Investigations of reactions involved in flameless atomic absorption procedures : Part IV. A theoretical study of factors influencing the determination of aluminium

High-temperature equilibrium calculations are used to study potential interferences in the determination of aluminium by flameless a.a.s. The conditions for the formation of interfering aluminium compounds like AlO(g), Al₂O(g), Al₂O₃(s), AlOH(g), AlH(g), AlHO₂(g), AlS(g), AlN(g), AlN(s) and AlCl(g) have been calculated. The influence of kinetic parameters on the equilibrium calculations for the reactions involving carbon—oxygen and carbon—sulphur has been established by varying the input amount of carbon. The results indicate that even in the nanomole range the presence of elements like H, O, N, Cl and S may cause severe interferences during the atomization step (2300–2900 K)     

Structural Consequences of S → Se Substitution in some Symmetrical [M(S2CNR2)3] Complexes

The consequences of replacement of the symmetrically chelate ligands in [M(E₂CNR₂)₃] (E = S, Se) complexes of potential 32 symmetry by analogous mixed S,Se unsymmetrical chelates are explored for both small (M = Co) and large (M = In) metal atoms, and R = primary (Et) and secondary (ⁱPr) alkyl substituents by way of low‐temperature single crystal X‐ray studies of [(Co(SSeCNEt₂)₃] ([Co(Se₂CNEt₂)₃] also determined as datum), and [In(SSeCNR₂)₃], R = Et, ⁱPr. The structure of [(ⁱPr₂N·CS·Se)₂] is also recorded.     

Synthese und Charakterisierung funktionalisierter β‐Hydroxydithiozimtsäuren und deren Ester. Komplexchemisches Verhalten gegenüber Nickel(II), Palladium(II) und Platin(II)

Synthesis and Analytical Characterization of Functionalized β‐Hydroxydithiocinnamic Acids and their Esters. Complex Chemistry towards Nickel(II), Palladium(II), and Platin(II) Starting from silyl‐protected 4‐hydroxy acetophenone ( 1 ) the 1,1‐ethenedihiolato complexes 3 – 5 were synthesised using carbon disulfide and potassium‐tert‐butylate as a base. After being deprotected, the resulting 4‐hydroxy‐substituted complexes 6 – 8 were esterified with DL‐α‐lipoic acid to obtain the compounds 9 – 11 . The resulting complexes were characterized using NMR spectroscopy, mass spectrometry and IR spectroscopy. 3‐substituted β‐hydroxydithiocinnamic acid methyl ester ( 12 ) was obtained via an analogous path of reaction using silyl‐protected 3‐hydroxy acetophenone ( 2 ), carbon disulfide and methyl iodide. After removing of the silyl group the resulting hydroxy group was esterified with DL‐α‐lipoic acid. Using the dithioacid ester 14 as a ligand the Ni^II ( 15 ), Pd^II ( 16 ) and Pt^II ( 17 ) [O,S] complexes were obtained.     

Investigations of reactions involved in electro-thermal atomic absorption procedures : Part 8. A theoretical and experimental study of factors influencing the determination of phosphorus

Ideal conditions for the determination of phosphorus by graphite-furnace atomic absorption spectrometry are investigated by the use of high-temperature equilibrium calculations. All reasonable reaction products resulting from the reaction between P, C, O, H, N, Ca and Ar are considered. The calculations show that phosphorus forms the volatile monoxide and dioxide molecules below 1800 K (P_o2? 10^-13 atm.). At higher temperatures the relative amount of atomic phosphorus is mainly controlled by the equilibrium between monatomic and diatomic phosphorus. The significance of the theoretical ' study was investigated experimentally. The relative amounts of P₂ and PO were monitored by molecular absorption using vaporization under isothermal conditions; the interfering effects of Ca, N₂, H₂, and O₂ on the atomic absorption signal for phosphorus were also studied. The sensitivity was greatly dependent on graphite tube conditions as well as the heating rate of the furnace. For CaHPO₄ the sensitivity for phosphorus was 4.5 × lO^-8 g. If samples were introduced into a preheated tube, this value was improved to 2 × 10^-9 g.     

Pfropfcopolymerisation von Cellulose mit zwei Vinylmonomeren

Zusammenfassung Die vorliegende Arbeit stellt eine Beschreibung von Experimenten dar, die die Erhöhung der Pfropfbereitschaft von trägen Komponenten durch Beimischung von aktiveren zum Ziele hatten.Das Trägermolekül war in allen Fällen Cellulose in Form von hochgradig gereinigtem Zellstoff. Durch die Verwendung von Mischsystemen aus Styrol und Methylmethacrylat gelang es, das trägere Styrol in bedeutend größerer Menge auf die Cellulose aufzupfropfen, als es bei Abwesenheit des aktiven Methylmethacrylats der Fall war.

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Grafting Polymerization of Cellulose with Two Vinyl Monomers

This paper describes experiments to increase the grafting of cellulose with components of poor reactivity by mixing them with highly reactive ones. A highly purified wood pulp was used as backbone. Using combinations of styrene and methyl methacrylate it was possible to graft considerably higher amounts of the poorly reacting styrene than in the absence of the highly reactive methyl methacrylate.

