Functionalization of the 4(5)methyl group of imidazoles: A novel synthesis of substituted imidazoles

Acyl vinyl phosphonium salts react with amidines to form imidazolyl phosphonium salts. These imidazolyl salts can be readily converted to multifunctional imidazoles with quantitative recovery of triphenyl phosphine.     

Nuclear magnetic resonance coupled microseparations

The increased separation efficiency afforded by reducing the size of the separation column has resulted in 'microseparations' becoming an important component in many chemical and biochemical applications. The coupling of microseparations with NMR detection is an area of increasing interest owing to the high structural information of NMR. In order to couple efficiently with the separation, the NMR detector must be reduced in size to correspond to that of the separation peak. This paper summarizes some of the approaches used in coupling NMR detection with pressure-driven and electrophoretic microseparations, the design of small NMR detectors and applications of this technology.     

Particle circulation and oxygen mass transfer in an immobilized cell bioreactor

Two important considerations in the design of an aerobic particulate immobilized cell bioreactor are the provision of sufficient oxygen to maintain the desired metabolism of the immobilized organism, and the biomass holdup (which is proportional to the number of immobilized cell particles in the reactor). The Circulating Bed Reactor, a reactor developed for use with those forms of immobilization that result in particles of essentially neutral buoyancy, operates with an expanded bed of circulating particles. The particle number density attainable in such a reactor has been found to be dependent upon the circulation cell aspect ratio, the individual particle properties, the static bed voidage of the particles, and the superficial gas velocity. The oxygen mass transfer characteristics have been found to be dependent upon the circulatory nature of the system, the particle (solids) holdup, the particle porosity, and the superficial gas velocity.     

An electronic aid for line selection for scanning inductively coupled plasma atomic emission spectrometers

This article is an electronic publication in Spectrochimica Acta Electronica (SAE), the electronic section of Spectrochimica Acta Part B (SAB). Accompanying this hard copy text is a disk containing the program, source flies, data files and a brief manual along with a few programming notes. The main article discusses the purpose of this work, and the Appendix provides brief instruction on the use of the program, manipulation of the data, and source code. An automatic file selection system for the control of a rapid scanning spectrometer performing atomic emission spectrometry has been developed using the PROLOG language. The system can be “taught” the elemental composition of a given sample type. It uses this information (when available) to generate a linear search strategy which minimizes the number of lines that need to be measured. The rules used by the system can be observed during system operation to allow a trace of the logic. Reading of the initial data base takes no more than 6 s and then decisions are made in less than 1 s per line.     

13C Chemical shifts of some azaindolizines versus electron charge distribution

Azaindolizines, which contain all possible combinations of nitrogen atoms within the five-membered ring moiety, are used as models for the investigation of a relationship between electron charge distribution and ¹³C shifts. A linear correlation is observed between the shifts and total rather than π-charge densities as calculated by the INDO-MO method. The average excitation energy (AEE) approximation in the theory of nuclear screening is shown to hold separately for the CH moieties and the carbon atoms at the ring junction in indolizines. An empirical correlation with charge densities is obtained from the AEE method, as a result of the compensation of effects within the local paramagnetic term and the prevailing contribution to the latter of the effective nuclear charge.¹³C shifts afford a reasonable measure of the total net charges at the carbon atoms of indolizines. The INDO calculations indicate that the π-charges follow the pattern suggested by simple resonance structures but the overall charge density depends heavily on σ-core polarization effects.     

Diverse spreading behavior of binary polymer nanodroplets

Molecular dynamics simulations are used to study the spreading of binary polymer nanodroplets in a cylindrical geometry. The polymers, described by the bead-spring model, spread on a flat surface with a surface-coupled Langevin thermostat to mimic the effects of a corrugated surface. Each droplet consists of chains of length 10 or 100 monomers with approximately 350,000 monomers total. The qualitative features of the spreading dynamics are presented for differences in chain length, surface interaction strength, and composition. When the components of the droplet differ only in the surface interaction strength, the more strongly wetting component forms a monolayer film on the surface even when both materials are above or below the wetting transition. In the case where the only difference is the polymer chain length, the monolayer film beneath the droplet is composed of an equal amount of short chain and long chain monomers even when one component (the shorter chain length) is above the wetting transition and the other is not. The fraction of short and long chains in the precursor foot depends on whether both the short and the long chains are in the wetting regime. Diluting the concentration of the strongly wetting component in a mixture with a weakly wetting component decreases the rate of diffusion of the wetting material from the bulk to the surface and limits the spreading rate of the precursor foot, but the bulk spreading rate actually increases when both components are present. This may be due to the strongly wetting material pushing out the weakly wetting material as it moves toward the precursor foot.     

