A selective gas chromatographic detector for polynuclear aromatics based on ultraviolet fluorescence

A vapor-phase fluorescence detector for the analysis of mixtures of polynuclear aromatic ring systems has been developed. This system utilizes wide bandpass excitation and wide band emission filters, thus increasing sensitivity and decreasing the complexity of previously designed instruments. The sensitivity of the detector has been demonstrated to be at the nanogram level with reasonable precision.     

Determination of carbonate in the presence of hydroxide : Part I. Analysis of first-derivative potentiometric curves

Mathematical consideration of the course of neutralization of a solution containing a moles of a strong base (e.g. sodium hydroxide) and a moles of a salt of a weak dibasic acid (e.g. sodium carbonate) with a strong acid (e.g. hydrochloric acid) shows that the first derivative of the titration curve should contain three maxima. The first, corresponding to neutralization of most of the hydroxide, is small (with height proportional to a^{$\text{1}\text{2}$}), displaced slightly from the equivalence point, and disappears for a less than 0.01 mol l^-1. The second corresponds to the conversion of most of the CO₃^2- to HCO₃^- and its height is almost independent of a. The third corresponds to the conversion of HCO₃^- to H₂CO₃, with height proportional to a^{$\text{1}\text{2}$}. The two minima are independent of a and of the dissociation constants of the weak acid. These conclusions were examined experimentally and were extended to the titration of hydroxide contaminated with a small amount of carbonate.     

Determination of the Wiener molecular branching index for the general tree

The many applications of the distance matrix, D(G), and the Wiener branching index, W(G), in chemistry are briefly outlined. W(G) is defined as one half the sum of all the entries in D(G). A recursion formula is developed enabling W(G) to be evaluated for any molecule whose graph G exists in the form of a tree. This formula, which represents the first general recursion formula for trees of any kind, is valid irrespective of the valence of the vertices of G or of the degree of branching in G. Several closed expressions giving W(G) for special classes of tree molecules are derived from the general formula. One illustrative worked example is also presented. Finally, it is shown how the presence of an arbitrary number of heteroatoms in tree-like molecules can readily be accommodated within our general formula by appropriately weighting the vertices and edges of G.     

Unified gas and supercritical fluid chromatography on 50 μm i.d. Columns

A unified approach to sequential gas and supercritical fluid Chromatography using 50 μm i.d. open tubular columns is described. Sample introduction is performed by means of a rotary injection valve. In order that linear velocities can be optimized independently, a second rotary valve in the chromatographic oven is used to direct the flow of column eluate to the flame ionization detector through either fused silica tubing in GC, or a frit restrictor in SFC. Applications of sequential GC-SFC on a 50 μm i.d. open tubular column are demonstrated, and comparisons made between sequential GC-SFC on 50 and 100 μm i.d. columns.     

Visible and near-IR luminescence via energy transfer in rare earth doped mesoporous titania thin films with nanocrystalline walls

Selected photoluminescence in the wavelength range of 600-1540 nm is generated by energy transfer from a light-gathering mesostructured host lattice to an appropriate rare earth ion. The mesoporous titania thin films, which have a well-ordered pore structure and two-phase walls made of amorphous titania and TiO₂ nanocrystallites, were doped with up to 8 mol% lanthanide ions, and the ordered structure of the material was preserved. Exciting the titania in its band gap results in energy transfer and it is possible to observe photoluminescence from the crystal field states of the rare earth ions. This process is successful for certain rare earth ions (Sm³⁺, Eu³⁺, Yb³⁺, Nd³⁺, Er³⁺) and not for others (Tb³⁺, Tm³⁺). A mechanism has been proposed to explain this phenomenon, which involves energy transfer through surface states on titania nanocrystals to matching electronic states on the rare earth ions.     

Experimental measurement and prediction of hydrate forming conditions in the nitrogen-propane-water system

Experimental data on initial hydrate formation conditions have been obtained for the nitrogen-propane-water system in the L₁HG, L₁L₂H, and L₁L₂HG regions, where L₁ is the water rich liquid phase, L₂ is the hydrocarbon rich liquid phase, H is the hydrate and the G is the vapor phase. The measurements covered a range of temperatures from about 275 to 293 K and pressures from about 0.3 to 17.0 MPa. The concentrations covered for the L₁HG region extended from 0.94 to 75.0 mole percent propane in the gas phase, and for the L₁L₂H region they extended from 83.1 to 99.0 mole percent in the condensed liquid phase. Four-phase measurements were made at concentrations of propane from 18.1 to 71.1 mole percent in the gas phase.The experimental data were used to find a fitted binary interaction parameter for predicting hydrate formation in systems containing nitrogen and propane.     

Application of cold neutron prompt-gamma activation analysis in environmental studies of aquatic plants

This paper describes the use of cold-neutron prompt-gamma activation analysis (CNPGAA) to determine carbon, nitrogen, and phosphorus in the aquatic plant Typha domingensis, commonly known as cattail, during spring and fall seasons. According to studies of the Florida Everglades, cattail replaces sawgrass as a result of nutrient enrichment from farm water runoff. Nutrient enrichment, especially phosphorus, in sediment and the water column can lead to undesirable expansion. Early signs of this expansion are apparent in the Apalachicola River floodplain near Apalachicola, Florida, USA. This research project is designed to use cattails as biomonitors of nutrient enrichment in the lower Apalachicola River floodplain. Determination of carbon, nitrogen, and phosphorus in cattail using cold neutron prompt-gamma activation has been developed in our previous studies at the CNPGAA facility at the National Institute of Standards and Technology (NIST), USA. The results of numerous field samples, collected from the study area during spring and fall seasons in 2002, will be presented in this paper.     

The autoxidation of 2-(2-aminophenyl)-3- methylindole

Fischer indolisation of 2-aminophenyl ethyl ketone phenylhydrazone using glacial acetic acid saturated with hydrogen chloride as catalyst affords 3-methylindolo(l′:2′-3:4)2-methylquinazoline and 2-(2-aminophenyl)-3-methylindole. The latter compound is autoxidised to 2-(2-amino-phenyl)-3-hydroxy-3-methyl-3H-indole, a reaction which is shown to be dependent upon the presence of the primary amino group at the 2-position of the 2-phenyl substituent and which is much slower than the corresponding autoxidation of 2-(2-hydroxyphenyl)-3-methylindole to 3-hydroxy-2-(2-hydroxyphenyl)-3-methyl-3H-indole previously reported.Nitration of isopropyl phenyl ketone occurs preferentially at the ortho- rather than the meta- positions of the benzene nucleus.