On the relationship between fluorescence and molecular geometry solvent-assisted formation of luminescent intramolecular exciplexes from anthronyl-substituted anthracenes

The fluorescence efficiency of 1′,2′-dihydro-spiro[anthracene-9(10H),3′-[3H]benz[de]anthracen]-10-one in 10 solvents of varying dielectric constant has been investigated. The observed exciplex luminescence is attributed to a solvent-assisted intramolecular charge-transfer interaction between the ground-state anthrone and excited-state anthracene moietis. The geometry of the exciplex is suggested to resemble that of a σ-π complex.     

The crystal structure of Cs[VOF3] · 12H2O

The crystal structure of $\text{Cs[VOF}{}_3\text{]}\text{·}\text{1}\text{2}\text{H}{}_2\text{O}$ has been determined and refined on the basis of three-dimensional X-ray diffractometer data (MoKα radiation). The structure is monoclinic, a = 7.710(2), b = 19.474(7), c = 7.216(2)Å, β = 116.75(1)°, V = 967.5ų, Z =8, space group Cc (No. 9). The final R and R_w were 0.0295 and 0.0300, respectively, for 1356 independent reflections and 117 variables.The structure contains two crystallographically different VOF₅ octahedra linked so as to form complex chains. Two non-equivalent octahedra share one FF edge, forming V₂O₂F₈ doublets. Two F atoms, connected to different V atoms within the doublet, form an edge in the adjacent equivalent V₂O₂F₈ unit thus continuing the chain. The VO distances are 1.583(7) and 1.595(7) Å. The VF distances are in the range 1.881-2.205 Å, mean value: 1.989 Å. The H₂O group is a crystal water molecule.     

A case study of de novo sequence analysis of N-sulfonated peptides by MALDI TOF/TOF mass spectrometry

The simplicity and sensitivity of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry have increased its application in recent years. The most common method of "peptide mass fingerprint" analysis often does not provide robust identification. Additional sequence information, obtained by post-source decay or collision induced dissociation, provides additional constraints for database searches. However, de novo sequencing by mass spectrometry is not yet common practice, most likely because of the difficulties associated with the interpretation of high and low energy CID spectra. Success with this type of sequencing requires full sequence coverage and demands better quality spectra than those typically used for data base searching. In this report we show that full-length de novo sequencing is possible using MALDI TOF/TOF analysis. The interpretation of MS/MS data is facilitated by N-terminal sulfonation after protection of lysine side chains (Keough et al., Proc. Natl. Acad. Sci. U.S.A. 1999, 96, 7131-7136). Reliable de novo sequence analysis has been obtained using sub-picomol quantities of peptides and peptide sequences of up to 16 amino acid residues in length have been determined. The simple, predictable fragmentation pattern allows routine de novo interpretation, either manually or using software. Characterization of the complete primary structure of a peptide is often hindered because of differences in fragmentation efficiencies and in specific fragmentation patterns for different peptides. These differences are controlled by various structural parameters including the nature of the residues present. The influence of the presence of internal Pro, acidic and basic residues on the TOF/TOF fragmentation pattern will be discussed, both for underivatized and guanidinated/sulfonated peptides.     

Confocal scanning microfluorometry of dual-labelled specimens using two excitation wavelengths and lock-in detection technique

A new technique for simultaneous recording of multiple fluorophores has been implemented in a confocal scanning laser microscope. Dual excitation wavelengths, intensity-modulated at different frequencies and two lock-in amplifiers tuned to the corresponding frequencies are used. In this way two fluorophores can be independently, albeit simultaneously, excited. This technique, Intensity-modulated Multiple-beam Scanning (IMS) microfluorometry, has the potential to virtually eliminate the cross-talk between fluorophores that often occurs when recording multiple-labelled specimens. Furthermore, it will offer simultaneous information about both the excitation and emission spectra of the fluorophores used. Also, variations in decay time over the image area can be studied independently and simultaneously for two fluorophores.     

Distributions modulo subgroups of GF(q)

The main purpose of this paper is to determine the number of symbols in each equivalence class modulo subgroups of $\text{GF(q)}{}^1$ for a certain class of linear recursive sequences with irreducible generating polynomial. The method used is to map sequences onto maximal linear recursive sequences.     

An electron spectroscopic determination of theL I energy in the elements Sodium (Z=11) to Copper (Z=29)

Energies of atomic electrons in theK andL shells of eighteen elements of low atomic numbers have been measured by electron spectroscopy. Tabulated values for theL _I energies are shown to be in need of considerable revision. AluminumKα radiation is shown to have high potentialities for ESCA studies.     

High resolution mass spectrometry of trimethylamine

High resolution shows that the four principal fragment peaks of trimethylamine are singlets. Close studies of the metastable transitions in the spectrum have established the origin of almost all fragment peaks.     

Reactions of cationic iron clusters with ammonia, models of nitrogen hydrogenation and dehydrogenation

The gas phase reactivities of small cationic iron clusters, Fen+ (n = 1-20), towards ammonia were investigated using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Sequential addition of ammonia molecules to the clusters was observed to be the dominating process for n > 4. In the case of n = 4 we observed addition of ammonia accompanied by dehydrogenation. This reaction was modelled using hybrid density functional theory. Clusters with n < 4 do not react with ammonia. Clusters Fen+ (n = 1-20) react with neither N2 nor H2 at around 10(-8) mbar. When dinitrogen was seeded into the expanding helium, mixed clusters of the type FenNm+ were observed. These ions react with H2, either by addition, or by substitution of N2. The clusters with m = 1 were isolated in separate experiments and reacted with H2, which showed that mixed clusters with n = 5-13 add up to 5 molecules of dihydrogen in successive slow reactions.     

Description of a Method for Automated Determination of Organic Pollutants in Water

Abstract

A method for automated determination of 73 organic pollutants in water is described. The compounds, which are key representatives for different types of pollutants are determined in two chromatographic runs. 11 halogenated aliphatic hydrocarbons are determined using capillary GC equipped with electron capture detector. The remaining pollutants, representing both basic/neutral and acidic compounds are determined by using GC/MS combined with an automated search computer program. The majority of the compounds have a limit of quantitation at 1 ig/1 or lower. The precision of the GC method is in the range of 1.8% to 4.3%, with an average of 3.2%. The precision for compounds determined by GC/MS is in the range of 1% to 38%, with an average of 14%.

So far 30 water samples representing both polluted fjord areas as well as effluents from municipal treatment plants, refineries, petrochemical industries and metallurgic industries have been analysed. The method has been found to be an interesting alternative to traditional methods for monitoring water quality, and has demonstrated its potential both as a screening method for detecting “hot spots” as well as for routine monitoring of specific hazardous compounds.