Determination of metallic iron, iron(II) oxide, and iron(III) oxide in a mixture

A procedure is described for the estimation of metallic iron, ferrous oxide, and ferric oxide when present together. The sample is treated with bromine dissolved in ethanol, and filtered. Iron in the filtrate is titrated iodometrically, and corresponds to the metallic iron present in the mixture. The oxide residue is dissolved in hydrochloric acid under a carbon dioxide atmosphere. The iron(II) formed, equivalent to FeO present, is titrated with a standard vanadate solution, and the total iron(III) (FeO + Fe₂O₃) in the titrated solution is then estimated iodometrically.     

Electron paramagnetic resonance and optical absorption spectral studies on chalcocite

A chalcocite mineral sample of Shaha, Congo is used in the present study. An electron paramagnetic resonance (EPR) study on powdered sample confirms the presence of Mn(II), Fe(III) and Cu(II). Optical absorption spectrum indicates that Fe(III) impurity is present in octahedral structure whereas Cu(II) is present in rhombically distorted octahedral environment. Mid-infrared results are due to water and sulphate fundamentals.     

Reachability,persistence, and constructive chemical reaction networks (part I): reachability approach to the persistence of chemical reaction networks

For a chemical reaction network, persistence is the property that no species tend to extinction if all species are initially present. We investigate the stronger property of vacuous persistence: the same asymptotic feature with a weaker requirement on initial states, namely that all species be implicitly present. By implicitly present, we mean for instance that if only water is present and the reaction network incorporates the information that water is made of hydrogen and oxygen, then hydrogen and oxygen are implicitly present. Persistence is inherently interesting and has implications for the global asymptotic stability of equilibrium states. Our main tools are the work of A. I. Vol’pert on the nullity and positivity of species concentrations, and the enabling notion of reachability. The main result states that a reaction network is vacuously persistent if and only if the set of all species is the only set of species that both is closed with respect to reachability and causes the implicit presence of all species. This paper is the first in a series of three articles. Two sequel papers introduce additional formalisms and use them to describe two large classes of reaction networks that are used as models in biochemistry and are vacuously persistent.     

The Compositional Aspects of Edible Flowers as an Emerging Horticultural Product

Edible flowers are becoming very popular, as consumers are seeking healthier and more attractive food products that can improve their diet aesthetics and diversify their dietary sources of micronutrients. The great variety of flowers that can be eaten is also associated with high variability in chemical composition, especially in bioactive compounds content that may significantly contribute to human health. The advanced analytical techniques allowed us to reveal the chemical composition of edible flowers and identify new compounds and effects that were not known until recently. Considering the numerous species of edible flowers, the present review aims to categorize the various species depending on their chemical composition and also to present the main groups of compounds that are usually present in the species that are most commonly used for culinary purposes. Moreover, special attention is given to those species that contain potentially toxic or poisonous compounds as their integration in human diets should be carefully considered. In conclusion, the present review provides useful information regarding the chemical composition and the main groups of chemical compounds that are present in the flowers of the most common species.     

Steady state and time-resolved fluorescence study of isoquinoline: reinvestigation of excited state proton transfer

In the present work we report some hitherto unnoticed features in the steady state and time-resolved measurements of isoquinoline in water and trifluoroethanol (TFE). Absorption spectra reveal that in water, neutrals as well cationic species are present. Emission spectrum shows structured features at shorter wavelengths accompanied with a broad band around 375 nm, which correspond to neutrals and cations respectively. However, time-resolved data indicate that protonation does not take place in the excited state in water. On the contrary, in stronger hydrogen bonding solvent TFE, distribution of decay components is observed and at longer wavelengths a small rise time is present. This is ascribed to neutral and cation-like species present in the ground as well as in the excited state. The difference in the results is explained in terms of different excited state potential energy surfaces for water and TFE; particularly, the presence of a rather small barrier for protonation in case of TFE.     

