Über heteroorganische Verbindungen, 39. Mitt.: Neue Darstellungsmethoden für Bis-(dialkylthiophosphinyl)-trisulfide. Reaktionsmechanismus

Zusammenfassung Dialkyl-dithiophosphinsäuren reagieren mit Morpholinoschwefelchlorid zu Bis-(dialkyl-thiophosphinyl)-trisulfiden. In Anwesenheit von Triäthylamin bilden sich die bisher unbekannten S-Morpholino-dialkyl-mercapto-dithiophosphinate, die, dem angenommenen Reaktionsmechanismus entsprechend, mit Chlorwasserstoff und Dithiophosphinsäuren die Bis-(dialkyl-thiophosphinyl)-trisulfide liefern. S-Morpholino-diäthyl-mercapto-dithiophosphinat und Diäthyldithiophosphinsäure setzen sich zu Bis-(diäthyl-thiophosphinyl)-trisulfid um.

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Heteroorganic compounds, XXXIX.: New methods for the preparation of bis-(dialkylthiophosphinyl)-trisulfides, and a reaction mechanism

Dialkyldithiophosphinic acids react with morpholinosulfenyl chloride to give bis-(dialkylthiophosphinyl)-trisulfides. In the presence of triethylamine the hitherto not described S-morpholino-dialkyl-mercapto-dithiophosphinates are formed. According to an assumed reaction mechanism the latter react with HCl and dithiophosphinic acids to give bis-(dialkyl-thiophosphinyl)-trisulfides. S-Morpholino-diethylmercapto-dithiophosphinate and diethyldithiophosphinic acid yield bis-(diethylthiophosphinyl)-trisulfide.

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38. Mitt.:L. Almasi undA. Hantz, Mh. Chem.100, 798 (1969).     

Artificial neural network for Cu quantitative determination in soil using a portable Laser Induced Breakdown Spectroscopy system

Laser Induced Breakdown Spectroscopy (LIBS) is an advanced analytical technique for elemental determination based on direct measurement of optical emission of excited species on a laser induced plasma. In the realm of elemental analysis, LIBS has great potential to accomplish direct analysis independently of physical sample state (solid, liquid or gas). Presently, LIBS has been easily employed for qualitative analysis, nevertheless, in order to perform quantitative analysis, some effort is still required since calibration represents a difficult issue. Artificial neural network (ANN) is a machine learning paradigm inspired on biological nervous systems. Recently, ANNs have been used in many applications and its classification and prediction capabilities are especially useful for spectral analysis. In this paper an ANN was used as calibration strategy for LIBS, aiming Cu determination in soil samples. Spectra of 59 samples from a heterogenic set of reference soil samples and their respective Cu concentration were used for calibration and validation. Simple linear regression (SLR) and wrapper approach were the two strategies employed to select a set of wavelengths for ANN learning. Cross validation was applied, following ANN training, for verification of prediction accuracy. The ANN showed good efficiency for Cu predictions although the features of portable instrumentation employed. The proposed method presented a limit of detection (LOD) of 2.3 mg dm^− 3 of Cu and a mean squared error (MSE) of 0.5 for the predictions.     

Investigation of nanostructured Fe3O4 polypyrrole core-shell composites by X-ray absorbtion spectroscopy and X-ray diffraction using synchrotron radiation

In this article, we focus on the structural peculiarities of nanosized Fe₃O₄ in the core-shell nanocomposites obtained by polymerization of conducting polypyrrole shell around Fe₃O₄ nanoparticles. The local structure of Fe atoms was determined from the Extended X-ray Absorption Fine Structure analysis using our own package computer programs. An X-ray diffraction method that is capable to determine average particle size, microstrains, as the particle size distribution of Fe₃O₄ nanoparticles is presented. The method is based on the Fourier analysis of a single X-ray diffraction profile using a new fitting method based on the generalized Fermi function facilities. The crystallites size obtained by X-ray diffraction spectra analysis was estimated between 3.2 and 10.3 nm. Significant changes in the first and the second Fe coordination shell in comparison with standard bulk were observed. The global and local structure of the nanosized Fe₃O₄ are correlated with the synthesis conditions of the core-shell polypyrrole nanocomposites.     

Yield stress and flow behavior of concentrated ferrofluid-based magnetorheological fluids: the influence of composition

In this paper, the magnetorheological (MR) and magnetoviscous properties of ferrofluid-based iron particle suspensions were investigated. The 2.1-µm mean size Fe particles were dispersed in high-concentration transformer oil-based ferrofluid, the iron particle volume fraction in the resulting nano-micro composite magnetorheological fluid samples varying from Φ _Fe = 5 to 40 %. The ferrofluid carrier has φ _p = 23 % solid volume fraction of magnetic nanoparticles stabilized with chemisorbed oleic acid monolayer and without any excess surfactant. In the absence of the field, the ferrofluid has a quasi-Newtonian behavior with a weak shear thinning tendency. The static yield stress shows an increase of about 3 orders of magnitude for an iron particle content of approx. Φ _Fe = 25 % (Φ _tot = 42.25 %), while above this value, a saturation tendency is observed. The dynamic yield stress (Bingham model) also increases with the magnetic induction and the particle volume fraction; however, the saturation of the MR effect is less pronounced. The relative viscosity change has a maximum at Φ _Fe = (10–15) % due to the accelerated increase of the effective viscosity of the composite for higher Fe content. Addition of micrometer-sized iron particles to a concentrated ferrofluid without any supplementary stabilizing agent proved to be a direct and simple way to control the magnetorheological and magnetoviscous behavior, as well as the saturation magnetization of the resulting nano-micro composite fluid to fulfill the requirements of their use in various MR control and rotating seal devices.     

