On-column polymer-imbedded graphite inlet electrode for capillary electrophoresis coupled on-line with flow injection analysis in a poly(dimethylsiloxane) interface

A method for coupling an electrophoretic driven separation to a liquid flow, using conventional fused-silica capillaries and a soft polymeric interface is presented. A novel design of the electrode providing high voltage to the electrophoretic separation was also developed. The electrode consisted of a conductive polyimide/graphite imbedded coating immobilized onto the capillary electrophoresis (CE) column inlet. This integrated electrode gave the same separation performance as a commonly used platinum electrode. The on-column electrode also showed good electrochemical stability in chronoamperometric experiments. In addition, with this electrode design, the electrode position relative to the inlet end of the CE column will always be constant and well defined. The on-line flow injection analysis (FIA)-CE system was used with electrospray ionization (ESI)-time of flight (TOF)-mass spectrometry detection. The preparation of the PDMS (poly(dimethylsiloxane)) interface for FIA-CE is described in detail and used for initial tests of the on-column polymer-imbedded graphite inlet electrode. In this interface, a pressure-driven liquid flow, a make up CE electrolyte and a CE column inlet meet in a two-level cross (95 microm ID) in the PDMS structure, enabling independent flow characterization.     

Local disruption of DNA-base stacking by bulky base surrogates

A novel biphenyl base surrogate disrupts 2-aminopurine base stacking while maintaining duplex integrity.     

Nonlinear analysis of dynamic binding in affinity capillary electrophoresis demonstrated for inclusion complexes of beta-cyclodextrin

The stability of the molecular host-guest inclusion complexes of beta-cyclodextrin with benzoate and four different hydroxybenzoates is investigated. For the measurement of the binding constants an experimental method is devised that is based on affinity capillary electrophoresis (ACE) with indirect UV absorbance detection. We derive an explicit equation for effective mobilities in ACE experiments without violation of rigorous mass balance. This equation is employed in the nonlinear least-squares analyses of the experimental data yielding binding constants of 48+/-2 M(-1) for benzoate, 299+/-38 M(-1) for 2-hydroxybenzoate, 37+/-1 M(-1) for 3-hydroxybenzoate, 228+/-9 M(-1) for 4-hydroxybenzoate, and 895+/-110 M(-1) in the case of 2,4-dihydroxybenzoate.     

Charge-transfer phenomena in novel,dual-component,sugar-based organogels

The synthesis of a new saccharide-based gelator (2) containing a donor moiety has been described. Gelation experiments of a dual-component gel consisting of a saccharide-based gelator bearing an acceptor group (1) and of 2 have been performed in a variety of organic solvents and water. Moreover, gelation tests at different molar ratios of 1 and 2 have been performed in water, octanol, and diphenyl ether. In these last two solvents a gel color change was observed, from colorless to yellow, upon cooling of the sample to room temperature. This phenomenon was further investigated by UV-visible spectroscopy, which revealed the presence of charge-transfer interactions in the gel, in octanol. Temperature-dependence UV spectroscopy confirmed that such interactions occur in the gel but not in the corresponding solution sample. Furthermore, T(gel) measurements show that dual-component gels of 1 and 2 present increased thermal stability at a 50:50 ratio of the two gelators, in dependence of the solvent. Transmission electron microscopy (TEM) images of the single-component gels in diphenyl ether revealed that they consist of a fibrous network, while the dual-component gel presents a novel, helical, fibrous-bundle structure.     

Catalytic Asymmetric Synthesis of α‐Arylpyrrolidines and Benzo‐fused Nitrogen Heterocycles

Herein, we report a practical two‐step synthetic route to α‐arylpyrrolidines through Suzuki–Miyaura cross‐coupling and enantioselective copper‐catalyzed intramolecular hydroamination reactions. The excellent stereoselectivity and broad scope for the transformation of substrates with pharmaceutically relevant heteroarenes render this method a practical and versatile approach for pyrrolidine synthesis. Additionally, this intramolecular hydroamination strategy facilitates the asymmetric synthesis of tetrahydroisoquinolines and medium‐ring dibenzo‐fused nitrogen heterocycles.     

