Determination of trace elements in marine plankton by inductively coupled plasma mass spectrometry (ICP-MS)

A method has been developed for the determination of 23 elements in marine plankton in which inductively coupled plasma (ICP) source mass spectrometry (MS) was used to quantify the elements in the solution after digestion in a mixture of hydrofluoric and nitric acids in sealed PTFE vessels in a microwave field. The procedure was validated by the analysis of a standard reference soil (SRM 2709 San Joaquin Soil) and a standard reference fresh water plankton (CRM 414). The method was applied to the analysis of several marine plankton samples grown under controlled conditions including several whose growth media had been enriched with selenium. Matrix induced signal suppressions and instrumental drift were corrected by internal standardization. The suitabilities of germanium, indium, rhodium, scandium and yttrium as internal standard elements were evaluated. Neither scandium nor yttrium could be used due to the presence of these elements in the samples, germanium was used for the determination of As, Co, Cu, Fe, Ni, Se, Si and Zn, indium was used for Al, Ba, Ca, Eu, Sr, and Tl, and rhodium was used for Cd, Cr, Hg, Mg, Pb, Sb, Sn, and V. For Al, Ca, Cr, Cu, Fe, Mg, Mn, Ni, Si, Sr, V, and Zn internal standardization did not completely compensate for the suppressive effect of the heavier elements and the solutions were diluted. However, for As, Ba, Cd, Co, Eu, Hg, Pb, Sb, Se, Sn and T1, it was possible to obtain accurate results despite the 35-40% suppression in the signals. Isobaric overlap was only a problem in the cases of 42Ca and 78Se; 44Ca and 77Se, respectively, were used. Memory effects were only observed with Hg for which a nitric acid-sodium chloride solution was the most effective wash-out solution. The marine plankton samples were able to tolerate a higher concentration of Hg as the selenium concentration increased.     

Synthesis and Properties of Thiophene and Dithiin Functionalized Tetrathiafulvalenes

Abstract

Syntheses of two analogues of tetrathiafulvalene (TTF), fused to 1,4-dithiin and thiophene rings, substituted with thiophene moieties, have been illustrated. The syntheses were accomplished through the reaction of a 1,8-diketone with phosphorus pentasulfide or Lawesson's reagent in boiling dry toluene. Conversion of the thioketones to their the oxo forms with mercury (II) acetate, was followed by self-coupling in freshly distilled boiling triethyl phosphite. Attempts for their electro-polymerizations through the thiophene groups at the peripherals were unsuccessful. Computational chemistry studies revealed that the thiophene groups did not exhibit enough spin densities to perform polymerization.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Chemical profile by LC–MS/MS,GC/MS and antioxidant activities of the essential oils and crude extracts of two Euphorbia species

In this study, it was aimed to investigate the chemical composition and antioxidant activities of two Euphorbia species. The major component of the fatty acid compositions obtained from the petroleum ether extracts was identified as palmitic acid for Euphorbia gaillardotii and Euphorbia macroclada. The main constituents of the essential oils were identified as arachidic acid for E. gaillardotii and tetratetracontane for E. macroclada. Among the 27 studied compounds, hesperidin, rutin, hyperoside and quinic, malic, gallic and tannic acids were found to be the most abundant compounds in the two Euphorbia species. The methanol extracts of E. gaillardotii and E. macroclada showed strong antioxidant activity in all tested methods. Particularly, IC₅₀ values of E. macroclada methanol extract that was the richest in terms of total phenolic-flavonoid contents were found to be lower than α-tocopherol and butylated hydroxytoluene in β-carotene bleaching, 2,2-diphenyl-1-picrylhydrazyl free and ABTS cation radical scavenging methods.     

Lifting Modules with Indecomposable Decompositions

A module M is called a “lifting module” if, any submodule A of M contains a direct summand B of M such that A/B is small in M/B. This is a generalization of projective modules over perfect rings as well as the dual of extending modules. It is well known that an extending module with ascending chain condition (a.c.c.) on the annihilators of its elements is a direct sum of indecomposable modules. If and when a lifting module has such a decomposition is not known in general. In this article, among other results, we prove that a lifting module M is a direct sum of indecomposable modules if (i) rad(M ^(I)) is small in M ^(I) for every index set I, or, (ii) M has a.c.c. on the annihilators of (certain) elements, and rad(M) is small in M.     

