Vibrational spectra and conformations of 1,4-cyclohexadiene and its oxygen analogues: ab initio and density functional calculations

The vibrational spectra and ring-puckering potential energy functions of 1,4-cyclohexadiene, 4H-pyran and 1,4-dioxin have been examined using a density functional theory (DFT) method as well as the Hartree–Fock (HF) and second-order Møller–Plesset (MP2) methods. The calculated vibrational frequencies and potential energy functions of those molecules have been compared with previously reported experimental data and MM3 results. For all three molecules, the DFT method using Becke's three-parameter functional (B3LYP) has led to the prediction of more accurate vibrational frequencies than the HF and MP2 methods. The enlargement of the basis set at the B3LYP levels has improved the accuracy of calculated vibrational frequencies. In particular, the C–O–C=C torsional force field parameters obtained from the B3LYP method have correctly predicted the ring-puckering potential energy functions of the oxygen-containing analogues, 4H-pyran and 1,4-dioxin, which could not be done by the MM3 method.     

Waiting time analysis for a tandem queue with correlated service

The effect on overall waiting time including service is investigated when there is positive correlation between the first and second stage service times in a two stage tandem system. The importance of understage waiting (or “buffer”) space is underlined. The analysis is an application of the authors' work reported in [1].     

Theoretical molecular structures for partially bonded complexes of trimethylamine with SO2 and SO3: ab initio and density functional theory calculations

The self-consistent reaction field (SCRF) method based on Onsager's reaction field theory is applied to investigate the effect of polar media on molecular structures of complexes of trimethylamime (TMA) with SO_x (x=2,3). The calculated SCRF N–S bond lengths at the MPW1PW91/6-311+G(3df) level are in satisfactory agreement with the experimental N–S bond lengths for the TMA–SO_x upon crystallization. The results are enough to demonstrate the usefulness of the reaction field theory in providing qualitative understanding of the medium effect on the partially bonded system such as TMA–SO_x.     

Development of a fully buffered molybdate electrolyte for capillary electrophoresis with indirect detection and its use for analysis of anions in Bayer liquor

A new counterion-buffered molybdate electrolyte was developed and optimized for simultaneous quantitative determination of up to eight anions (chloride, sulphate, oxalate, fluoride, formate, malonate, succinate, and acetate) in Bayer liquor by capillary electrophoresis with indirect detection at 214 nm. The separation parameters were optimized in respect to separation of the critical analyte group fluoride-formate-malonate, with the optimal electrolyte prepared from molybdic trioxide containing 5.0 mmol/L MoO3, 1.3 mmol/L cetyltrimethylammonium bromide (CTAB), and buffered with diethanolamine (DEA) to pH 9.2 (ca. 20 mM DEA). Total length of separation capillary was 80 cm, resulting in run time of under 4 min. The method is suitable for a wide concentration range of the analytes (1-50 mg/L) with linear calibration plots (R2 = 0.9983-0.9999). Relative standard deviations were 0.05%-0.07% for migration times and 0.67%-2.04% for peak areas. The detection limits were in the range of 0.17-0.51 mg/L or 2-10 micromol/L (hydrostatic injection of 30 s of 1000 x diluted sample). Due to its good buffering capacity, the electrolyte exhibited an excellent ruggedness and good tolerance to the alkaline samples. Consequently, Bayer liquor samples could be diluted as little as 100 x which allows more sensitive determination of minor components over previous methods. The method was successfully applied to analysis of Bayer liquor samples with recoveries in the range of 95-105%.     

Effect of chlorine on adsorption/ultrafiltration treatment for removing natural organic matter in drinking water

In drinking water treatment, prechlorination is often applied in order to control microorganisms and taste-and-odor-causing materials, which may influence organics removal by adsorption and membrane filtration. Thus, the addition of chlorine into an advanced water treatment process using a hybrid of adsorption and ultrafiltration (UF) was investigated in terms of natural organic matter (NOM) removal and membrane permeability. A comparison between two adsorbents, iron oxide particles (IOP) and powdered activated carbon (PAC), was made to understand the sorption behavior for NOM with and without chlorination. Chlorine modified the properties of dissolved and colloidal NOM in raw water, which brought about lower TOC removal, during IOP/UF. The location of IOPs, whether they were in suspension or in a cake layer, affected NOM removal, depending on the presence of colloidal particles in feedwater. Chlorine also played a role in reducing the size of particulate matter in raw water, which could be in close association with a decline in permeate flux after chlorination.     