Synthesis of TS-1 molecular sieves using a new Ti source

The incorporation of Ti in the MFI structure using a cheap and easy to handle source, the hexafluorotitanic acid, was successfully achieved without the formation of contaminant phases. The TS-1 samples with 1%, 2%, and 2.5% Ti present a linear increase in the cell parameters. This indicates that the Ti present in the solid is incorporated into the framework, and this is confirmed by infrared analysis. The TS-1 particles present morphology that is typical of the MFI structure. The UV-vis diffuse reflectance results indicate the existence of tetra- and hexacoordinated framework Ti species. Independent of Ti content, all of the samples present similar activity for the oxidation of cyclohexene using hydrogen peroxide as an oxidant agent. Also, a high selectivity for the formation of the corresponding epoxide is observed.     

Method to isolate and characterize oligomers present in the aqueous phase in emulsion copolymerization

In order to model the entry of radical in emulsion copolymerization, a study of the oligomers present in the aqueous phase is necessary. In this work a new method for separation and characterization of the aqueous phase has been developed. MALDI-ToF-MS was found to be a powerful technique in order to characterize the oligomers present in the aqueous phase. It is for the first time that full chemical composition and molecular weight information of the oligomers present in the aqueous phase in emulsion copolymerization has been obtained. The methodology was shown to be semi-quantitative and several factors were studied, for example temperature effects, interference of latex particles present in serum of the aqueous phase and type of ionizing salt in MALDI. It was shown that the methodology works well, even though we are dealing with small quantities of oligomers and the possibility of mass discrimination in MALDI-ToF-MS.     

Need for further inelastic scattering measurements at X-ray energies

With recent improvements in both theory and experiment for scattering of X-rays from atoms, it is possible now to make a more quantitative comparison, and see whether agreement is being obtained within the much more stringent limits set by the present calculations and measurements. Comparing with present theory, measured whole atom Compton scattering cross sections in the photon energy range 11–40 keV using synchrotron X-ray sources demonstrate that a dramatic improvement in the precision of scattering measurements has been achieved. However, circumstances are also identified in which further experimental data is needed in order to test the adequacy of present theoretical approaches.     

Improvement on macroscopic compressibility approximation and beyond

A numerical procedure is proposed to extend the thermodynamic perturbation expansion (TPE) to a higher order. It is shown that the present second order term is superior to that due to a macroscopic compressibility approximation (MCA), a local compressibility approximation, and a superposition approximation by Barker and Henderson [Rev. Mod. Phys. 48, 587 (1976)]. Extensive model calculation and comparison with simulation data available in literature and supplied in the present report indicate that the present third order TPE is superior to a previous second order TPE based on the MCA, two previous perturbation theories, which are respectively based on an analytical mean spherical approximation for an Ornstein-Zernike equation, and an assumed explicit functional form for the Laplace transform of radial distribution function multiplied by radial distance, and a recent generalized van der Waals theory. The present critical temperature for a hard core attractive Yukawa fluid of varying range is in very good agreement with that due to a hierarchical reference theory. The present third order TPE is computationally far more modest than the self-consistent integral equation theory, and therefore is a viable alternative to use of the latter.     

Identification of biologically active triterpenes and sterols present in hexane extracts from Miconia species using high-resolution gas chromatography

In this work we describe the identification of the biologically active triterpenes and sterols present in the hexane extracts of six species of Miconia using gas chromatography. The main compounds present in these extracts are beta-amyrin, alpha-amyrin, and beta-sitosterol. The technique employed herein is shown to be a valuable and rapid tool for determining biologically active triterpenes and sterols present in non-polar extracts.     

