Analysis of urban dust (PM<Subscript>2</Subscript>/PM<Subscript>10-2</Subscript>) in Daejeon city by instrumental neutron activation analysis

Summary As part of an air pollution monitoring study, airborne particulate matter (PM₂/PM_10-2) samples were collected from 2000 to 2003 at two sampling sites in an urban region, Daejeon, the middle of Korea. Mass concentrations of both fine and coarse fractions and that of the black carbon in the fine particles were measured using the Gent stacked filter unit sampler and the smoke stain reflectometer, respectively. In the collected samples the concentrations of 24 elements were analyzed using instrumental neutron activation analysis. Monitored data were investigated for their temporal trends under different environmental conditions and their seasonal correlation patterns. Crustal enrichment factors were also estimated to establish the contribution between anthropogenic and crustal origin. Patterns for airborne particle matter (APM) and elemental concentrations, seasonal variation of some marker elements were investigated. The results can be applied for the investigation of further air pollution sources and for the evaluation of air quality.     

Selection rules for Raman scattering from eigenmodes of spherical nanoparticles

The elastic vibrations of spherical nanoparticles have been widely studied by Raman scattering. However, there exist more than one set of selection rules for Raman scattering from these vibrations. For instance, Kanehisa has stated that only torsional modes with angular momentum l = 2 are Raman-active, while Tanaka et al. proposed that spheroidal modes of even l and torsional modes of odd l are Raman-active. These contradict selection rules of Duval which states that only spheroidal modes of l = 0 or 2 are Raman-active. Our present calculations based on a macroscopic model show that all torsional modes have vanishing intensity in the Raman spectrum.     

Scaling Function Between the Exponential-6 and the Generalized Lennard-Jones Potential Functions

The van der Waals forces for non-bonded interaction can be expressed either by the Exponential-6 or by the Lennard-Jones(m-n) potential functions, whereby m > n. Hitherto a relationship exists between the Exponential-6 and the Lennard-Jones(12-6) potential functions, with a scaling factor = 13.772 at or near the equilibrium and = 12.0 for long range interaction. This paper attempts to develop relationships between Exponential-6 and a more generalized Lennard-Jones(m-n). Analysis reveals that the relationship exists only when n = 6 and that two sets of scaling factors (as functions of index m) applies for the relationship between Exponential-6 and the Lennard-Jones(m-6), whereby m > 6.     

Synthesis of 1-alkoxy-5-alkyluracils

1-Alkoxy-5-alkyluracils 2a-f have been prepared by the reaction of 2-alkyl-3-methoxyacryloyl isocyanates 8a-b with alkoxyamines 9a-c followed by cyclization of the resulting N-alkoxy-N'-(2-alkyl-3-methoxyacryloyl)ureas 10a-f. The isocyanates 8a-b were prepared from ethyl 2-alkylacrylates 3a-b in 5 steps.     

Steric Stabilization of Colloids by Poly(dimethylsiloxane) in Carbon Dioxide: Effect of Cosolvents

Steric stabilization and flocculation of colloids with surface-grafted poly(dimethylsiloxane) (PDMS) chains are examined in liquid and supercritical carbon dioxide with and without hexane as a cosolvent. Neither poly(methyl methacrylate) (PMMA) nor silica particles with grafted 10,000 g/mol PDMS could be stabilized in pure CO(2) at pressures up to 345 bar at 25 degrees C and 517 bar at 65 degrees C without stirring. The addition of 15 wt% hexane to CO(2) led to stable dispersions with sedimentation velocities of 0.2 mm/min for 1-2 μm PMMA particles. The critical flocculation pressure of the colloids in the hexane/CO(2) mixture, determined from turbidity versus time measurements, was found to be the same for silica and PMMA particles and was well above the upper critical solution pressure for the PDMS-CO(2) system. The addition of a nonreactive cosolvent, hexane, eliminates flocculation of PMMA particles synthesized through dispersion polymerization in CO(2) with PDMS-based surfactants. Copyright 2000 Academic Press.     

