Quantitation in capillary electrophoresis-mass spectrometry

CE-MS has evolved into a strong alternative to LC-MS. Most of CE-MS applications deal with characterization and identification. However, quantitative aspects have gained importance in, e.g., pharmaceutical and biotechnological applications. Here we summarize and evaluate various methodological aspects in order to achieve sensitive and reproducible results. Similar to LC-MS, aspects of matrix influence on the electrospray process need to be carefully addressed when quantitative results are intended by CE-MS. Due to a more complicated coupling special emphasis needs to be put on the CE-MS interface. Generally linearity over more than three orders of magnitude can be achieved by CE-ESI-MS. Furthermore, a literature survey has been performed in order to give an overview over quantitative measurements performed by CE-MS. The precision can be doubled when changing from a structural related to an isotopically labeled internal standard. Thus a level of precision better than 5% RSD can be achieved.     

Capillary zone electrophoresis of natural organic matter

This paper presents an in-depth look at the use of capillary electrophoretic (CE) techniques for the fingerprinting and characterization of humic substances and natural organic matter. These materials are highly heterogeneous in structure and show all characteristics of mixtures unliked in analytical chemistry. The electrophoretic approach, however, allows the determination of mobility distributions in different solution conditions, representative of the effective charge and size distribution status of the components present. A tabulated review covers over 50 references on the subject and highlights the possibilities and problems encountered in the analysis of such polydisperse materials with CE methods. In a second part of the article the consequences of experimental and buffer parameters on the behavior of humic materials in CE are presented.     

On a characterization of polynomials by divided differences

Summary We consider the functional equationf[x ₁,x ₂,, x _n ] =h(x ₁ + +x _n ) (x ₁,,x _n K, x _j x _k forj k), (D) wheref[x ₁,x ₂,,x _n ] denotes the (n – 1)-st divided difference off and prove Theorem. Let n be an integer, n 2, let K be a field, char(K) 2, with # K 8(n – 2) + 2. Let, furthermore, f, h: K K be functions. Then we have that f, h fulfil (D) if, and only if, there are constants a_j K, 0 j n (a := a_n, b := a_{n – 1}) such thatf = ax ⁿ +bx ^{n – 1} + +a ₀ and h = ax + b.     

The relative importance of temperature and isotope effects on the dipole oscillator strength distribution of H2

Summary The calculation of the effects of temperature and isotopic composition on the energy weighted moments of the dipole oscillator strength distribution of H₂ in the random phase approximation to the polarization propagator are reported. It is seen that the effect of isotopic composition is small, while that of temperature is of an order accessible to experiment. We find that all the mean excitation energiesI , for =–1, 0, 1, decrease with temperature as does the dipole oscillator strength momentS() for >0, while the opposite is true for <0. These effects are interpreted in terms of the bond length dependence of the excitation energies.     

The structure of magnesium alanate

Mg(AlH(4))(2) was produced as a nanocrystalline powder by metathesis of NaAlH(4) and MgCl(2). Starting with a structure estimation which was developed from an evaluation of FTIR data and comparison of structural properties of two solvent adducts, quantum chemical calculations were performed on the density functional theory (DFT) level. The calculated atomic positions were used to simulate an X-ray powder diffraction pattern, based on a trigonal unit cell. The simulated pattern was congruent to experimental data. Thus, magnesium alanate exhibits a CdI(2) layer structure, the layers being formed by Mg atoms occupying the Cd sites and AlH(4) tedrahedra occupying the sites of the iodine atoms in CdI(2).     

Über Na2PrO3 und Na2TbO3

On Na₂PrO₃ and Na₂TbO₃ Using an exchange reaction of Na₂O with Li₈TbO₆ (Na : Tb = 2.1 : 1; au-tube; 750°C, 30 d) yellow-orange colored single crystals of Na₂TbO₃ could be prepared for the first time. Na₂TbO₃ crystallizes monoclinic in C2/c (Z = 8; a = 576.92(6), b = 1001.27(9), c = 1117.91(14) pm, β = 99.98(1)°). According to four-circle data the Li₂SnO₃-type of structure is adopted (PW 1100, MoKα , 1935 I₀ (hkl), R = 4.86%, R_w = 3.63% for all 928 unique reflexions). By a similar exchange reaction of Na₂O with Li₈PrO₆ for the first time single crystals of Na₂PrO₃ could be prepared, too (Na : Pr = 2.2 : 1; au-tube; 700°C; 23 d). The structure determination reveils that there is a variant of the NaCl-type of structure, which ressembles to the Li₂SnO₃-type of structure (PW 1100, MoKα , 2199 I₀ (hkl)), R = 8.88%, R_w = 5.21% for all 947 unique reflexions; C2/c, Z = 8, a = 678.78(5), b = 977.47(7), c = 1080.38(9) pm, β = 108,4(1)°. In contrast to Na₂TbO₃ there are no layers according to NaO(Na_1/3Tb_2/3)O. All octahedral intersticies are occupied systematically with Pr⁴⁺ and Na⁺ : (Na_2/3Pr_1/3)O(Na_2/3Pr_1/3)O.     