Investigation of pituitary adenylate cyclase activating polypeptide in human gynecological and other biological fluids by using MALDI TOF mass spectrometry

Pituitary adenylate cyclase activating polypeptide (PACAP) is a multifunctional and pleiotropic neuropeptide. PACAP has diverse effects in the endocrine system, among others, it plays important roles in oogenesis, implantation and development of the nervous system. However, it is not known whether PACAP is present in the fluids of the human reproductive organs. The aim of the present study was to determine, by means of mass spectrometry and radioimmunoassay, whether PACAP is present in human amniotic fluid, ovarian follicular fluid and cervico-vaginal fluid. Samples were obtained from healthy adult volunteers. Our MALDI TOF and MALDI TOF/TOF spectrometry results show that PACAP38 is present in all of the follicular fluid samples, and PACAP-like immunoreactivity was also measured by radioimmunoassay. However, we did not find the characteristic peak representing the unmodified 38 amino acid form of the peptide in normal cervico-vaginal smear and amniotic fluid samples. Furthermore, we analyzed other body fluids for comparison, such as human nasal fluid, saliva and aqueous humor. PACAP was not found in these latter samples. In summary, the present study provides evidence for the presence of PACAP in human follicular fluid, suggesting a role in oocyte function, but determination of the exact physiological significance awaits further investigation.     

Site-selective spectroscopy of garnet crystals doped with chromium ions

Site-selective spectroscopy is a tool that can be used to uncover the presence of multiple sites available to optically active ions in host lattices. In this Article, we present techniques that can be applied to appraise the different sites that may occur in systems where charge compensation is required or in systems where such compensation is not present. We then consider some garnet crystals doped with chromium ions. For the Cr-doped garnets (YAG, GGG, GSGG, and CYMGG), we present luminescence and lifetime data over a wide temperature range, and infer not only the presence of different centers, but also the interaction among them as a function of temperature.     

Temperature dependence of OH(8;6) equilibration in an air-like gas ensemble

We present a quantum state-resolved computational investigation of the equilibration of rovibrationally excited OH, present as the minor component in an air-like mixture of N(2) and O(2), over the temperature range 100-1200 K. Generic features of the equilibration that are present over the entire range are identified, and the increase in speed of the principal energy exchange mechanism as the temperature increases is quantified. The data demonstrate that partitioning of excess energy and angular momentum among the modes of the three different molecules is independent of the magnitude of excess energy and of its form. The rotational temperature of OH is found to vary widely over the equilibration process, varying with number of collision cycles and with initial temperature. However, at equilibration, the rotational temperature of OH is invariably the lowest of all modes of all three species present in the ensemble. This suggests that rotational temperatures of OH obtained from rotational state populations are unlikely to provide a reliable guide to other modal temperatures in ensembles of the kind we consider.     

Analysis by liquid chromatography‐tandem mass spectrometry of biophenolic compounds in olives and vegetation waters,Part I

Biophenolic compounds constitute a complex mixture in olives and derived products. In this work, ion‐spray tandem mass spectrometry coupled with liquid chromatography is applied to the identification and quantification of biophenols present in complex matrices such as olives and vegetation waters. The extraction and purification method for the biophenol present in both the matrices is reported. Using this approach the main biophenols found, in three different variety of olives, were: tyrosol, hydroxytyrosol, oleoside methyl ester, oleoside dimethyl ester, and oleuropein. In vegetation water the biophenols are present in lower amounts than in olives.     

First enantioselective synthesis and absolute stereochemistry assignment of new monocyclic sesquiterpenes from Artemisia chamaemelifolia

We herein report the first enantioselective synthesis of two new monocyclic sesquiterpenes from Artemisia chamaemelifolia starting from an enantiopure building block. The key feature of the present approach is to allow complete control of all the stereogenic centers present in the natural products and to elucidate their absolute stereochemistry, which to date is unknown.     

Phase equilibria in polymer solutions

A theoretical study of phase equilibria in multicomponent polymer solutions is presented. The treatment is based on the virial expansion of the osmotic pressure. A program for the numerical determination of phase diagrams is worked out and applied to the polystyrene-cyclohexane system. The present approach is compared with the Flory-Huggins theory of polymer solutions, which is shown to represent a special class of approximations in the present treatment.     