Synthesis of highly functionalized BEDT-TTF analogues incorporating 1,4-dithiin rings from 1,8-diketones

Employment of 1,8-diketone ring formation reaction led to the synthesis of tetrathiafulvalene derivatives having diphenyl-1,4-dithiin ring together with dihydroxyl, dimethyl, MEM and diphenylthiophene groups. Spectroelectrochemistry of ET and its fully unsaturated analogue 4 was compared. While both displayed nearly similar behaviours, ET started to precipitate as the second oxidation potential is reached. CV studies indicated that the fully unsaturated 4 and tetraphenyldithiophene 20 have the highest oxidation potentials, while diphenyldithiindimethylthio 16 displayed the lowest oxidation potentials. CV measurements indicated that the combination of dithiin and hydroxyl groups help lowering the oxidation potentials. It is surprising that while the presence of dithiin ring results in higher oxidation potentials, hydroxyl groups lower the potentials. Single crystal structure of 13, having both dithiin and 1,4-dithiepine rings, was examined and it was observed that dithiin and dithiepine rings form angles of 20.52° and 25.65° with the planar TTF core in cis form as both rings bent about their S?S axis to give a boat conformation.     

Nonthermal Atomization Using Atom Traps in Flame AAS

The most sensitive atomic spectrometric technique has been ETA-AAS for many years. Recently, ICP-MS has emerged as an approach which provides even lower detection limits, but at considerably higher instrument and running costs. Flame AAS, on the other hand, is still being used widely in many laboratories in world. Therefore, alternative approaches for better sensitivity using flame AAS should be relevant and important.     

More Than 12 % Polarization and 20 Minute Lifetime of 15N in a Choline Derivative Utilizing Parahydrogen and a Rhodium Nanocatalyst in Water

Hyperpolarization techniques are key to extending the capabilities of MRI for the investigation of structural, functional and metabolic processes in vivo. Recent heterogeneous catalyst development has produced high polarization in water using parahydrogen with biologically relevant contrast agents. A heterogeneous ligand‐stabilized Rh catalyst is introduced that is capable of achieving ¹⁵N polarization of 12.2±2.7 % by hydrogenation of neurine into a choline derivative. This is the highest ¹⁵N polarization of any parahydrogen method in water to date. Notably, this was performed using a deuterated quaternary amine with an exceptionally long spin‐lattice relaxation time (T₁) of 21.0±0.4 min. These results open the door to the possibility of ¹⁵N in vivo imaging using nontoxic similar model systems because of the biocompatibility of the production media and the stability of the heterogeneous catalyst using parahydrogen‐induced polarization (PHIP) as the hyperpolarization method.     

A new reaction of P4S10 and Lawesson's reagent; a new method for the synthesis of dithieno[3,2-b;2,3-d]thiophenes

A new reaction of P₄S₁₀ and Lawesson's reagent for the synthesis of fused thiophenes has been uncovered. It has given easy access to the synthesis of derivatives of the technologically important heterocycle dithieno[3,2-b;2^′,3^′-d]thiophene, DTT. Electrochemical polymerization of one of the derivatives has been demonstrated.     

Determination of fingerprints contents of different extracts and parts of six endemic Salvia taxa by GC–MS: Source species for valuable compounds with drug or drug potential

Public use of Salvia species and their importance in the scientific world is continually increasing. It is known that this use and the importance of Salvia species are mostly due to the terpenoid compounds that they contain. In this context, the terpenoid–steroid–flavonoid contents of extracts of six endemic Salvia (S. kurdica, S. pseudeuphratica, S. rosifolia, S. siirtica, S. cerino-pruinosa var. cerino-pruinosa and S. cerino-pruinosa var. elazigensis) species prepared with different solvents were determined by gas chromatography–mass spectrometry. Within the framework of the ingredient analysis, content analysis of the ethanol extracts of the root, branch, leaf and flower parts of the species collected in the same period between 2015 and 2017 years was performed. In general, extracts prepared with chloroform and ethanol were found to contain a wide variety of compounds while petroleum ether extracts were found to contain much less varied compounds. In addition, in general, root extracts are richer in terpenoid compounds than aerial part extracts. Some species can be used as source species in terms of ferruginol, cryptanol, 6,7-dehydroroyleanone, lup-(20)29-ene-2α-hydroxy-3β-acetate, salvigenin and β-sitosterol contents (52,114.28, 75,979.08, 101,247.41, 40,071.29, 33,952.13 and 34,010.90 μg analyte/g extract, respectively).