Efficient synthesis of tertiary amines from secondary amines

Reliable N-alkylations of secondary amines have been developed. By using DIAD and TPP (or PS-TPP) a variety of secondary amines can be converted to the corresponding tertiary amines in good to excellent yields with diverse alkylhalides; no formation of quaternary amine salts are observed. These protocols are amenable to combinatorial chemistry libraries, and are also useful for the syntheses of secondary amines by an acid lysis of the cleavable tertiary amino resins.     

Alkyltrimethylammonium surfactant-mediated extractions: characterization of surfactant-rich and aqueous layers, and extraction performance

Most surfactants employed for extraction purposes contain strongly absorbing chromophores, and therefore cannot be used with the ultraviolet-visible HPLC detector because of the high background created. Alkyltrimethylammonium surfactants, which do not have strongly absorbing chromophores, have shown promise as an extractant compatible with HPLC-ultraviolet-visible detection. In our extraction procedure, alkyltrimethylammonium surfactants are added to a sample containing organic analytes in distilled water. Sodium chloride is next added, then the entire sample is shaken. Before centrifugation, 1-octanol is added to aid in the two phase formation of surfactant-rich and aqueous phases. In this paper, we present the results of our studies on the extraction behavior of an alkyltrimethylammonium surfactant technique using various organic compounds as test probes. Specifically studied are the extraction behavior of organic bases, isomers of varying polarity and a zwitterionic species that has different charges at various pH values. Results from multiple extractions to obtain quantitative recovery of analytes is also presented. The composition of each phase is elucidated through the interpretation of data obtained from thermogravimetric and carbon, hydrogen and nitrogen (CHN) instrumentation.     

Field and pressure response of Yb compounds close to a quantum critical point

YbCu_5−x Al _x provides the possibility to tune ground state properties by a change of the valence due to the Cu/Al substitution, by pressure as well as by the application of a magnetic field. Near to the critical concentration x _cr≈1.5 non-Fermi-liquid properties (NFL) are obvious, obeying hyperscaling. If magnetic order sets in for x>1.5, the application of moderate magnetic fields quenches order and again NFL features become evident. Hyperscaling in this case indicates strongly interacting spin fluctuations.     

Chemoenzymatic synthesis of 4-diphosphocytidyl-2-C-methyl-d-erythritol: a substrate for IspE

Enantiomerically pure 2-C-methyl-d-erythritol 4-phosphate 1 (MEP) is synthesized from 1,2-O-isopropylidene-α-d-xylofuranose via facile benzylation in good yield. Subsequently, 1 is used for enzymatic synthesis of 4-diphosphocytidyl-2-C-methyl-d-erythritol 2 (CDP-ME) using 4-diphosphocytidyl-2-C-methyl-d-erythritol synthase (IspD). The chemoenzymatically synthesized 2 can be used as substrate for assay of IspE and for high throughput screening to identify IspE inhibitors.     

Synthesis of the asperparaline core by a radical cascade

A concise access to the pentacyclic core structure of the asperparalines is described. The key step is a radical cascade sequence comprised of a 1,6-hydrogen atom transfer followed by 6-exo-trig and 5-exo-trig cyclizations.     

A parallel dual-electrode detector for capillary electrophoresis

An approach to on-capillary dual-electrode detection for CE using a parallel electrode configuration has been developed. The parallel configuration provides two operating modes. In the first mode, one working electrode is held at an oxidizing potential and the second working electrode is held at a reducing potential. This results in redox cycling of analytes between the oxidized and reduced forms, enhancing sensitivity compared to single-electrode detection. In the second mode, both working electrodes are held at different oxidizing potentials. This mode provides electrochemical characterization of electrophoretic peaks. In the redox cyclying mode, signal enhancement of up to twofold was observed for the dual-electrode detection of phenolic acid standards compared to single-electrode detection. Variation in response of less than 10% from electrode to electrode was determined (at a concentration of 60 nM) indicating reproducible fabrication. LODs were determined to be as low as 5.0 nM for dual-electrode configuration. Using the dual-potential mode peak identification of targeted phenolic acids in whiskey samples were confirmed based on both migration time and current ratios.     

Characterization of a specific arabinosyltransferase activity involved in mycobacterial arabinan biosynthesis

Mycobacterium smegmatis strains that contain inactivated EmbA or EmbB proteins are unable to synthesize terminal Arabeta1-->2Araalpha1-->5(Arabeta1-->2Araalpha1-->3)Araalpha1-->5Araalpha1-->(Ara(6)) motif in the cell wall polysaccharide arabinogalactan. Instead, the mutants contain a linear Arabeta1-->2Araalpha1-->5Araalpha1-->5Araalpha1-->(Ara(4)) motif, suggesting that these proteins are involved in the synthesis or transfer of the disaccharide Arabeta1-->2Araalpha1--> to an internal 5-linked Ara. Therefore, we synthesized a linear Arabeta1-->2Araalpha1-->5Araalpha1-->5Araalpha1-->5Araalpha1--> with an octyl aglycon as an arabinosyl acceptor in cell-free assays. A facile assay was developed using the chemically synthesized glycan, membrane, and particulate cell wall as the enzyme source, and 5-phosphoribose diphosphate pR[(14)C]pp as the arabinose donor. The results unequivocally show that two arabinofuranosyl residues were added at the tertiary -->5Araalpha1--> of the synthetic glycan. This activity was undetectable in strains of M. smegmatis where embB or embA had been genetically disrupted. Normal activity could be restored only in the presence of both EmbA and EmbB proteins.