Direct mass spectrometric analysis of Bacillus spores

Spores from the Bacillus species, B. cereus, B. anthracis, B. thuringensis, B. lichenformis, B. globigi, and B. subtilis, were examined by direct probe mass spectrometry using electron ionization (EI) and positive and negative chemical ionization (CI). Molecular ions from free fatty acids and nucleic acids were observed in the 70eV spectra as were fragments from glycerides. Spectra obtained with isobutane positive chemical ionization (CI(+)) were dominated by ions associated with pyranose compounds such as N-acetylglucosamine (NAG). Unlike the positive ion spectra, the negative ion spectra of the spores were very simple and contained few peaks. The M(-.) ion from dipicolinic acid (DPA) was the base peak in the negative ion spectra of all spore species except those from B. lichenformis. The negative ion of DPA produced such a strong signal that 10(8) colony forming units (CFUs) of B. cereus spores could be detected directly in 0.5 g of ground rice. Principal component analysis (PCA) of the spectra revealed that only CI(+) spectra contained differences that could be used to identify the spectra by species. Differentiation of the CI(+) spectra by PCA was attributed to variances in the peaks associated with the bacterial polymer poly(3-hydroxybutyrate) (PHB) and NAG. Similar differences in PHB and NAG peaks were detected in the CI(+) spectra of a suite of vegetative Bacillus stains grown with various media.     

CAROTENOID-TO-BACTERIOCHLOROPHYLL SINGLET ENERGY TRANSFER IN CAROTENOID-INCORPORATED B850 LIGHT-HARVESTING COMPLEXES OF Rhodobacter sphaeroides R-26.1

Four carotenoids, 3,4,7,8-tetrahydrospheroidene, 3,4,5,6-tetrahydrospheroidene, 3,4-dihydrospheroidene and spheroidene, have been incorporated into the B850 light-harvesting complex of the carotenoidless mutant, photosynthetic bacterium, Rhodobacter sphaeroides R-26.1. The extent of π-electron conjugation in these molecules increases from 7 to 10 carbon-carbon double bonds. Carotenoid-to-bacteriochlorophyll singlet state energy transfer efficiencies were measured using steady-state fluorescence excitation spectroscopy to be 54 ± 2%, 66 ± 4%, 71 ± 6% and 56 ± 3% for the carotenoid series. These results are discussed with respect to the position of the energy levels and the magnitude of spectral overlap between the S, (2′AJ state emission from the isolated carotenoids and the bacteriochlorophyll absorption of the native complex. These studies provide a systematic approach to exploring the effect of excited state energies, spectral overlap and excited state lifetimes on the efficiencies of carotenoid-to-bacteriochlorophyll singlet energy transfer in photosynthetic systems.     

Phenylated polyimides via bifunctional monomers

The synthesis of two phenylated bifunctional monomers, dimethyl 4-(4-(p-aminophenoxy)phenyl)-3,5,6-triphenylphthalate and dimethyl 4-(4-(4-(p-aminophenoxy)phenoxy)phenyl)-3,5,6-triphenylphthlate, was accomplished. Polymerization in solution or by a bulk polymerization procedure yielded a series of low molecular weight phenylated polyimides. The polymers were soluble in chlorinated hydrocarbons and exhibited thermal stabilities comparable to other polyimide systems.     

Pulsed power modeling of very-large-aperture,transverse-discharge CO2 lasers

Discharge behavior of large-aperture (10–70 cm) CO₂ lasers is computed using a coupled particle kinetics-equivalent circuit model. Pulsed power systems that produce a single excitation pulse are only able to satisfy the preionization, ignition, and impedance matching conditions for interelectrode gaps 40–50 cm. Double-pulse systems are required for larger gaps, not only to optimize electrical efficiency, but to avoid oscillatory behavior which can lead to arc formation during the second cycle.     

Ion aging effects on the dissociative-attachment instability in CO2 lasers

Onset of the dissociative-attachment instability requires that the rate coefficient for electron detachment (k _d) from negative ions be below a critical value. The predominant negative and positive ions in a CO₂N₂He gas-discharge plasma are known to change with time. As secondary by-products form and the predominant negative-ion species changes from CO ₃ ^– to NO ₂ ^– , a decrease ink _d occurs destabilizing the discharge. Since NO ₂ ^– and NO ₃ ^– are largely unreactive with respect to associative detachment,k _d depends in a sensitive fashion on the concentration of certain minority negative ions (O^–, O ₂ ^– ) and neutrals (CO, O, N). The sufficient conditions for the dissociative-attachment instability are much less sensitive to changes in the electron-ion and ion-ion recombination rate coefficients resulting from the ion aging process.     

Dipolare (1:1)-Addukte aus der Reaktion von 3-Amino-2H-azirinen mit 1,3,4-Oxadiazol- und 1,3,4-Thiadiazol-2(3H)-onen

Dipolar 1:1 Adducts from the Reaction of 3-Amino-2H-azirines with 1,3,4-Oxadiazol- and 1,3,4-Thiadiazol-2(3H)-ones 3-Amino-2H-azirines 1 react with 5-(trifluoromethyl)-1,3,4-oxadiazol-2(3H)-one ( 2 ) as well as with different 5-substituted 1,3,4-thiadiazol-2(3H)-ones ( 5a–e ) in 2-propanol at room temperature to give dipolar 1:1 adducts of type 3 and 6 , respectively, in reasonable-to-good yields (Schemes 3 and 6, Tab. 1 and 2). The structure of two of these dipolar adducts, 6a and 6e , which are formally donor-acceptor-stabilized azomethin imines, have been elucidated by X-ray crystallography (Figs. 1-4). In the reaction of 2 and sterically crowded 3-amino-2H-azirines 1c–e with a 2-propyl and 2-propenyl substituent, respectively, at C(2), a 4,5-dihydro-1,2,4-triazin-3(2H)-one of type 4 is formed as minor product (Scheme 3 and Table 1). Independent syntheses of these products proved the structure of 4 . Several reaction mechanisms for the formation of compounds 3 and 4 are discussed, the most likely ones are described in Scheme 4: reaction of 2 as an NH-acidic compound leads, via a bicyclic zwitterion of type A , to 3 as well as to 4 . In the latter reaction, a ring-expanded intermediate B is most probable.     

