container material (polyethylene, polypropylene, polystyrene, borosilicate glass and flint glass), storage time (0-86 days), and temperature (22 degrees and 4 degrees ) on the cadmium content found by graphite-furnace atomic-absorption spectrometry for spiked and unspiked urine samples has been studied. No loss of cadmium occurred for at least 10 and 28 days when unspiked and spiked samples respectively, were stored in polyethylene containers at 22 degrees . For storage up to 3-4 days at 22 degrees , polypropylene, polystyrene, borosilicate glass and flint glass containers were also found suitable. Storage at 4 degrees was not effective in preventing loss of cadmium.     

Reachability,persistence, and constructive chemical reaction networks (part II): a formalism for species composition in chemical reaction network theory and application to persistence

Chemical Reaction Network Theory uses mathematics to study systems of reactions and infer their properties from their structure. At the onset is an abstract definition of a chemical reaction network which is very general and is pertinent beyond chemistry, e.g. in modeling interactions of microscopic and macroscopic living species. This allows the theory to provide widely applicable theorems. It also results in that the idea of chemical composition is mostly used implicitly in examples to illustrate theorems, not explicitly to establish new properties. In this paper we propose a formalism for species composition in a way that generalizes the idea of atomic composition—for instance, elementary species will extend the idea of atoms. We envision that this formalism could lead to more theorems on classes of networks that are of interest in biochemistry. Toward that prospect, we prove that if there is no isomerism among elementary species, and if a newly formalized and widely applicable reversibility condition holds, then a reaction network is vacuously persistent: no species will tend to extinction if all species are implicitly present at initial time. This paper is the second in a series of three articles. The first paper studies vacuous persistence and the third one probes a class of enzymatic networks.     

Correlation of transverse and rotational diffusion coefficient: a probe of chemical composition in hydrocarbon oils

Measurements of relaxation time and diffusion coefficient by nuclear magnetic resonance are well-established techniques to study molecular motions in fluids. Diffusion measurements sense the translational diffusion coefficients of the molecules, whereas relaxation times measured at low magnetic fields probe predominantly the rotational diffusion of the molecules. Many complex fluids are composed of a mixture of molecules with a wide distribution of sizes and chemical properties. This results in correspondingly wide distributions of measured diffusion coefficients and relaxation times. To first order, these distributions are determined by the distribution of molecular sizes. Here we show that additional information can be obtained on the chemical composition by measuring two-dimensional diffusion-relaxation distribution functions, a quantity that depends also on the shape and chemical interactions of molecules. We illustrate this with experimental results of diffusion-relaxation distribution functions on a series of hydrocarbon mixtures. For oils without significant amounts of asphaltenes, the diffusion-relaxation distribution functions follow a power-law behavior with an exponent that depends on the relative abundance of saturates and aromatics. Oils with asphaltene deviate from this trend, as asphaltene molecules act as relaxation contrast agent for other molecules without affecting their diffusion coefficient significantly. In waxy oils below the wax appearance temperature a gel forms. This is reflected in the measured diffusion-relaxation distribution functions, where the restrictions due to the gel network reduce the diffusion coefficients without affecting the relaxation rates significantly.