Continuous beds with vancomycin as chiral stationary phase for capillary electrochromatography

Enantiomeric separations in capillary electrochromatography (CEC) carried out using a continuous-bed chiral stationary phase (CSP) based on the macrocyclic antibiotic, vancomycin, is presented. The continuous beds were prepared from methacryloxypropyl modified fused silica capillaries (100 microm ID) by in situ copolymerization of N-(hydroxymethyl)acrylamide and piperazine diacrylamide with vinyl sulfonic acid comonomer used to introduce ionic functionality and thus a strong electroosmotic flow (EOF). The CSP was subsequently prepared by immobilizing the vancomycin stationary phase by reductive amination. Preliminary results have indicated that an extremely strong EOF is obtained in both the nonaqueous polar organic (15.2 x 10(-5) cm2 V(-1) s(-1) and the aqueous reversed-phase modes of operation (8.5 x 10(-5) cm2 V(-1) s(-1)). Enantioselectivity was obtained for four racemic compounds, the best of which was in the case of thalidomide which was separated in 10 minutes with high resolution (Rs = 2.5) and efficiency (120,000 plates meter(-1)) values.     

Nuclear corrections in neutrino-nucleus deep inelastic scattering and their compatibility with global nuclear parton-distribution-function analyses

We perform a global χ2 analysis of nuclear parton distribution functions using data from charged current neutrino-nucleus (νA) deep-inelastic scattering (DIS), charged-lepton-nucleus (?(±)A) DIS, and the Drell-Yan (DY) process. We show that the nuclear corrections in νA DIS are not compatible with the predictions derived from ?(±)A DIS and DY data. We quantify this result using a hypothesis-testing criterion based on the χ2 distribution which we apply to the total χ2 as well as to the χ2 of the individual data sets. We find that it is not possible to accommodate the data from νA and ?(±)A DIS by an acceptable combined fit. Our result has strong implications for the extraction of both nuclear and proton parton distribution functions using combined neutrino and charged-lepton data sets.     

Development of a Combined Standard Additions/Internal Standards Method to Quantify Residual PEG in Ethoxylated Surfactants by MALDI TOFMS

Measuring the residual polyethylene glycol (PEG) in polyethylene oxide (PEO)-based surfactants is important to fully understanding the performance of these materials. Traditional methods of quantitating PEG in PEO-based surfactants can be time-consuming and struggle with low amounts or overlapping molecular mass distributions. This paper describes a matrix-assisted laser desorption/ionization (MALDI) mass spectrometry method developed to quantitate residual PEG in a series of ethoxylated surfactants. The technique addresses the difficulties faced in doing quantitative MALDI experiments by utilizing both internal standard and standard additions protocols. The method produces excellent straight line standard addition plots, and the quantitative results are verified using both a constructed standard and an independent traditional chromatographic separation.     

Investigations of matrix-assisted laser desorption/ionization sample preparation by time-of-flight secondary ion mass spectrometry

Matrix-assisted laser desorption/ionization (MALDI) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) analyses are compared to gain insight into some of the details of sample preparation for MALDI analysis of synthetic polymers. ToF-SIMS imaging of MALDI samples shows segregation of the cationization agent from the matrix crystals. The amount of observed segregation can be controlled by the sample preparation technique. Electrospray sample deposition minimizes segregation. Comparing ToF-SIMS and MALDI mass spectra from the same samples confirms that ToF-SIMS is significantly more surface sensitive than MALDI. This comparison shows that segregation of the oligomers of a polymer sample can occur during MALDI sample preparation. Our data indicate that MALDI is not as sensitive to those species dominating the sample surface as to species better incorporated into the matrix crystals. Finally, we show that matrix-enhanced SIMS can be an effective tool to analyze synthetic polymers, although the sample preparation conditions may be different than those optimized for MALDI.     

