Role of the C3-substituted derivatives of cinchonidine in the enantioselective hydrogenation of ethyl pyruvate on Pt-alumina catalyst in AcOH

Summary The enantioselective hydrogenation of ethyl pyruvate (EtPy) was studied on Pt-alumina catalysts modified by C3-substituted cinchonidines (NC, A, B, C1, C2in Fig. 1) and for comparison by DHCDand MeO-DHCDin AcOH. The effect of the C3-substituent on the reaction rate and the enantioselectivity were examined. Using the Engelhard 4759 catalyst under mild experimental conditions (room temperature, hydrogen pressure 1 bar) such as DHCDthe (R)-ethyl lactate formed in excess (e.e.max: 79-91%)</o:p>     

Nematic phase transitions in mixtures of thin and thick colloidal rods

We report experimental measurements of the phase behavior of mixtures of thin (charged semiflexible fd virus) and thick (fd-PEG, fd virus covalently coated with polyethylene glycol) rods with diameter ratio varying from 3.7 to 1.1. The phase diagrams of the rod mixtures reveal isotropic-nematic, isotropic-nematic-nematic, and nematic-nematic coexisting phases with increasing concentration. In stark contrast to predictions from earlier theoretical work, we observe a nematic-nematic coexistence region bound by a lower critical point. Moreover, we show that a rescaled Onsager-type theory for binary hard-rod mixtures qualitatively describes the observed phase behavior.     

Determination of <Superscript>93</Superscript>Zr in nuclear power plant wastes

A radioanalytical method (based on separation using UTEVA columns and ICP-MS measurement) has been used for determination of ⁹³Zr in 37 nuclear power plant samples. As ⁹³Nb might affect the detection of ⁹³Zr, Monte Carlo activation model was used to calculate the expected ⁹³Zr/^natZr mass ratio, which was compared to measured ones. It was found, that a decontamination factor of 10³ is sufficient to get a measurement uncertainty of less than 10%.     

GC–MS Studies of Thiophenes in the Supercritical Fluid CO2 and Solvent Extracts of Tagetes patula L.

The intact plant parts and genetically modified hairy root clone #TpA6 of Tagetes patula were extracted with supercritical fluid CO₂ extraction (SFE) and a conventional solvent extraction. SFE optimization included the variation of fluid CO₂ pressure, dynamic time, and the addition of methanol modifier co-solvent. The four characteristic thiophene metabolites, 5-(3-buten-1-ynyl)-2,2′-bithienyl (BBT), 2,2′:5′,2″-terthiophene (α-T), 5-(4-acetoxy-1-butynyl)-2,2′-bithienyl (BBTOAc), and 5-(3,4-diacetoxy-1-butynyl)-2,2′-bithienyl [BBT(OAc)₂], were analysed by GC–MS. The proposed SFE method allowed the selective extraction of thiophenes in 60 min dynamic time with supercritical CO₂ without modifier co-solvent, at 30 MPa and 40 °C. The SFE and the reference solvent extraction yielded similar results. The SFE of intact roots and flowers yielded 717 ± 31.3 and 480 ± 26.6 μg g^?1 α-T, respectively, while the leaves did not contain considerable amounts of thiophenes. Remarkable amounts of BBT, BBTOAc, and BBT(OAc)₂ were characteristic of the SFE of hairy root cultures.     

Comparative study of new shell-type,sub-2 μm fully porous and monolith stationary phases,focusing on mass-transfer resistance

Today sub-2 μm packed columns are very popular to conduct fast chromatographic separations. The mass-transfer resistance depends on the particle size but some practical limits exist not to reach the theoretically expected plate height and mass-transfer resistance. Another approach applies particles with shortened diffusion path to enhance the efficiency of separations. In this study a systematical evaluation of the possibilities of the separations obtained with 5 cm long narrow bore columns packed with new 2.6 μm shell particles (1.9 μm nonporous core surrounded by a 0.35 μm porous shell, Kinetex™, Core-Shell), packed with other shell-type particles (Ascentis Express™, Fused-Core), totally porous sub-2 μm particles and a 5 cm long narrow bore monolith column is presented. The different commercially available columns were compared by using van Deemter, Knox and kinetic plots. Theoretical Poppe plots were constructed for each column to compare their kinetic performance. Data are presented on polar neutral real-life analytes. Comparison of a low molecular weight compounds (MW = 270–430) and a high molecular weight one (MW ∼ 900) was conducted. This study proves that the Kinetex column packed with 2.6 μm shell particles is worthy of rivaling to sub-2 μm columns and other commercially available shell-type packings (Ascentis Express or Halo), both for small and large molecule separation. The Kinetex column offers a very flat C term. Utilizing this feature, high flow rates can be applied to accomplish very fast separations without significant loss in efficiency.     

New chiral catalysts: synthesis and fragmentation pattern of C9-o-silanized cinchonidines

Summary We synthesized C9-O-silyl ethers of cinchonidine and dihydrocinchonidine (1-8), seven of which have not been known before. The structures of the compounds were verified by ESI-ion-trap MS and ¹H-NMR. Fragmentation of silyl ethers containing Si-phenyl bonds was studied for the first time. The compounds obtained will be utilized as chiral catalysts of certain asymmetric syntheses.</o:p>     

Robust UHPLC Separation Method Development for Multi-API Product Containing Amlodipine and Bisoprolol: The Impact of Column Selection

This paper describes a new and fast ultra-high pressure liquid chromatographic separation of amlodipine and bisoprolol and all their closely related compounds, for impurity profiling purposes. Computer-assisted method development was applied and the impact of several state-of-the-art stationary phase column chemistries (50 × 2.1 mm, sub-2 μm, and core–shell type materials) on the achievable selectivity and resolution was investigated. The work was performed according to quality by design principles using design of experiment with three experimental factors; namely the gradient time (t _G), temperature (T), and mobile phase pH. Thanks to modeling software, it was proved that the separation of all compounds was feasible on numerous column chemistries within <10 min, by proper adjustments of variables. It was also demonstrated that the reliability of predictions was good, as the predicted retention times and resolutions were in good agreement with the experimental ones. The final, optimized method separates 16 peaks related to amlodipine and bisoprolol within 7 min, ensuring baseline resolution between all peak-pairs.     

Die Papierelektrophorese von Phenolen

Zusammenfassung Es wird über die Papierelektrophorese ein-und mehrwertiger teilweise auch substituierter Phenole sowie einiger saurer Kupplungskomponenten für Azofarbstoffe berichtet. Nachweismittel und Wanderungsweiten unter vergleichbaren Versuchsbedingungen werden angegeben, desgleichen wird versucht, Zusammenhänge zwischen Konstitution und Laufweite zu finden.DiplomarbeitI. Szabolcs, Techn. Hochschule, Wien 1959.