Solventless continuous flow homogeneous hydroformylation of 1-octene

The hydroformylation of 1-octene under continuous flow conditions is described. The system involves dissolving the catalyst, made in situ from [ Rh(acac)(CO)(2)] (acacH = 2,4- pentanedione) and [RMIM][TPPMS] ( RMIM = 1-propyl (Pr), 1-pentyl (Pn) or 1-octyl (O)-3-methyl imidazolium, TPPMS = Ph2P(3-C6H4SO3)), in a mixture of nonanal and 1-octene and passing the substrate, 1-octene, together with CO and H-2 through the system dissolved in supercritical CO2 (scCO(2)). [PrMIM][TPPMS] is poorly soluble in the medium so heavy rhodium leaching (as complexes not containing phosphine) occurs in the early part of the reaction. [PnMIM][ PPMS] affords good rates at relatively low catalyst loadings and relatively low overall pressure (125 bar) with rhodium losses <1 ppm, but the catalyst precipitates at higher catalyst loadings, leading to lower reaction rates. [OMIM][ TPPMS] is the most soluble ligand and promotes high reaction rates, although preliminary experiments suggested that rhodium leaching was high at 5-10 ppm. Optimisation aimed at balancing flows so that the level within the reactor remained constant involved a reactor set up based around a reactor fitted with a sight glass and sparging stirrer with the CO2 being fed by a cooled head HPLC pump, 1-octene by a standard HPLC pump and CO/H-2 through a mass flow controller. The pressure was controlled by a back pressure regulator. Using this set up, [OMIM][ TPPMS] as the ligand and a total pressure of 140 bar, it was possible to control the level within the reactor and obtain a turnover frequency of ca. 180 h(-1). Rhodium losses in the optimised system were 100 ppb. Transport studies showed that 1-octene is preferentially transported over the aldehydes at all pressures, although the difference in mol fraction in the mobile phase was less at lower pressures. Nonanal in the mobile phase suppresses the extraction of 1-octene to some extent, so it is better to operate at high conversion and low pressure to optimise the extraction of the products relative to the substrate. CO and H2 in the mobile phase also suppress the extraction effciency by as much as 80%.

Carbonation and pH in Mortars Manufactured with Supplementary Cementitious Materials

An investigation of carbonation in mortars and methods of measuring the degree of carbonation and pH change is presented. The mortars were manufactured using ordinary portland cement, pulverized fuel ash, ground granulated blast-furnace slag, metakaolin, and microsilica. The mortars were exposed to a carbon dioxide-rich environment 5% CO2 to accelerate carbonation. The resulting carbonation was measured using phenolphthalein indicator and thermogravimetric analysis. The pH of the pore fluid and a powdered sample, extracted from the mortar, was measured to give an accurate indication of the actual pH of the concrete. The pH of the extracted powder mortar sample was found to be similar to the pH of the pore fluid expressed from the mortars. The thermogravimetric analysis suggested two distinct regions of transport of CO2 within mortar, a surface region where convection was prevalent and a deeper region where diffusion was dominant. The use of microsilica has been shown to decrease the rate of carbonation, while pulverized fuel ash and ground granulated blast-furnace slag have a detrimental effect on carbonation. Metakaolin has little effect on carbonation.

Neurokinin A is the predominant tachykinin in human bronchoalveolar lavage fluid in normal and asthmatic subjects