Magnetic resonance studies of copper (II) sorbitol complex,in solution,reveal a supramolecular structure compatible to the crystal structure

Although the Cu²⁺-sorbitol complex [Cu²⁺-Sorb] structure in crystalline state has been determined by X rays, it is not known in solution, where most studies of this complex are performed. Therefore, the goal of this work was to obtain information about the structure of this complex in aqueous solution using nuclear magnetic resonance and electron paramagnetic resonance spectroscopies. The magnetic resonance results indicate that the complex is formed at approximately pH 12. In this pH the sorbitol ¹H relaxation times were so short (broad line) that was not possible to use standard nuclear magnetic resonance parameters (nuclear Overhauser effect and spin–spin coupling constants values) to solve the three-dimensional structure. However, valuable structural information about the complex in solution was obtained. The relaxation results indicate that the Cu²⁺ ions are buried in the structure and not accessible to solvent; the ¹H and ¹³C spectra shows strong paramagnetic shift effect indicating short distance between these nuclei and Cu²⁺ in the structure. No electron paramagnetic resonance signal was observed in pH 12 indicating strong Cu²⁺- Cu²⁺ dipolar interaction, compatible to Cu²⁺-Cu²⁺ distances measured in crystal, from 1.148 to 1.393 Angstroms. The complex self-diffusion coefficient (D) of 1.58 × 10⁻¹⁰ m²/s value, determined by Diffusion-Ordered Spectroscopy, is compatible to a molecular weight of 3–6 KDa. Therefore, these results corroborate that the [Cu²⁺-Sorb] complex is assembled in solution, at pH 12, with several structural parameters compatible to the toroidal hexadecacuprate supramolecular structure determined in solid state.     

Sterically stabilized water based magnetic fluids: Synthesis,structure and properties

Magnetic fluids (MFs), prepared by chemical co-precipitation followed by double layer steric and electrostatic (combined) stabilization of magnetite nanoparticles dispersed in water, are presented. Several combinations of surfactants with different chain lengths (lauric acid (LA), myristic acid (MA), oleic acid (OA) and dodecyl-benzene-sulphonic acid (DBS)) were used, such as LA+LA, MA+MA, LA+DBS, MA+DBS, OA+DBS, OA+OA and DBS+DBS. Static light scattering, transmission electron microscopy, small angle neutron scattering, magnetic and magneto-rheological measurements revealed that MFs with MA+MA or LA+LA biocompatible double layer covered magnetite nanoparticles are the most stable colloidal systems among the investigated samples, and thus suitable for biomedical applications.     

Iron/iron oxides core-shell nanoparticles by laser pyrolysis: Structural characterization and enhanced particle dispersion

Well-dispersed nanoparticles with iron/iron carbide core and iron oxide shell structures may constitute an excellent magnetic material for different applications as magnetic nanofluids, contrast agents in magnetic resonance imaging, sensors and catalysts. Based on the ability of the CO₂ laser pyrolysis technique to synthesize nanoparticles of the Fe/Fe₂O₃ core-shell type, we further improve the powder dispersion by first collecting the nanoparticles in a toluene bubbler, positioned downstream and prior to the collection filter. Structural characterisation of the samples by electron microscopy and X-ray diffraction was performed. Conditions in which clusters contain a reduced number of nanoparticles (around 50) are evidenced. Mean core-shell particle sizes of 15 nm were estimated. Finally, preliminary results on the morphology of iron/iron oxide core-shell nanoparticles as hydrocarbon-based magnetic nanofluids are presented.     

Effect of humic substances on the electrochemical reduction of p -nitrophenol

p-Nitrophenol (PNP) is the main hydrolysis product of methylparathion (MP), one of the most commonly used organophosphate insecticides in the world. Such a product is very toxic for human and animals. Humic substances (HS) are natural recalcitrant organic matter found in soil and waters that have an ability to interact, immobilize, and degrade pesticides. This article presents electroanalytical and UV-Visible studies, conducted to understand the effect of the HS on the PNP reduction process and therefore to understand how the HS can influence PNP degradation in the environment. Electroanalytical results showed that the HS benefit the reduction of the nitro-group of PNP by electrocatalysis. UV-Visible spectra showed that the catalytic effect of HS occurs due to the interection between the PNP and the HS followed by a proton donor mechanism.