Dodecacarbonyltriosmium catalysed formation of bis(4-N,N-dimethylaminophenyl)methane from N,N-dimethylaniline

Os₃(CO)₁₂ catalyses the conversion of NMe₂Ph to (4-NMe₂C₆H₄)₂CH₂ and NHMePh in refluxing N,N-dimethylaniline. This reaction is similarly catalysed by H₄Os₄(CO)₁₂, while (4-NHMeC₆H₄)₂CH₂ may be obtained from NHMePh. In this case, however, NMe₂Ph and NH₂Ph are also formed, and after longer reaction times mixed products of type (4-NRR′C₆H₄)₂CH₂ (R or R′ = H or Me) are obtained. The formation of H₃Os₃(CH)(CO)₉ indicates methyl transfer from nitrogen to osmium which may be a key step in the catalysis, but it does not appear that clusters are essential since Fe(CO)₅ and Cr(CO)₆ are also weakly active.     

Chiral Co(III)(salen)-catalysed hydrolytic kinetic resolution of racemic epoxides in ionic liquids

In the chiral Co(III)(salen)-catalysed HKR of racemic epoxides, in the presence of ionic liquids, Co(II)(salen) complex is oxidised without acetic acid to catalytically active Co(III)(salen) complex during reaction and, moreover, this oxidation state is stabilised against reduction to Co(II) complex which enables the reuse of the recovered catalyst for consecutive reactions without extra reoxidation.     

Highly sensitive signal detection of duplex dye-labelled DNA oligonucleotides in a PDMS microfluidic chip: confocal surface-enhanced Raman spectroscopic study

Rapid and highly sensitive detection of duplex dye-labelled DNA sequences in a PDMS microfluidic channel was investigated using confocal surface enhanced Raman spectroscopy (SERS). This method does not need either an immobilization procedure or a PCR amplification procedure, which are essential for a DNA microarray chip. Furthermore, Raman peaks of each dye-labelled DNA can be easily resolved since they are much narrower than the corresponding broad fluorescence bands. To find the potential applicability of confocal SERS for sensitive bio-detection in a microfluidic channel, the mixture of two different dye-labelled (TAMRA and Cy3) sex determining Y genes, SRY and SPGY1, was adsorbed on silver colloids in the alligator teeth-shaped PDMS microfluidic channel and its SERS signals were measured under flowing conditions. Its major SERS peaks were observable down to the concentration of 10(-11) M. In the present study, we explore the feasibility of confocal SERS for the highly sensitive detection of duplex dye-labelled DNA oligonucleotides in a PDMS microfluidic chip.     

Use of a photocatalytic membrane reactor for the removal of natural organic matter in water: Effect of photoinduced desorption and ferrihydrite adsorption

The photocatalytic degradation of natural organic matter (NOM) would be an attractive option in the treatment of drinking water. The performance of a submerged photocatalytic membrane reactor (PMR) was investigated with regard to the removal of NOM and the control of membrane fouling. In particular, this work focused on the adsorption and desorption of humic acids (HA) and lake water NOM at the surface of TiO₂ photocatalyts and ferrihydrite (FH) adsorbents in the PMR for water treatment. The addition of FH particles with a large sorption capacity helped remove the NOM released from TiO₂ particles, but FH suspended in water affected the photocatalysis of lake water NOM with a low specific UV absorbance (SUVA) value. To prevent the UV light being scattered by FH without any photocatalytic activity, FH particles were attached to a submerged microfiltration (MF) membrane, which contributed to a greater removal of NOM during long-term PMR operation. The further removal of NOM from aqueous solution was achieved due to the synergistic effect of TiO₂ photocatalysis and FH adsorption in PMR while minimizing the influence of photoinduced desorption of NOM. No significant membrane fouling occurred when the submerged PMR was operated even at high flux levels (>25 L/m² h), as long as photocatalytic decomposition took place.