Mass spectrometry and UV‐VIS spectrophotometry of ruthenium(II) [RuClCp(mPTA)2](OSO2CF3)2 complex in solution

Ruthenium(II) complexes are of great interest as a new class of cancerostatics with advantages over classical platinum compounds including lower toxicity. The stability of the [RuClCp(mPTA)₂](OSO₂CF₃)₂ complex (I) (Cp cyclopentadienyl, mPTA N‐methyl 1,3,5‐triaza‐7‐phosphaadamantane) in aqueous solution was studied using spectrophotometry, matrix‐assisted laser desorption/ionization (MALDI) and laser desorption/ionization (LDI) time‐of‐flight (TOF) mass spectrometry (MS). Spectrophotometry proves that at least three different reactions take place in water. Dissolution of I leads to fast coordination of water molecules to the Ru(II) cation and then slow hydrolysis and ligand exchange of chloride and mPTA with water, hydroxide or with trifluoromethane sulfonate itself. Via MALDI and LDI of the hydrolyzed solutions the formation of singly positively charged ions of general formula RuCl_p(Cp)_q(mPTA)_r(H₂O)_s(OH)_t (p = 0–1, q = 0–1, r = 0–2, s = 0–5, t = 0–2) and of some fragment ions was shown. The stoichiometry was determined by analyzing the isotopic envelopes and computer modelling. The [RuClCp(mPTA)₂](OSO₂CF₃)₂ complex can be stabilized in dilute hydrochloric acid or in neutral 0.15 M isotonic sodium chloride solution. Copyright © 2009 John Wiley & Sons, Ltd.     

A preconcentration system using polyamine Metalfix-Chelamine resin for the on-line determination of palladium(II) and platinum(IV) by inductively coupled plasma optical emission spectrometry

A new matrix separation/preconcentration method is developed for the on-line determination of palladium(II) and platinum(IV) in complex matrices using a sequential ICP-OES instrument. These metals are preconcentrated in a microcolumn packed with Metalfix-Chelamine, a polymeric functionalised resin containing the tetraethylenepentamine group. The hydrodynamic and chemical conditions of the flow system affecting the loading and elution steps are optimised off-line using a mixture of 1.0 mol L⁻¹ thiourea and 2.0 mol L⁻¹ NaClO₄ in 4.0 mol L⁻¹ HCl which proved to be the most effective solution for the simultaneous elution of Pd(II) and Pt(IV). High enrichment factors of nearly 35 are achieved for both metals and the detection limits (LOD) are 22 ng L⁻¹ for platinum and 2.5 ng L⁻¹ for palladium. The accuracy of the method was tested by analysing a used pellet catalyst (certified reference material NIST 2556) and trace metal solutions resulting from the leaching of this material. Despite the fact that this CRM contains zirconium and large amounts of aluminium and lead, a high level of agreement was achieved demonstrating the efficiency of the resin in eliminating interfering elements.     

Electroosmotic flow changes due to interactions of background electrolyte counter-ions with polyethyleneimine coating in capillary zone electrophoresis of proteins

The properties and behavior of polyethyleneimine (PEI) covalently coated capillaries with respect to different background electrolytes used in capillary zone electrophoresis (CZE) are described. The coating stability and changes of inner surface charge in the capillary were followed by measurement of electroosmotic flow (EOF). Interest was focused mainly on conjugate bases of carboxylic acids as anionic background electrolyte components (acetate, citrate, malate, malonate, tartrate, and succinate). An interesting phenomenon was observed in PEI-coated capillaries: The direction (and the magnitude) of EOF depends on the composition of the background electrolyte and at a certain pH it can undergo reversible change. Ionic complex formation was suggested as a hypothesis to explain this behavior. With this knowledge, the PEI-coated capillary was used for the separation of basic proteins in the above-mentioned background electrolytes. A standard protein mixture of cytochrome c, ribonuclease A, and lysozyme at a concentration of 0.25 mg/mL each was chosen as model sample.     

Bambus[n]urils: a new family of macrocyclic anion receptors

A recently discovered anion receptor is jointed by three related macrocycles differing in the number of glycoluril units and type of substitution. The synthesis is carried out in nonpolar solvents compared to aqueous media used in the case of the original macrocycle. The size of macrocycle is controlled by a template. A hexameric macrocycle with benzyl substitution binds halide anions with an affinity exceeding 10(9) M(-1) while a tetrameric analog does not bind any of the investigated anions.     

