A new photochemically removable protecting group for amines

A new arylmethylsulfonyl chloride reacts with secondary or primary amines to give sulfonamides which can be photochemically cleaved, making it suitable for use as a photoremovable protecting group.     

General deoxyribozyme-catalyzed synthesis of native 3'-5' RNA linkages

An elusive goal for nucleic acid enzymology has been deoxyribozymes that ligate RNA rapidly, sequence-generally, with formation of native 3'-5' linkages, and in preparatively useful yield. Using in vitro selection, we have identified Mg2+- and Zn2+-dependent deoxyribozymes that simultaneously fulfill all four of these criteria. The new deoxyribozymes operate under practical incubation conditions and have modest RNA substrate sequence requirements, specifically D downward arrowRA for 9DB1 and A downward arrowR for 7DE5 (D = A, G, or U; R = A or G). These requirements are comparable to those of deoxyribozymes such as 10-23 and 8-17, which are already widely used as biochemical tools for RNA cleavage. We anticipate that the 9DB1 and 7DE5 deoxyribozymes will find immediate practical application for RNA ligation.     

Open-tubular capillary electrochromatography/electrospray ionization-mass spectrometry using polymeric surfactant as a stationary phase coating

We describe the use of the polymeric surfactant poly(sodium undecylenic sulfate) (poly-SUS) as a stationary phase coating in open-tubular capillary electrochromatography (OT-CEC) coupled with electrospray ionization-mass spectrometry (ESI-MS) for the analysis of beta-blocker and benzodiazepine analytes. The production of a polymeric surfactant coating on the capillary inner wall involves (i) adsorption of the cationic polymer poly(diallyldimethylammonium chloride) (PDADMAC) to the inner surface of capillary, and (ii) adsorption of the negatively charged poly-SUS onto the cationic polymer layer via strong physical interaction of the two polymer layers. As compared with micellar electrokinetic chromatography (MEKC) coupled with ESI-MS, the main advantage of this proposed method is minimization of introduction of the monomeric or polymeric surfactant into the mass spectrometer, thus avoiding the interference of the nonvolatile micelle in ESI-MS. The effects of buffer pH and applied voltage on the separation of the analytes are also discussed. Under optimum conditions, four of the five beta-blockers and four benzodiazepines are separated.     

(18)O]-oxygen incorporation reveals novel pathways in spiroacetal biosynthesis by Bactrocera cacuminata and B. cucumis

The origins of the oxygen atoms in 1,7-dioxaspiro[5.5]undecane (1) and hydroxyspiroacetal (2) from Bactrocera cacuminata, and in 2,8-dimethyl-1,7-dioxaspiro[5.5]undecane (3) and hydroxyspiroacetal (4) from B. cucumis, have been investigated by incorporation studies from both [(18)O(2)]-dioxygen and [(18)O]-water. Combined GC-MS examination and high-field NMR analysis have demonstrated that all oxygen atoms in 1 and 2 from B. cacuminata are dioxygen derived, but in contrast, the spiroacetals 3 and 4 from B. cucumis incorporate one ring oxygen from water and one ring oxygen (and the hydroxyl oxygen in 4) from [(18)O(2)]-dioxygen. These results reveal not only the generality of monoxygenase mediation of spiroacetal formation in Bactrocera sp., but also an unexpected complexity in their biosynthesis. A general paradigm accommodating these and other observations is presented.     

Characterization of single- and double-stranded DNA on gold surfaces

Single- and double-stranded deoxy ribonucleic acid (DNA) molecules attached to self-assembled monolayers (SAMs) on gold surfaces were characterized by a number of optical and electronic spectroscopic techniques. The DNA-modified gold surfaces were prepared through the self-assembly of 6-mercapto-1-hexanol and 5'-C(6)H(12)SH -modified single-stranded DNA (ssDNA). Upon hybridization of the surface-bound probe ssDNA with its complimentary target, formation of double-stranded DNA (dsDNA) on the gold surface is observed and in a competing process, probe ssDNA is desorbed from the gold surface. The competition between hybridization of ssDNA with its complimentary target and ssDNA probe desorption from the gold surface has been investigated in this paper using X-ray photoelectron spectroscopy, chronocoulometry, fluorescence, and polarization modulation-infrared reflection absorption spectroscopy (PM-IRRAS). The formation of dsDNA on the surface was identified by PM-IRRAS by a dsDNA IR signature at approximately 1678 cm(-)(1) that was confirmed by density functional theory calculations of the nucleotides and the nucleotides' base pairs. The presence of dsDNA through the specific DNA hybridization was additionally confirmed by atomic force microscopy through colloidal gold nanoparticle labeling of the target ssDNA. Using these methods, strand loss was observed even for DNA hybridization performed at 25 degrees C for the DNA monolayers studied here consisting of attachment to the gold surfaces by single Au-S bonds. This finding has significant consequence for the application of SAM technology in the detection of oligonucleotide hybridization on gold surfaces.     

