The tandem ring-closing metathesis-isomerization approach to 6-deoxyglycals

Protected 3,6-dideoxyglycals have been synthesized de novo as single isomers starting from ethyl lactate by using the tandem RCM-isomerization reaction as the key step. Different relative configurations become accessible by addition of vinyl- or allyl-metal compounds to protected lactaldehydes under Cram-chelate or Felkin-Anh control. The concept is exemplified for glycals of L-rhodinose and L-amicetose, as well as for ring-expanded non-natural analogues thereof. This novel approach to glycals is also applicable to the synthesis of disaccharide glycals via a reiterative strategy, as exemplified for the dimer of L-rhodinose and its non-natural ring expanded analogue.     

Tetrameric Cubic Structures of Two Solvated Lithium Enolates

The structures of the crystalline lithium enolates derived from 3, 3-dimethyl-2-butanone and from cyclopentanone have been determined by X-ray analysis. Both structures are tetrameric aggregates based on a Li₄O₄-cube, each Li⁺-ion being additionally bonded to the O-atom of a tetrahydrofuran solvent molecule.     

Influence of Process Parameters on the Reaction Kinetics of the Chromium‐Catalyzed Trimerization of Ethylene

In this paper we report the results of an extensive experimental kinetic study carried out on the novel ethylene trimerization catalyst system, comprising the chromium source [CrCl₃(thf)₃] (thf=tetrahydrofuran), a Ph₂P‐N(iPr)‐P(Ph)‐N(iPr)H (PNPNH) ligand (Ph=phenyl, iPr=isopropyl), and triethylaluminum (AlEt₃) as activator. It could be shown that the initial activity shows a first‐order dependency on the ethylene concentration. Also, a first‐order dependency was found for the catalyst concentration. The initial activity follows a typical Arrhenius behavior with an experimentally determined activation energy of 52.6 kJ mol^?1. At elevated temperatures (ca. 80 °C), a significant deactivation was observed, which can be tentatively traced back to a ligand rearrangement in the presence of AlEt₃. After a fast initial phase, a pronounced ‘kink’ in the ethylene‐uptake curve is observed, followed by a slow, almost linear, further increase of the total ethylene consumption. The catalyst composition, in particular the ligand/chromium and the cocatalyst/chromium molar ratio, has a strong impact on the catalytic performance of the trimerization of ethylene.     

Structural and redox properties of VOx and Pd/VOx thin film model catalysts studied by TEM and SAED

The oxidation of pure V(2)O(3) and Pd/V(2)O(3) films was studied by Transmission Electron Microscopy (TEM) and Selected Area Electron Diffraction (SAED) in the temperature range 673-773 K. Thin films of V(2)O(3) were prepared by reactive deposition of V metal in 10(-2) Pa O(2) on NaCl(001) cleavage faces. Pd particles were epitaxially grown on NaCl(001) and subsequently embedded in V(2)O(3). Oxidation of both pure V(2)O(3) and Pd/V(2)O(3) at 673 K transforms V(2)O(3) into a platelet-like V(2)O(5) structure. At temperatures T>or= 773 K, a reconstruction of the platelet-like V(2)O(5) structure into an array of oblong and needle-type V(2)O(5) nanocrystals of different size occurs. Subsequent reduction of the so-prepared structures in 1 bar H(2) at 573-673 K results in the formation of the cubic VO phase, whereby the external shape of the original crystals is partially maintained. Upon oxidation at 723 K, Pd is transformed into PdO, but its formation is suppressed in comparison with Pd supported on Al(2)O(3) and occurs only at an about 100 K higher temperature than on Pd/Al(2)O(3). The Pd particles are stabilized against oxidation up to 673 K, PdO decomposes upon reduction in hydrogen between 573 and 673 K.     

Perfluorophenyl–Phenyl Interactions in the Crystallization and Topochemical Polymerization of Triacetylene Monomers

A series of symmetrically and unsymmetrically substituted octa‐2,4,6‐triyne‐1,8‐diol derivatives with benzoyl, 4‐dodecyloxybenzoyl, as well as perfluorobenzoyl substituents were prepared and investigated with respect to their crystal structures and topochemical polymerizability. Single‐crystal structures for several of these triacetylene monomers have been obtained and proved that the perfluorophenyl–phenyl interactions played a decisive role in the molecular packing. As a consequence of the geometric requirements imposed by the perfluorophenyl–phenyl interactions, packing parameters appropriate for a topochemical triacetylene polymerization in the sense of either a 1,6‐ or a 1,4‐polyaddition along different crystallographic axes were observed in two cases, and UV irradiation led to successful polymerization. Raman as well as solid‐state ¹³C NMR spectra of the obtained polymers revealed that the polymerization had predominantly proceeded in the form of a 1,4‐polyaddition.     

Structural control of surface layer proteins at electrified interfaces investigated by in situ Fourier transform infrared spectroscopy

In situ Fourier Transform Infrared (FTIR) Spectroscopy complemented by Electrochemical Quartz Microbalance (EQMB) investigations allowed a detailed insight into the influence of the electrode potential on competing adsorption processes and bonding mechanisms of buffer ions and S-layer protein molecules of Lysinibacillus sphaericus CCM2177 at an electrified liquid/gold interface. The S-layer proteins adsorb on gold polarized positively of the point of zero charge by displacing perchlorate anions in the Helmholtz plane by their carboxylate groups. This is indicated by an increase of the peptide and carboxylate infrared absorption signals accompanied by a decrease of the perchlorate signal. S-layers interlinked laterally with Ca(2+) ions, positive of the point of zero charge, resulted in the formation of a crystalline layer participating in the Helmholtz layer. In contrast to the absence of the Ca(2+)-linkers, S-layers remain structurally intact also in the negative polarization domain where the Helmholtz layer is solely sustained by mainly solvated cations without participation of the negatively charged protein carboxylate functions.     

Application of affinity capillary electrophoresis for charge heterogeneity profiling of biopharmaceuticals

Charge heterogeneity profiling is important for the quality control (QC) of biopharmaceuticals. Because of the increasing complexity of these therapeutic entities [1], the development of alternative analytical techniques is needed. In this work, flow‐through partial‐filling affinity capillary electrophoresis (FTPFACE) has been established as a method for the analysis of a mixture of two similar monoclonal antibodies (mAbs). The addition of a specific ligand results in the complexation of one mAb in the co‐formulation, thus changing its migration time in the electric field. This allows the characterization of the charged variants of the non‐shifted mAb without interferences. Adsorption of proteins to the inner capillary wall has been circumvented by rinsing with guanidine hydrochloride before each injection. The presented FTPFACE approach requires only very small amounts of ligands and provides complete comparability with a standard CZE of a single mAb.