Evaluation of protocols for reproducible electrospray in-source collisionally induced dissociation on various liquid chromatography/mass spectrometry instruments and the development of spectral libraries

Mass spectral libraries provide a tool for identifying unknown compounds using both molecular weight and fragmentation information. Mass spectrometers with electrospray ionisation (ESI) and atmospheric chemical ionisation (ApCI) sources have the capability to produce data of this type using in-source collisionally induced dissociation (CID), and in-source CID libraries can be created. Due to the variation in electrospray source design from different instrument manufacturers, the production of reproducible in-source CID spectra that can be used in libraries for all instrument types is not a trivial task. To date, the evaluation of the production of in-source CID libraries has tended to focus on similar instruments from one manufacturer. The studies have also tended to focus on specific compound classes, with a limited molecular weight range.This report describes the findings from the investigation of protocols for the creation of mass spectral libraries using ESI in-source CID on six instruments from four different manufacturers. The overall goal was to create a spectral library for the identification of unknowns. The library could then be applied across all manufacturers' electrospray instruments.Two different experimental protocols were attempted. The first used a tuning compound to establish standard ESI source conditions, with fixed fragmentation potentials. The second involved the attenuation of the [M + H](+) ion to a known degree. A diverse range of compounds (pharmaceutical, photographic, pesticides) was tested to establish the reproducibility of the spectra on the six instruments. Both protocols produced spectra on the various instruments that in many cases were very similar. In other examples, the spectra differed not only in their relative ion abundances, but also in terms of the spectral content. Important observations regarding the effect of ion source design are also reported.The degree of spectral reproducibility was calculated off-line by comparing the five most abundant ions (20% for each ion that matches) from each spectrum on each instrument. This approach was adopted, as we do not possess a software package that met our requirements for spectral comparison. Match factors (% fit) were calculated by comparing each spectrum against the spectra recorded for the same compound and then for all other compounds, on each instrument. The % fit values derived by the off-line approach gave a clear view of the spectral reproducibility from instrument to instrument and also discriminated the spectra of the various compounds from each other. The applicability of this approach was tested using a blind trial in which several compounds were presented as unknowns, their in-source CID spectra recorded and the five-ion approach used for identification.     

DESTRUCTION OF PHOTOREACTIVATING ENZYME BY 365 nm RADIATION*

Abstract— Following the observation that in vivo photoreactivation of 365-nm-induced pyrimidine dimers could not be observed chemically, a study was made of the inactivation of photoreactivating enzyme activity by this near-ultraviolet wavelength. It was observed that: (1) Dimers induced in extracted bacterial DNA by 365 nm radiation are completely photoreactivable and are monomerized as an exponential function of the photoreactivation time. (2) Photoreactivability of 254-nm-induced damage in Escherichia coli B/r Hcr is progressively destroyed in vivo as a function of the dose of 365 nm radiation. (3) The ability of the yeast photoreactivating enzyme to monomerize dimers induced at 365 nm in bacterial DNA is destroyed in vitro as a function of the dose of 365 nm radiation, and at a rate comparable to killing of E. coli. These results are consistent with biological measurements which indicate that photoreactivability of ultraviolet (near and far) lethal damage is reduced by exposure of the bacteria to 365 nm radiation.     

Ultraviolet action spectra for DNA dimer induction, lethality, and mutagenesis in Escherichia coli with emphasis on the UVB region

Abstract —Ultraviolet (UV) action spectra were obtained for lethality and mutagenesis (reversion to tryptophan independence) in Escherichia coli WP2s for wavelengths 254–405 nm with detailed analysis in the UVB region (290–320 nm). Parallel chemical assay yields of pyrimidine dimers in DNA of E. coli RT4 were determined at the same wavelengths. Spectral regions isolated from a Xe arc and resonance lines from a high-pressure Hg-Xe arc lamp were both used for irradiation. In all cases, precise energy distributions throughout the isolated Xe bands regions were defined.
Lethality, mutagenesis, and dimer induction all decreased in efficiency in a similar fashion as the wavelengths of the radiation increased. Between 300 and 320 nm, all characteristics measured showed differences of about two and a half orders of magnitude. Between these wavelengths, the values of the three end points used either coincide with or parallel the absorption spectrum of DNA. The mutagenesis action spectrum coincides closely with the absorption spectrum of DNA. The lethality spectrum is closely parallel to the mutagenicity spectrum; the points, however, consistently occur at about 2 nm longer wavelengths. A calculation derived from the slope of the UVB spectra reveals that a 1-nm shift of the solar UV spectrum to shorter wavelengths would result in a 35% increase in its mutagenic potential. At 325 nm, both biological action spectra show sharp decreases in slope. In addition, above 325 nm the spectra for lethality. mutagenicity, and dimer formation diverge sharply; lethalities at these UVA wavelengths were approximately tenfold greater relative to mutagenicity than at shorter wavelengths. The relative yield of dimer formation by 365 nm radiation is intermediate between the yields for lethality and mutagenesis.     

Mutagenic effects of near ultraviolet and visible radiant energy on continuous cultures of escherichia coli

Abstract— –The induction of mutation to phage T5 resistance by near ultraviolet (u.v.) and visible light was studied in chemostat cultures of Escherichia coli strains B/r and B/r/1, trp. The visible light mutation rate to phage T5 resistance was independent of growth rate over the range studied. This result is consistent with a photochemical mechanism of mutagenesis. Changeovers, in which a faster growing subpopulation takes over the culture, usually causing the mutant frequency to decline sharply, occur more frequently in chemostat cultures irradiated with visible light than in cultures treated with far u.v. or caffeine. A preliminary action spectrum was obtained with aerated chemostats that revealed effective wavelengths to be between 330 nm and 500 nm. Wavelengths longer than 500 nm were not effective. Wavelengths longer than 340 nm were not mutagenic in anaerobic chemostats. This oxygen requirement for mutagenesis between 340 nm and 500 nm is consistent with a photodynamic mechanism of action. In aerated cultures, wavelengths between 400 nm and 500 nm were as effective as wavelengths between 330 nm and 400 nm. A number of naturally occurring compounds, including riboflavin and vitamin K, are consistent with the data as candidates for the chromophore responsible for near u.v. and visible light mutagenesis.