The influence of sulfur substitution on the atomic displacement in Bi2Ti2O7

To clarify the role of A₂O′ and B₂O₆ networks on cation displacement observed in Bi₂Ti₂O′O₆, we used density functional theory calculations to examine the effect of sulfur substitution on the O′ and O sites on lone pair formation and resulting atomic displacement observed in Bi₂Ti₂O′O₆. Cation displacement in bismuth titanate is suppressed only when S is substituted on the O′ site. Analysis of the electronic structure shows that S substitution on the O′ site suppresses the formation of the asymmetric p-type lone pair by modifying the Bi-anion hybridization. Lone pair formation is favored in Bi₂Ti₂O′S₆ and the atomic displacement is larger than that observed in Bi₂Ti₂O′O_6. This enhanced displacement is due to weaker Bi-S versus Bi-O interactions leading to significantly stronger hybridization between the Bi and O′ states in Bi₂Ti₂O′S₆. We also induced lone pair formation in a metallic bismuth pyrochlore oxide (Bi₂Ru₂O′O₆) by modifying the Bi-O interactions through S substitution on the B₂O₆ network, indicating atomic displacement on the A₂O′ network may be achieved by modifying the B₂O₆ network.     

Quantum effects in the Gowdy T3 cosmology

The Gowdy T³ Cosmology is an exact solution to the vacuum Einstein equations interpreted to be a single polarization of gravitational waves propagating in an anisotropic, spatially inhomogeneous background. The classical behavior is reviewed and related to standard cosmological parameters. Canonical quantization of the dynamical degrees of freedom is reviewed. An adiabatic vacuum state is constructed. Adiabatic regularization is used to obtain non-divergent stress-energy tensor vacuum expectation values. Casimir energy terms due to T³ imposed discrete modes are evaluated. The vacuum expectation values are analyzed in early and late time limits and evaluated numerically. The regularized expectation value is used as a source for the classical background spacetime in the spirit of semi-classical gravity. An entirely vacuum expectation value source term produces essentially the time reverse of the classical evolution. Classical stress-energy added to the source restores the classical behavior at late times only. The combined system collapses from infinite to small but non-zero volume and reexpands. The classical singularity is replaced by a symmetric bounce.     

A perceptual learning investigation of the pitch elicited by amplitude-modulated noise

Noise that is amplitude modulated at rates ranging from 40 to 850 Hz can elicit a sensation of pitch. Here, the processing of this temporally based pitch was investigated using a perceptual-learning paradigm. Nine listeners were trained (1 hour per day for 6-8 days) to discriminate a standard rate of sinusoidal amplitude modulation (SAM) from a faster rate in a single condition (150 Hz SAM rate, 5 kHz low-pass carrier). All trained listeners improved significantly on that condition. These trained listeners subsequently showed no more improvement than nine untrained controls on pure-tone and rippled-noise discrimination with the same pitch, and on SAM-rate discrimination with a 30 Hz rate, although they did show some improvement with a 300 Hz rate. In addition, most trained, but not control, listeners were worse at detecting SAM at 150 Hz after, compared to before training. These results indicate that listeners can learn to improve their ability to discriminate SAM rate with multiple-hour training and that the mechanism that is modified by learning encodes (1) the pitch of SAM noise but not that of pure tones and rippled noise, (2) different SAM rates separately, and (3) differences in SAM rate more effectively than cues for SAM detection.     

Solid‐State Gas Sensors Developed from Functional Difluoroboradiazaindacene Dyes

This article describes the synthesis and characterization of several new difluoroboradiazaindacene (BODIPY?) dyes functionalized at the central 8‐position by a phenyliodo, phenylheptynoate or phenylheptynoic fragment and at the 3‐ or 3/5‐position(s) by 4‐dimethylaminophenylstyryl residue(s). Single‐crystal structural determinations confirm the planarity of the dyes, while the absorption and fluorescence spectroscopic properties are highly sensitive to the state of protonation (or alkylation) of the terminal anilino donor group(s). Reversible color tuning from green to blue for absorption and from colorless (i.e., near‐IR region) to red for fluorescence is obtained on successive addition of acid and base. The difunctionalized derivative is especially interesting in this respect and shows two well‐resolved pK_a values of 5.10 and 3.04 in acetonitrile. Addition of the first proton causes only small spectral changes and deactivates the molecule towards addition of the second proton. It is this latter step that accommodates the large change in absorption and emission properties, due to the reversible extinction of the intramolecular charge‐transfer character inherent to this type of dye. The main focus of the work is the covalent anchoring of the dyes to inert, porous polyacrylate beads so as to form a solid‐state sensor suitable for analysis of gases or flowing liquids. The final material is highly stable—its performance is undiminished after more than one year—and fully reversible over many cycles. The sensitivity is such that reactions can be followed by the naked eye and the detection limit is about 600 ppb for HCl and about 80 ppb for ammonia. Trace amounts of diphosgene can be detected, as can alkylating agents. The sensing action is indiscriminate and also operates when the beads are dispersed in aqueous media.