Diastereoselective synthesis of 2-aminoalkyl-3-sulfonyl-1,3-oxazolidines on solid support

Herein we report our investigation on the oxidation of solid-support-bound amino alcohols to their corresponding aldehydes. These aldehydes were converted into diastereomerically pure (>10:1) 2,4-cis-2-aminoalkyl-3-sulfonyl-1,3-oxazolidines using optically pure 1,2-amino alcohols. The relative configuration was determined using the nuclear Overhauser effect (NOE). The synthesized oxazolidines, which were obtained in high purities, represent a new, diverse scaffold for the solid-phase synthesis of libraries directed toward a pharmacological target.     

Zwei neue Metatitanate mit fünffach koordiniertem Titan: CsNaTiO3 und RbNaTiO3

Two New Metatitanates with Five-coordinated Titanium: CsNaTiO₃ and RbNaTiO₃ [1] The new oxides CsNaTiO₃ (I) and RbNaTiO₃ (II) are obtained by heating well grounded mixtures of the binary oxides in Ni-tubes as colourless platelike crystals. I: CsO_0.56, NaO_0.48 and TiO₂, Cs:Na:Ti = 1.1:1.1:1.0; 600°C, 61 d as well as CsO_0.97, NaO_0.48 and Ti₂O₃, Cs:Na:Ti = 1.5:3.0:1.0; 760°C, 27 d. II: RbO_0.52, NaO_0.48 and TiO₂, Rb:Na:Ti = 1.1:1.1:1.0; 750°C, 14 d as well as RbO_0.98, NaO_0.48 and Ti₂O₃, Rb:Na:Ti = 1.5:3.1:1.0; 760°C, 27 d. CsNaTiO₃ (orthorhombic, Cmcm) is nearly isostructural with KNaTiO₃ [2]; a = 601.4(1) pm, b = 1 120.3(1) pm, c = 563.4(1) pm (Guinier-Simon-Data, Z = 4). RbNaTiO₃ (monoclinic, C2/c) is isostructural with KNaTiO₃; a = 590.3(1) pm, b = 1 098.4(1) pm, c = 555.1(0) pm, β = 92.15° (Guinier-Simon-Data, Z = 4). Both structures are determined by using four-circle diffractometer data (CsNaTiO₃: Siemens AED2, 2 896I_o(hkl), MoKα , R = 2.4%, R_w = 2.3%; RbNaTiO₃: Philips PW 1 100, 2 743I_o(hkl), AgKα , R = 9.9%, R_w = 8.9%; additional data see text). The Madelung Part of Lattice Energy (MAPLE), Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR) and the Charge Distribution in Solids are calculated and discussed.     

Über Oxorhodate der Alkalimetalle: β-LiRhO2

On Oxorhodates of Alkali Metals: β-LiRhO₂ We prepared hitherto unknown β-LiRhO₂ in form of black, cubic single crystals, O⁴–F4₁32, a = 841.27(6) pm, Z = 16. For a first time in case of such metal oxides we find one of the possible variants of order between the NaCl-type with random distribution and the complete ordered types like α-NaFeO₂ as a single crystal (four-circle-diffractometer PW 1100, AgKα, 100 von 109 I₀(hkl), R = 9.10%, R_w = 5.46%). The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, were calculated and discussed.     

Synthesis of quinolines, 2-quinolones, phenanthridines, and 6(5h)-phenanthridinones via palladium[0]-mediated Ullmann cross-coupling of 1-bromo-2-nitroarenes with beta-halo-enals, -enones, or -esters

Palladium[0]-mediated Ullmann cross-coupling of 1-bromo-2-nitrobenzene (1 R = H) and its derivatives with a range of beta-halo-enals, -enones, or -esters readily affords the corresponding beta-aryl derivatives, which are converted into the corresponding quinolines, 2-quinolones, phenanthridines, or 6(5H)-phenanthridinones on reaction with dihydrogen in the presence of Pd on C or with TiCl(3) in aqueous acetone. [reaction: see text]