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Nach einem Vortrag, den der erstgenannte der Autoren im Rahmen der Arbeitstagung des Vereins Österreichischer Chemiker am 27. September 1968 in Wien gehalten hat.     

Fabrication of magnetically separable mesostructured silica with an open pore system

Magnetically separable mesostructured silica with an unobstructed pore system was fabricated through the deposition of cobalt nanoparticles on the outer surface of the submicron-sized silica particles. These cobalt nanoparticles were further protected by a nanometer-thick carbon shell against acid erosion. Due to the fact that the magnetic particles are grafted on the outer surface of the porous silica, the pores are still accessible for further modification, which could widen the application range of porous silica.     

Evaluation of methods to measure differential 15N labeling of soil and root N pools for studies of root exudation

To study patterns of root exudation, the effectiveness of different techniques for in situ 15N labeling of Brassica napus, Centaurea jacea and Lolium perenne with ammonium nitrate was tested. Stem infiltration was found to effectively label plants with thicker stems, whereas, for grass species, cutting and immersing the leaf tips into 15N solution proved to be most effective. A microdiffusion technique to isolate ammonium, combined with conventional cation-exchange chromatography to separate nitrate from amino-N compounds thereafter, was found suitable for separation of the N fractions of plant and soil extracts for 15N determination. All three species were then cultivated in nutrient solution and labeled with 15NH4 15NO3 by stem feeding for 42 hours. Kinetics of 15N labeling of bulk roots and shoots as well as hot water extractable material were assessed, and up to 1.1 at% 15N excess (APE) was found in nutrient solutions. The main amino acids exuded by L. perenne were glycine, serine, alanine and aspartic acid. To assess the suitability of this set of methods to study root exudation in field settings, L. perenne was grown without fertiliser addition in pots containing low-nutrient soil. Plants were 15N labeled via tip immersion and 15N and N concentrations were analysed in shoots, roots and soils during a 48-h interval. Shoots reached 1.25 APE, roots and soil 0.10 and 0.005 APE, respectively. Between 4% (48 h) and 6% (24 h) of total plant 15N was exuded by roots into the soil. In roots amino acids comprised the largest proportion of the soluble 15N pool, whereas soil 15N levels were similar for amino acids and ammonium, exceeding those of nitrate. Mechanisms for the shift within N fractions from roots to soils are briefly discussed.     

Operational variables in high-performance liquid chromatography-electrospray ionization mass spectrometry of peptides and proteins using poly(styrene-divinylbenzene) monoliths

Capillary reversed-phase high-performance liquid chromatography (RP-HPLC) utilizing monolithic poly(styrene-divinylbenzene) columns was optimized for the coupling to electrospray ionization mass spectrometry (ESI-MS) by the application of various temperatures and mobile phase additives during peptide and protein analysis. Peak widths at half height improved significantly upon increasing the temperature and ranged from 2.0 to 5.4 s for peptide and protein separations at 70 degrees. Selectivity of peptide elution was significantly modulated by temperature, whereas the effect on proteins was only minor. A comparison of 0.10% formic acid (FA), 0.050% trifluoroacetic acid (TFA), and 0.050% heptafluorobutyric acid (HFBA) as mobile phase additives revealed that highest chromatographic efficiency but poorest mass spectrometric detectabilities were achieved with HFBA. Clusters of HFBA, water, and acetonitrile were observed in the mass spectra at m/z values >500. Although the signal-to-noise ratios for the individual peptides diverged considerably both in the selected ion chromatograms and extracted mass spectra, the average mass spectrometric detectabilities varied only by a factor of less than 1.7 measured with the different additives. Limits of detection for peptides with 500 nl sample volumes injected onto a 60 mm x 0.20 mm monolithic column were in the 0.2-13 fmol range. In the analysis of hydrophobic membrane proteins, HFBA enabled highest separation selectivity at the cost of lower mass spectral quality. The use of 0.050% TFA as mobile phase additive turned out to be the best compromise between chromatographic and mass spectrometric performance in the analysis of peptides and proteins by RP-HPLC-ESI-MS using monolithic separation columns.     

Cation-induced collapse of low-molecular-weight polyacrylic acid in the dispersion of barium titanate

Observations on the steric layers formed by the adsorption of low-molecular-weight polyacrylic acid (PAA) were taken using the colloidal probe method in an atomic force microscope. The effects of divalent barium ions and of monovalent potassium ions at varying concentrations were observed on the repulsive interaction profiles. High ionic concentrations screened double-layer forces to small distances, whereby the acting forces were reduced to steric interactions. De Gennes scaling theory was used to model the effect of electrolyte on an aqueous barium titanate system, which was stabilized with PAA. The brush model was found to represent the force curves better than the mushroom model. The collapse of PAA layers with increasing salt approximated a grafted polymer brush in monovalent electrolyte, but the addition of barium ions caused markedly less steric collapse. It is suggested that the formation of a Ba(2+)-PAA complex in the adsorbed layer increases its compressibility parameter.