BACKGROUND—Multiple sensory neuropeptides are present in human airways and may contribute to diseases such as asthma. This study quantified and characterised substance P (SP), neurokinin A (NKA), and calcitonin gene related peptide (CGRP) immunoreactivity in bronchoalveolar lavage fluid in asthmatic and normal subjects.
METHODS—Using specific radioimmunoassay (RIA), SP, NKA and CGRP were measured in bronchoalveolar lavage fluid from asthmatic subjects (n = 5), normal subjects (n = 5), atopic non-asthmatic subjects (n = 6), and asthmatic subjects four hours after allergen challenge (n = 12). Peptide immunoreactivity was characterised using high performance liquid chromatography (HPLC) and RIA.
RESULTS—No SP or CGRP immunoreactivity was detected in any of the fractions from samples after extraction, HPLC, and RIA. Non-specific binding resulted in spurious SP immunoreactivity being detected in bronchoalveolar lavage fluid when no extraction process was employed. NKA was detected in significant amounts in asthmatic (median 550, range 425-625 pg/ml) and normal subjects (median 725, range 350-1425 pg/ml). The level of NKA was significantly higher in the asthmatic subjects after allergen challenge (median 750, range 350-1250 pg/ml) than in unchallenged asthmatic subjects (median 600, range 425-600 pg/ml, p<0.01).
CONCLUSIONS—Extraction and characterisation of peptides from bronchoalveolar lavage fluid must be performed to ensure that the measured immunoreactivity represents target peptide. NKA is present in bronchoalveolar lavage fluid in high concentrations and is the predominant tachykinin. The concentrations of NKA are similar in normal subjects and subjects with mild asthma.

FTIR analysis of water in supercritical carbon dioxide microemulsions using monofunctional perfluoropolyether surfactants

We describe perfluoropolyether (PFPE) surfactants which are capable of stabilising the water/CO2 interface and present FTIR spectroscopic evidence for the formation of water in supercritical carbon dioxide microemulsions. A wide variety of single chain surfactants of differing chain lengths but similar structure has been screened and the effect of the surfactant chain length on the water uptake was studied. The ammonium carboxylate of the PFPE surfactant Krytox FSL(TM) with an average molecular weight of 2500 g mol(-1) was demonstrated to be the surfactant capable of dissolving the most water out of all the tested surfactants and hence to have the optimum chain length. (C) 2002 Elsevier Science B.V. All rights reserved.

Correlation of synovial fluid cytokine levels with histological and clinical parameters of primary and revision total hip and total knee replacements

We retrieved synovial tissue and fluid samples from patients undergoing primary total hip replacement (THR) (n 15), revision of aseptically loose THR (n 12), primary total knee replacement (TKR) (n 13) and revision of aseptically loose TKR (n 6). Several histological parameters were assessed on a relative scale of 1-4. Primary TJRs were clinically evaluated for degree of osteoarthrosis. Revision TJRs were assessed for migration of the implant, gross loosening and the degree of radiolucency. Cytokine levels in synovial fluid were determined with ELISA.

Chronic treatment with a stable obestatin analogue significantly alters plasma triglyceride levels but fails to influence food intake, fluid intake, body weight, or body composition in rats.

Obestatin (OB(1-23) is a 23 amino acid peptide encoded on the preproghrelin gene, originally reported to have metabolic actions related to food intake, gastric emptying and body weight. The biological instability of OB(1-23) has recently been highlighted by studies demonstrating its rapid enzymatic cleavage in a number of biological matrices. We assessed the stability of both OB(1-23) and an N-terminally PEGylated analogue (PEG-OB(1-23)) before conducting chronic in vivo studies. Peptides were incubated in rat liver homogenate and degradation monitored by LC-MS. PEG-OB(1-23) was approximately 3-times more stable than OB(1-23). Following a 14 day infusion of Sprague Dawley rats with 50 mol/kg/day of OB(1-23) or a N-terminally PEGylated analogue (PEG-OB(1-23)), we found no changes in food/fluid intake, body weight and plasma glucose or cholesterol between groups. Furthermore, morphometric liver, muscle and white adipose tissue (WAT) weights and tissue triglyceride concentrations remained unaltered between groups. However, with stabilised PEG-OB(1-23) we observed a 40% reduction in plasma triglycerides. These findings indicate that PEG-OB(1-23) is an OB(1-23) analogue with significantly enhanced stability and suggest that obestatin could play a role in modulating physiological lipid metabolism, although it does not appear to be involved in regulation of food/fluid intake, body weight or fat deposition.