Hypervalent Iodine Based Reversible Covalent Bond in Rotaxane Synthesis

Reversible covalent bonds play a significant role in achieving the high‐yielding synthesis of mechanically interlocked molecules. Still, only a handful of such bonds have been successfully employed in synthetic procedures. Herein, we introduce a novel approach for the fast and simple preparation of interlocked molecules, combining the dynamic bond character of bis(acyloxy)iodate(I) anions with macrocyclic bambusuril anion receptors. The proof of principle was demonstrated on rotaxane synthesis, with near‐quantitative yields observed in both the classical and “in situ” approach. The rotaxane formation was confirmed in the solid‐state and solution by the X‐ray and NMR studies. Our novel approach could be utilized in the fields of dynamic combinatorial chemistry, supramolecular polymers, or molecular machines, as well inspire further research on molecules that exhibit dynamic behavior, but owing to their high reactivity, have not been considered as constituents of more elaborate supramolecular structures.     

Mass spectrometry of nanodiamonds

Detonation nanodiamonds (NDs) were studied by time‐of‐flight mass spectrometry (TOF MS). The formation of singly charged carbon clusters, C, with groups of clusters at n = 1–35, n ∼160–400 and clusters with n ∼8000 was observed. On applying either high laser energy or ultrasound, the position and intensity of the maxima change and a new group of clusters at n ∼70–80 is formed. High carbon clusters consist of an even number of carbons while the percentage of odd‐numbered clusters is quite low (≤5–10%). On increasing the laser energy, the maximum of ionization (at n ∼200 carbons) is shifted towards the lower m/z values. It is suggested that this is mainly due to the disaggregation of the original NDs. However, the partial destruction of NDs is also possible. The carbon clusters (n ∼2–35) are partially hydrogenated and the average value of the hydrogenation was 10–30%. Trace impurities in NDs like Li, B, Fe, and others were detected at high laser energy. Several matrices for ionizing NDs were examined and NDs themselves can also be used as a matrix for the ionization of various organic compounds. When NDs were used as a matrix for gold nanoparticles, the formation of various gold carbides Au_mC_n was detected and their stoichiometry was determined. It was demonstrated that TOF MS can be used advantageously to analyze NDs, characterize their size distribution, aggregation, presence of trace impurities and surface chemistry. Copyright © 2009 John Wiley & Sons, Ltd.     

Laser ablation of AgSbS2 and cluster analysis by time‐of‐flight mass spectrometry

Thin films of AgSbS₂ are important for phase‐change memory applications. This solid is deposited by various techniques, such as metal organic chemical vapour deposition or laser ablation deposition, and the structure of AgSbS₂(s), as either amorphous or crystalline, is already well characterized. The pulsed laser ablation deposition (PLD) of solid AgSbS₂ is also used as a manufacturing process. However, the processes in plasma have not been well studied. We have studied the laser ablation of synthesized AgSbS₂(s) using a nitrogen laser of 337 nm and the clusters formed in the laser plume were identified. The ablation leads to the formation of various single charged ternary Ag_pSb_qS_r clusters. Negatively charged AgSbS, AgSb₂S, AgSb₂S, AgSb₂S and positively charged ternary AgSbS⁺, AgSb₂S⁺, AgSb₂S, AgSb₂S clusters were identified. The formation of several singly charged Ag⁺, Ag, Ag, Sb, Sb, S ions and binary Ag_pS_r clusters such as AgSb, Ag₃S^?, SbS (r = 1–5), Sb₂S^?, Sb₂S, Sb₃S (r = 1–4) and AgS, SbS⁺, SbS, Sb₂S⁺, Sb₂S, Sb₃S (r = 1–4), AgSb was also observed. The stoichiometry of the clusters was determined via isotopic envelope analysis and computer modeling. The relation of the composition of the clusters to the crystal structure of AgSbS₂ is discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Laser ablation of ternary As‐S‐Se glasses and time‐of‐flight mass spectrometric study

Ternary chalcogenide As‐S‐Se glasses, important for optics, computers, material science and technological applications, are often made by pulsed laser deposition (PLD) technology but the plasma composition formed during the process is mostly unknown. Therefore, the formation of clusters in a plasma plume from different glasses was followed by laser desorption ionization (LDI) or laser ablation (LA) time‐of‐flight mass spectrometry (TOF MS) in positive and negative ion modes. The LA of glasses of different composition leads to the formation of a number of binary As_pS_q, As_pSe_r and ternary As_pS_qSe_r singly charged clusters. Series of clusters with the ratio As:chalcogen = 3:3 (As₃S, As₃S₂Se⁺, As₃SSe), 3:4 (As₃S, As₃S₃Se⁺, As₃S₂Se, As₃SSe, As₃Se), 3:1 (As₃S⁺, As₃Se⁺), and 3:2 (As₃S, As₃SSe⁺, As₃Se), formed from both bulk and PLD‐deposited nano‐layer glass, were detected. The stoichiometry of the As_pS_qSe_r clusters was determined via isotopic envelope analysis and computer modeling. The structure of the clusters is discussed. Copyright © 2009 John Wiley & Sons, Ltd.