Metallkomplexe mit biologisch wichtigen Liganden. CXLVII [1] Struktur und Eigenschaften von Pfeiffers Nickel(II)‐Schiff‐Base‐Komplex aus Salicylaldehyd und Glycinester

Metal Complexes with Biological Important Ligands. CXLVII [1] Structure and Properties of Pfeiffer's Nickel(II) Schiff Base Complex from Salicylaldehyde and Glycine Ester. The structure of the planar nickel(II) complex reported by Paul Pfeiffer with two Schiff base ligands from salicylaldehyde and glycine ethylester and with trans‐NiO₂N₂ arrangement was determined by X‐ray diffraction. The finding by Pfeiffer that this complex reacts with oxygen to give the bis(O, N‐imine) complex Ni(OC₆H₄CH=NH)₂ under C‐N cleavage could be confirmed by spectroscopic data, and a reaction path is suggested.     

Polysulfonylamine. CLX [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 10 [2] Die dreidimensionalen Koordinationspolymere M[(CH3SO2)2N] mit M = Kalium,Rubidium, Caesium (isotype Strukturen für M = K,Rb)

Polysulfonylamines. CLX. Crystal Structures of Metal Di(methanesulfonyl)amides. 10. The Three‐Dimensional Coordination Polymers M[(CH₃SO₂)₂N], where M is Potassium, Rubidium, Cesium (Isotypic Structures for M = K, Rb) Low‐temperature X‐ray crystal structures are reported for KA (monoclinic, space group P2₁/c, Z′ = 1), RbA (isotypic and isostructural with KA), and CsA (monoclinic, P2₁/n, Z′ = 1), where A^— denotes the anion obtained by deprotonation of the strong nitrogen acid (MeSO₂)₂NH. In KA and RbA, the anion is distorted into a rare C₁ conformation, whereas the standard C₂ conformation is retained in the cesium complex. The structures consist of three‐dimensional coordination networks, in which each cation adopts an irregular (O₆N)‐heptacoordination by forming close contacts to one (O, N)‐chelating, one (O, O)‐chelating and three κ¹O‐bonding ligands; however, the coordination number for Cs⁺ is effectively increased to 8 by a very short Cs···Cs contact distance of 422.5 pm. The crystal packings of the isotypic compounds KA and RbA display lamellar layer substructures that involve six independent ligand‐metal bonds and comprise an internal cation lamella and peripheral regions built up from anion monolayers; the 3D framework is completed by one independent M—O bond cross‐linking the layer substructures. In contrast, CsA features anion monolayers that intercalate planar zigzag chains of cations (Cs···Cs alternatingly 422.5 and 487.5 pm, Cs···Cs···Cs 135.7°), whereby each chain is surrounded and coordinated by four anion stacks and each anion stack connects two cation chains. All structures exhibit close C—H···A interanion contacts consistent with weak hydrogen bonding.     

15‐Hydroperoxy‐PGE2: Intermediate in Mammalian and Algal Prostaglandin Biosynthesis

Arachidonic‐acid‐derived prostaglandins (PGs), specifically PGE₂, play a central role in inflammation and numerous immunological reactions. The enzymes of PGE₂ biosynthesis are important pharmacological targets for anti‐inflammatory drugs. Besides mammals, certain edible marine algae possess a comprehensive repertoire of bioactive arachidonic‐acid‐derived oxylipins including PGs that may account for food poisoning. Described here is the analysis of PGE₂ biosynthesis in the red macroalga Gracilaria vermiculophylla that led to the identification of 15‐hydroperoxy‐PGE₂, a novel precursor of PGE₂ and 15‐keto‐PGE₂. Interestingly, this novel precursor is also produced in human macrophages where it represents a key metabolite in an alternative biosynthetic PGE₂ pathway in addition to the well‐established arachidonic acid‐PGG₂‐PGH₂‐PGE₂ route. This alternative pathway of mammalian PGE₂ biosynthesis may open novel opportunities to intervene with inflammation‐related diseases.