Study of structural change in Wyodak coal in high pressure CO2 by small-angle neutron scattering

Small angle neutron scattering (SANS) has been applied to examine the effect of high pressure CO2 on the structure of Wyodak coal. Significant decrease in the scattering intensities upon exposure of the coal to high pressure CO2 showed that high pressure CO2 rapidly adsorbs on the coal and reaches to all pores in the structure. This is confirmed by strong and steep exothermic peaks observed on DSC scans during coal/ CO2 interactions. In situ small angle neutron scattering on coal at high pressure CO2 atmosphere showed an increase in scattering intensities with time suggesting that after adsorption, high pressure CO2 immediately begins to diffuse into the coal matrix, changes the macromolecular structure of the coal, swells the matrix and probably creates microporosity in coal structure by extraction of volatile components from coal. Significant decrease in the glass transition temperature of coal caused by high pressure CO2 also confirms that CO2 at elevated pressures dissolve in the coal matrix, results in significant plasticization and physical rearrangement of the coal’s macromolecular structure.

Analyzing laser plasma interferograms with a continuous wavelet transform ridge extraction technique: the method

Laser plasma interferograms are currently analyzed by extraction of the phase-shift map with fast Fourier transform (FFT) techniques [Appl. Opt. 18, 3101 (1985)]. This methodology works well when interferograms are only marginally affected by noise and reduction of fringe visibility, but it can fail to produce accurate phase-shift maps when low-quality images are dealt with. We present a novel procedure for a phase-shift map computation that makes extensive use of the ridge extraction in the continuous wavelet transform (CWT) framework. The CWT tool is flexible because of the wide adaptability of the analyzing basis, and it can be accurate because of the intrinsic noise reduction in the ridge extraction. A comparative analysis of the accuracy performances of them new tool and the FFT-based one shows that the CWT-based tool produces phase maps considerably less noisy and that it can better resolve local inhomogeneties. (C) 2001 Optical Society of America.

Preparation of a molecularly imprinted polymer for the solid-phase extraction of scopolamine with hyoscyamine as a dummy template molecule

Molecularly imprinted polymers (MIPs) selective for scopolamine were produced using hyoscyamine (a close structural analogue) as template molecule. The produced polymers were used as media for solid-phase extraction, exhibiting selective binding properties for the analyte from biological samples. Human and calf urine and serum were processed on the MIP under various extraction protocols. The best performance was observed after loading the analyte in aqueous environment facilitating retention on the MIP by non-selective hydrophobic interactions. The MIPs were subsequently washed using an optimised solvent system to enable selective desorption of the analyte. Other related and non-related compounds were accessed to evaluate molecular recognition properties. Recoveries of up to 79% were achieved for the analyte of interest from biological samples.

Effect of cataract extraction on SITA perimetry in patients with glaucoma

PURPOSE: To evaluate the effect of cataract extraction on Swedish Interactive Thresholding Algorithm (SITA) perimetry in patients with coexisting cataract and glaucoma. PATIENTS AND METHODS: This is a retrospective noncomparative interventional study. Thirty-seven consecutive patients with open-angle glaucoma who had cataract extraction alone or combined with trabeculectomy were included. All patients had SITA-standard 24-2 visual fields before and after the surgery. The main outcome measures were changes in mean deviation (MD) and pattern standard deviation (PSD). Additionally, changes in best-corrected visual acuity, intraocular pressure, and number of glaucoma medications were also studied. RESULTS: Visual field tests were performed 3.9±4.4 months before surgery and 4.1±2.8 months after surgery. Mean visual acuity improved after the surgery, from 0.41±0.21 to 0.88±0.32 (P

Effect of cataract extraction on frequency doubling technology perimetry in patients with glaucoma

Aim: To evaluate the effect of cataract surgery on frequency doubling technology (FDT) perimetry in patients with coexisting cataract and glaucoma. Methods: In this consecutive prospective cohort study 27 patients with open angle glaucoma scheduled for cataract extraction alone or combined with trabeculectomy were enrolled. All patients underwent FDT threshold C-20 visual fields within 3 months before and 3 months after surgery. Changes in mean deviation (MD) and pattern standard deviation (PSD) were evaluated. Additionally, changes in best corrected logMAR visual acuity (VA), intraocular pressure (IOP), and number of glaucoma medications were also studied. Results: 22 patients completed the study. VA improved after surgery, from 0.47 (SD 0.19) to 0.12 (0.17) (p