CGC using a programmable electronic pressure controller

Capillary gas chromatographic separations were performed with an electronic pressure control system developed to provide precise closed-loop control of inlet pressure through the use of a solid state micro-machined pressure sensor and electronically controlled proportional valve. The closed-loop control of the electronic system provided better precision than the open-loop control achieved by manual pressure regulation. Closed-loop control can perform pressure programming, which can be combined with temperature programming to optimize separations. The pressure sensor monitors the integrity of the flow system and singals the controller to reduce flow in the presence of a sudden loss of system pressure.     

Neuropeptide imaging on an LTQ with vMALDI source: The complete ‘all-in-one’ peptidome analysis

Direct tissue imaging was performed on dissected insect tissue using a MALDI ion trap to visualize endogenous neuropeptides. Coupling tissue imaging to tandem MSⁿ allows for the identification of previously known species and the ability to identify new ones by de novo sequencing, as searchable databases for insects are sparse. Direct tissue imaging is an attractive technique for the study of neuropeptides as minimal sample preparation is required prior to mass spectrometry. We successfully identified neuropeptides present in the corpora cardiaca and allata of Acheta domesticus (the house cricket). Diagnostic fragments at low m/z were used to distinguish between lipids and neuropeptides. The distribution of peptides appears to be more differentially localized than that of phospholipids, which seem to be more evenly distributed within the tissue.     

Starburst dendrimer-supported pseudostationary phases for electrokinetic chromatography

Pseudo-stationary phases for electrokinetic chromatography were prepared by the alkylation of starburst dendrimers (SBDs). The SBD-supported pseudo-stationary phase with dodecyl groups showed higher efficiency than short-akyl derivatives, and maintained the hydrophobic property inthe presence of methanol. The dodecyl-modified SBD provided wide migration time windows ar high methanol content to effect the separation of sixteen aromatic hydrocarbons, the priority pollutants designated by EPA, in 65% methanol. The selectivity of polymer-supported pseudo-stationary phase can be varied simply by changing the length of the alkyl groups. The dodecyl SBD showed relatively similar selectivity as sodium dodecyl culfate micelle, whereas short alkyl derivatives showed preference towards rigid and planar compounds based on the rigid and planar compounds based on the rigid polymer backbones. The selectivity of SBD-supported pseudo-stationary phases was dominated by the chain length of the alkyl groups, with the minor effect of the structure of the core and the generation of SBD where alkyl groups were attached.     

Synthesis and properties of cross-linkable DNA duplex using 4-amino-2-oxo-6-vinyl-1,3,5-triazine

We synthesized the DNA oligonucleotide containing a new cross-linkable 4-amino-2-oxo-6-vinyltriazine (AOVT) nucleobase analogue (Et-AOVT) and evaluated these properties. Our results of the cross-link assay and thermal denaturing assay of duplexes containing AOVT demonstrated that the additional aza of AOVT has an impact on the duplex stability and crosslink properties. Our data suggests that the additional 5-aza of AOVT is involved in the hydrogen bonding with the complementary guanine, and this hydrogen bonding system successfully flipped the reactive vinyl group out to the major groove of the duplex demonstrating a new paradigm of a “cross-linkable duplex”.     

Efficient Synthesis of Polycyclic γ-Lactams by Catalytic Carbonylation of Ene-Imines via Nickelacycle Intermediates

The nickel(0)-catalyzed carbonylative cycloaddition of 1,5- and 1,6-ene-imines with carbon monoxide (CO) is reported. Key to this reaction is the efficient regeneration of the catalytically active nickel(0) species from nickel carbonyl complexes such as [Ni(CO)₃L]. A variety of tri- and tetracyclic γ-lactams were thus prepared in excellent yields with 100 % atom efficiency. Preliminary results on asymmetric derivatives promise potential in the synthesis of enantioenriched polycyclic γ-lactams.     

Production of Alkyl Aryl Sulfides from Aromatic Disulfides and Alkyl Carboxylates via a Disilathiane–Disulfide Interchange Reaction

The results of this study show that disilathiane is an effective mediator in the synthesis of alkyl aryl sulfides with disulfides and alkyl carboxylates. Mechanistic studies suggest that disilathiane promotes cleavage of the sulfur–sulfur bond of disulfides to generate thiosilane as a key intermediate. Diselenides were also applicable to this transformation to produce the corresponding selenides.