Anatoxins and degradation products, determined using hybrid quadrupole time-of-flight and quadrupole ion-trap mass spectrometry: forensic investigations of cyanobacterial neurotoxin poisoning

The potent neurotoxins from cyanobacteria, anatoxin-a (AN), its methyl analogue, homoanatoxin-a (HMAN), and their degradation products, have been studied using nano-electrospray hybrid quadrupole time-of-flight mass spectrometry (QqTOF-MS). The anatoxin degradation products, which are readily produced in vivo by either reduction or epoxidation, were also examined in this study. The high mass accuracy QqTOF-MS data was used to confirm formula assignments for major product ions and quadrupole ion-trap (QIT)-MS was used to construct fragmentation pathways for anatoxins. Significant differences between these fragmentation pathways were observed. Comparisons between the spectra of compounds that differ in side-chain length (the AN and HMAN series) were used to identify ions that are characteristic of the homologues. The application to forensic samples in which the principal neurotoxin had undergone rapid biodegradation has been demonstrated and used to confirm anatoxin poisoning of dogs.     

Imidoylketene-alpha-oxoketenimine and alpha-oxoketene-alpha-oxoketene rearrangements. 1,3-shifts of substituted phenyl groups

1,3-phenyl shifts interconvert imidoylketenes 1 and alpha-oxoketenimines 2 and, likewise, alpha-oxoketenes 3 automerize by this 1,3-shift. These rearrangements usually take place in the gas phase under conditions of flash vacuum thermolysis. Energy profiles calculated at the B3LYP/6-31G(d,p) and B3LYP/6311 + G(3df,2p)//B3LYP/6-31G(d,p) levels demonstrate that electron donating substituents (D) in the migrating phenyl group and electron withdrawing ones (W) in the non-migrating phenyl group, can stabilise the transition states TS1 and TS2 to the extent that activation barriers of ca. 100 kJ mol(-1) or less are obtained; i.e. enough to make these reactions potentially observable in solution at ordinary temperatures. The calculated transition state energies DeltaG(TS1) show an excellent correlation with the Hammett constants sigma(p)(W) and sigma(p+)(D).     

Directed evolution of the dioxygenase complex for the synthesis of furanone flavor compounds

Herein we report a new preparation of 4-hydroxy-2,5-dimethyl-2,3-dihydrofuran-3-one, the flavor compound strawberry furanone, based on a ‘green’ approach with a minimum number of steps. The first step is an enzymatic dioxygenation of p-xylene to form cyclohexadiene-cis-diol, followed by ring opening via ozonolysis, and ring closure to form the furanone. In efforts to improve the efficiency of the enzymatic step, a directed evolution approach was taken to increase the substrate specificity and selectivity of the toluene dioxygenase enzyme system.     

Vierdimensionale quadratische Divisionsalgebren über Hilbert-Körpern

Zusammenfassung Inhalt der vorliegenden Untersuchung ist eine Klassifizierung der vierdimensionalen quadratischen Divsionsalgebren über einem Hilbert-Körper. Die Anregung dazu entstammt einer Arbeit von Kuz'min [6], in der endlichdimensionale reelle Divisionsalgebren durch Aussagen über ihre Multiplikationskonstanten charakterisiert werden. Der Schwerpunkt liegt dort auf den quadratischen Divisionsalgebren. Deren Struktur wird wesentlich durch quadratische Formen bestimmt. Deshalb ist es naheliegend, diese Algebren für eine allgemeinere Klasse von Körpern mit einer überschaubaren Theorie der quadratischen Formen zu betrachten. A Fröhlich [5] hat eine axiomatische Beschreibung für eine Klasse von Körpern, die sogenannten Hilbert-Körper, gegeben, die eine Theorie der quadratischen Formen wie die -adischen Zahlen oder die reellen Zahlen haben. Diese Körper legen wir in der Untersuchung zugrunde. Eine genauere Motivation für das Vorgehen und einen Ausblick auf die Ergebnisse gibt die folgende Einleitung.Die Verfasserin dankt Herrn Prof. Dr. K. Strambach, Erlangen, für die Anregung und Begleitung dieser Arbeit und Herrn Prof. Dr. L. Bröcker, Münster, für die konstruktiven Vorschläge zur Überarbeitung des ursprünglichen Manuskiptes.     

Eine Topologie auf der Menge der endlichdimensionalen nichtassoziativen Algebren über einem lokalen Körper

Motivated by an investigation ofKuz'min [2], in this note we introduce a topology on the set of nonassociative algebras of a fixed dimensionr< over a local fieldF. We obtain a space, which is notT ₁. If the trivial algebra is removed, the remaining subspace is quasicompact. The space is homeomoprhic to the group of square classes ofF ^*; forr3 the space is notT ₁. The set of division algebras is open in.