Regioselective hydroborations of methylvinylchlorosilanes

The regioselectivity of the hydroboration of the methylchlorovinylsilanes, Cl_nMe_3?nSiCHCH₂ (n= 0 ? 3), has been investigated using BH₃←THF, 9-BBN, disiamyl- and dicyclohexylborane. Methylation of the adducts with methylmagnesium bromide is complicated by formation of tetraalkylboronates. Alkaline hydrogen peroxide oxidation of the boronates gives reasonable yields of the corresponding α- and β-trimethylsilylethanols forn= 0 and 1. Forn= 2 and 3, conversion of the adducts to the corresponding α- and β- deuteroethylsilanes by treatment with excess sodium methoxide in methanol-0-d provides a more effective means of derivatization. Addition of the alkenes,n= 2 or 3, to excess BH₃←THF givesca. 90% of the α-boro-organo-chlorosilanes. For all of the alkenes, the dialkylboranes giveca. 80% of the β-boron adducts.     

Size-based analysis of incinerator fly ash using gravitational SPLITT fractionation, sedimentation field-flow fractionation, and inductively coupled plasma-atomic emission spectroscopy

Fly ash has been regarded as hazardous because of its high adsorption of toxic organic and/or inorganic pollutants. Fly ash is also known to have broad distributions of different chemical and physical properties, such as size and density. In this study, fly ash emitted from a solid waste incinerator was pre-fractionated into six sub-populations by use of gravitational SPLITT fractionation (GSF). The GSF fractions were then analyzed by sedimentation field-flow fractionation (SdFFF) and ICP–AES. SdFFF analysis showed the fly ash has a broad size distribution ranging from a few nanometers up to about 50 µm. SdFFF results were confirmed by electron microscopy. Inductively coupled plasma–atomic emission spectroscopy (ICP–AES) analysis of the GSF fractions showed the fly-ash particles contain a variety of inorganic elements including Ca, Si, Mg, Fe, and Pb. The most abundant in fly ash was Ca, followed by Si then Mg. No correlations were found between trace element concentration and particle size.     

Arbophylline, a novel heptacyclic indole with a cage skeleton incorporating an acetal moiety

A new indole alkaloid, arbophylline, possessing a novel heptacyclic cage skeleton, and incorporating an acetal function, was obtained from the Malayan Kopsia arborea. The structure was established by spectroscopic analysis and a possible biogenetic pathway from an akuammiline-type precursor is presented.     

Nuclear Coordinate dependence of electronic transition moments in orbitally forbidden transitions: A new interpretation of deuterium isotope effects

The nuclear coordinate dependence of electronic transtion moments has been investigated for the purpose of finding new interpretations of deuterium isotope effects on spectral intensities and radiative decay rates in orbitally forbidden electronic transitions. By using “AO following nuclei” wavefunctions as the building block for the electronic wavefunction in the adiabatic BO vibronic wavefunction, the spin-free hamiltonian is diagonalized to generate eigenfunctions and eigen-energies. It is found that the electronic transtion moments based on these eigenfunctions show dependences upon the vibrational modes which are not directly involved in vibronic coupling. This leads to interpretations of the deuterium isotope effects in T₁ → S₀ radiative transitions of aromatic hydrocarbons and S₀ → S₁ absorption in pyrazine which are not based on the conventional Herzberg—Teller or non-BO coupling.     

Electronic relaxation of molecular exciplexes in the vapor phase

Interaction of electronically excited TCNB (tetracyanobenzone) and ground-state MB (methylated benzenes) leads to the formation of fluorescent exciplexes in the vapor phase. Studies of exciplex fluorescence as a function of excess vibrational energy in TCNB and of temperature and pressure of added buffer gas, lead to the conclusion that the low-frequency inter-molecular vibrations play a very important role in the radiationless deactivation of exciplexes. The results also indicate that collisional relaxation of low-frequency intermolecular vibrations proceeds much more rapidly than that of high-frequency intramolecular vibrations.