A density functional theory for Lennard-Jones fluids in cylindrical pores and its applications to adsorption of nitrogen on MCM-41 materials

A density functional theory (DFT) constructed from the modified fundamental-measure theory and the modified Benedict-Webb-Rubin equation of state is presented. The Helmholtz free energy functional due to attractive interaction is expressed as a functional of attractive weighted-density in which the weight function is a mean-field-like type. An obvious advantage of the present theory is that it reproduces accurate bulk properties such as chemical potential, bulk pressure, vapor-liquid interfacial tension, and so forth when compared with molecular simulations and experiments with the same set of molecular parameters. Capabilities of the present DFT are demonstrated by its applicability to adsorption of argon and nitrogen on, respectively, a model cylindrical pore and mesoporous MCM-41 materials. Comparison of the theoretical results of argon in the model cylindrical pore with those from the newly published molecular simulations indicates that the present DFT predicts accurate average densities in the pore, slightly overestimates the pore pressure, and correctly describes the effect of the fluid-pore wall interaction on average densities and pressures in the pore. Application to adsorption of nitrogen on MCM-41 at 77.4 K shows that the present DFT predicts density profiles and adsorption isotherms in good agreement with those from molecular simulations and experiments. In contrast, the hysteresis loop of adsorption calculated from the mean-field theory shifts toward the low pressure region because a low bulk saturated pressure is produced from the mean-field equation of state. The present DFT offers a good way to describe the adsorption isotherms of porous materials as a function of temperature and pressure.     

Sensitive detection of soy (Glycine max) by real-time polymerase chain reaction targeting the mitochondrial atpA gene

Detection of trace amounts of allergens is essential for correct labeling of food products by the food industry. PCR-based detection methods currently used for this purpose are targeting sequences of DNA present in the cell nucleus. In addition to nuclear DNA, a substantial amount of mitochondrial DNA (mtDNA) copies are present in the cytoplasm of eukaryotic cells. The nuclear DNA usually consists of a set of DNA molecules present in two copies per cell, whereas mitochondrial DNA is present in a few hundred copies per cell. Thus, an increase in sensitivity can be expected when mtDNA is used as the target. In this study, we present a reporter probe-based real-time PCR method amplifying the mitochondrial gene of the alpha chain of adenosine triphosphate synthetase from soy. Increase in sensitivity was examined by determining the minimal amount of soy DNA detectable by mtDNA and nuclear DNA (nDNA) amplification. Additionally, the LOD of soy in a food matrix was determined for mtDNA amplification and compared to the LOD determined by nDNA amplification. As food matrix, a model spice spiked with soy flour was used. Sensitivity of PCR-based soy detection can be increased by using mtDNA as the target.     

Gas-liquid chromatography and gas-liquid chromatography combined with mass spectrometry of a butyl ester formulation of (2,4-dichlorophenoxy) acetic acid.

A method is presented for the analysis of (2,4-dichlorophenoxy)acetic acid (2,4-D) in commercial formulations, together with concurrent detection and quantitation of related compounds. The method is based on direct gas-liquid chromatographic (GLC) analysis of the formulation to estimate the various esters present, and on an analysis of the total 2,4-D present involving a prior cleanup, alkaline hydrolysis, acidification and n-butylation steps. This procedure also quantitates any other related acids or phenols present. A step which would extract dioxin impurities is also included. The method was checked by the accepted acid-base estimation of 2,4-D content, GLC, and by subjecting radioactive-labelled herbicide to the above procedures.     

A simple method for calculating reliable atomic charges in large molecules

Modifications are made to a previously developed scheme for calculating atomic charge which uses orbital electronegativity and which requires minimal calculational effort. The introduced changes are a result of deficiencies noted in the earlier method which were due to an inadequate accounting of effects from neighboring atom charges. Results obtained using the modified scheme for both model compounds as well as larger molecules of interest to biochemistry are compared to previous results and also to several levels of ab initio calculations. It is shown that a definite improvement is obtained and that the present method gives very good correlations with each calculational level. Comparisons are also made with other methods that use electronegativity theory. It is shown that the present scheme represents a definite improvement over alternate orbital electronegativity methods and is roughly comparable to a higher level scheme that utilizes atomic electronegativity values. A discussion comparing the latter method with the present one is included. Because of the small amount of calculational effort involved, the results indicate that the present method could be quite useful in providing reliable atomic charges for large molecular systems.