Confirmation of vanadium complex formation using electrospray mass spectrometry and determination of vanadium speciation by sample stacking capillary electrophoresis

Capillary zone electrophoresis (CZE) with UV detection was used to determine vanadium species. Nitrilotriacetic acid (NTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), ethylene glycol-bis(2-aminoethylether)-tetraacetic acid (EGTA) and 2,6-pyridinedicarboxylic acid (PDCA) were investigated to determine whether these ligands formed stable anionic complexes with vanadium. Of all the ligands studied HEDTA was the most suitable ligand because it gave the largest UV response with reasonable migration time. Electrospray mass spectrometry (ES-MS) was used to confirm the formation of [VO₂(HEDTA)]²⁻ and [VO(HEDTA)]¹⁻ in solution. An electrolyte containing 25 mM phosphate, 0.25 mM tetradecyltrimethylammonium bromide (TTAB) at pH 5.5 was optimum for the separation of these anionic vanadium complexes. Sample stacking techniques, including large-volume sample stacking (LVSS) and field-amplified sample injection (FASI), were tested to improve the sensitivity. Best sensitivity was obtained using FASI, with detection limits of 0.001 μM, equivalent to 0.4 μg L⁻¹, for [VO₂(HEDTA)]²⁻ and 0.01 μM, equivalent to 3.4 μg L⁻¹ for [VO(HEDTA)]¹⁻. The utility of the method for the speciation of V(IV) and V(V) was demonstrated using ground water samples.     

2'-O-[2-[N,N-(dialkyl)aminooxy]ethyl]-modified antisense oligonucleotides

[structure] Oligonucleotides with two novel modifications, 2'-O-?2-[N, N-(dimethyl)aminooxy]ethyl? (2'-O-DMAOE) and 2'-O-?2-[N, N-(diethyl)aminooxy]ethyl? (2'-O-DEAOE), have been synthesized. These modifications exhibit high binding affinity to target RNA (and not to DNA) and enhance the nuclease stability of oligonucleotides considerably with t(1/2) > 24 h as a phosphodiester.     

Photon Asymmetry of Deuteron Photodisintegration Between 160 and 410 MeV

 The photon asymmetry Σ of the reaction has been measured across the photon energy range 160–410 MeV at the Mainz Microtron MAMI. Linearly polarized photons were obtained from coherent bremsstrahlung and their energies were determined with the Glasgow tagging spectrometer. The large acceptance detector DAPHNE enabled the outgoing protons to be measured over the complete azimuthal range and for polar angles from 35° to 155° in the c.m. system. The data are compared with existing results and recent theoretical calculations. Received August 22, 1998; accepted for publication February 8, 1999     

Upgrade of the Glasgow photon tagging spectrometer for Mainz MAMI-C

The Glasgow photon tagging spectrometer at Mainz has been upgraded so that it can be used with the 1500MeV electron beam now available from the Mainz microtron MAMI-C. The changes made and the resulting properties of the spectrometer are discussed.     

Determination of the neutron electric form factor in the D(e,e′n)p reaction and the influence of nuclear binding

The electric form factor of the neutron G _E,n has been determined at the Mainz Microtron MAMI at the low momentum transfer Q ²= 0.15 (GeV/c)² in a measurement of the recoil polarisation ratio P _x/P_z in the quasifree reaction D(e,e′n)p. At this Q ² the influence of the nuclear binding is strong. A purely kinematical model is used to get some insight into the effect of the initial Fermi momentum distribution of the neutron. The influence of the final state interaction is determined quantitatively by a model of Arenh?vel et al.. After the corresponding corrections a value of G _E,n(0.15 (GeV/c)²) = 0.0481±0.0065_stat±0.0053_syst is obtained. Received: 12 April 1999     

The angular distribution of the 12C(γ,pn) reaction for Eγ=120−150 MeV

The angular distribution of nucleons emitted in the ¹²C(γ,pn) reaction has been measured using tagged photons at the Mainz microtron MAMI. The variation of the reaction strength with the polar angles of the two emitted nucleons is reported for E_γ=120−150 MeV. The proton angular distribution peaks at more backward angles than the ²H(γ,p) differential cross section indicating a departure from the simple quasi-deuteron model of 2N photo-emission. The distribution shape is in reasonable agreement with microscopic theoretical models which include both π- and ρ-exchange. Received: 3 September 1997 / Revised version: 17 December 1997