Experimental evidence of a relationship between monomer plasma residence time and carboxyl group retention in acrylic acid plasma polymers

Decreasing carboxyl retention in deposits from the glow region of an acrylic acid plasma was measured by X-ray photoelectron spectroscopy and chemical derivatisation as the collection distance from the monomer vapour inlet was increased. Volatilisation of plasma polymerised acrylic acid was detected after trifluoroethanol derivatisation; this is correlated with evaporation of low molecular weight components observed previously.     

Parameters affecting the use of the lac repressor system in eukaryotic cells and transgenic animals

Elements of the lactose operon were used to study parameters affecting gene expression in cultured cells and transgenic animals. A Lac repressor protein containing a nuclear transport signal was shown to inhibit expression of a reporter gene by interacting with lac operator sequences. In cultured cells, operator sequence, operator placement and induction parameters were all shown to be important for obtaining tight repression of a reporter gene followed by high level expression upon induction. Induction levels were also dependent on the reporter gene, with the luciferase gene yielding higher induction levels than the chloramphenicol acetyltransferase gene. In transgenic animals, the lacI mRNA was not detected in the C57BL/6 mouse strain until the animal was exposed to a demethylating agent. After 5-azacytidine treatment, expression of lacI mRNA was detected in the brain, heart, kidney, lung and ovary. In the FVB transgenic mouse strain, expression of lacI mRNA was detected without 5-azacytidine treatment in the kidney, liver, lung, and testes. Preliminary experiments with double transgenic animals containing both lacI and operator/luciferase transgenes showed a decrease in luciferase expression compared to the luciferase-only animals in both tissue extracts and transgenic fetal primary cultures, although IPTG induction was not achieved in these animals or primary cultures. The applicability and challenges of the system for regulation of gene expression are discussed.     

Premature introduction of progestin-only contraceptive methods during lactation

INTRODUCTIONS: Cochlear implants are used for the rehabilitation of bilaterally deaf patients. Due to the improvements in speech processing they might be also useful for patients with residual hearing and some speech understanding. METHODS: Pre- and postoperative speech understanding scores in 26 patients receiving implants were evaluated in a retrospective study. RESULTS: The preoperative pure-tone threshold in the implanted ear was between 80 and 115 dB in the frequency range of 500 to 2000 Hz. On the contralateral side the mean threshold was 10 dB better. The mean score for the number test was 11.3%, for the monosyllables below 5%. Postoperatively speech understanding improved significantly up to 97% for numbers and 48% for monosyllables (tested with the Freiburger Speech Test). Cochlear implantation also benefits patients with residual hearing and some speech understanding with hearing aids under optimum conditions. The speech understanding scores must be below certain limits. General selection criteria cannot yet be specified. The individual decision must be based upon several criteria, especially the speech understanding scores in quiet and noise under optimum conditions. A prospective study is needed to develop generally applicable criteria.     

The relative contribution of selected carpal bones to global wrist motion during simulated planar and out-of-plane wrist motion

The present study assesses the endocrinological, endometrial histology and vaginal ultrasound profiles of nomegestrol acetate subdermal implant users at varying times after insertion. Follicle stimulatory hormone, luteinizing hormone, oestradiol, progesterone, vaginal ultrasound assessment of the ovaries and the histological dating of the endometrium were serially assessed for a period of 50 days immediately after the insertion, and after at 6 months and 12 months of use. The endocrinological results of this prospective observational clinical trial indicated that 75% of the cycles across the study period in Uniplant users were anovulatory, 63% showing development of a persistent non-luteinized follicle. Anovulatory cycles devoid of follicular development were seen primarily in the first months after Uniplant insertion. Ovulatory cycles represented 25% of the Uniplant cycles. Inadequate luteal phase or disregulation of follicular growth was a common feature of ovulatory cycles. In conclusion, these findings suggest that the contraceptive mechanisms of a single nomegestrol acetate subdermal implant involve prevention of follicular growth, development of a persistent non-luteinized follicle, inadequate luteal phase and disruption of the endometrial architecture.     

An X-ray photoelectron spectroscopic investigation into the chemical structure of deposits formed from hexamethyldisiloxane/ oxygen plasmas

The effect of oxygen addition to microwave-sustained plasmas of hexamethyldisiloxane (HMDSO) has been investigated. Attention was directed to the solid products formed on aluminium substrates (plasma deposits). To enable a quantitative analysis of these, X-ray photoelectron spectroscopy (XPS) of standard silicon-containing materials was carried out. When suitable charge correction is applied to the XP spectra of HMDSO/O₂ plasma deposits, a number of very clear trends emerge. From changes in elemental composition, core line binding energies (Si2p, C 1s, and O 1s) and widths, we show how oxygen addition to the plasma affects the chemical nature of the plasma deposit. The data reported also provide (some limited) information on the reactions taking place in the plasma.     

Pt/Sn bimetallic catalysts for the electro-oxidation of methanol: poisoning by silicate and phosphate unions

The influence of silicate and phosphate anions on the performance of Pt/Sn electrodeposited catalysts for the electro-oxidation of methanol has been studied. Both anions were found to have serious poisoning effects on the catalyst, whereas platinum catalysts were unaffected. The poisoning mechanism in both cases was thought to be initiated by the formation of either stannosilicates or stannophosphates species followed by the build-up of polymeric silicate or phosphate that ultimately blocks the active sites. The origin of the poisoning mechanism in both cases was found to be chemical rather than electrochemical. In the case of silicate, the poisoning species could be removed and the catalytic activity restored by chemical treatment with sulphuric acid.     

A study of the low temperature nitration of cellulose in mixed acids

The low temperature surface and bulk nitration of cellulose has been investigated by electron spectroscopy for chemical analysis (ESCA), ¹³C-NMR and X-ray diffraction. Acid mix composition has been probed at room temperature and at low temperatures (0–20°C) by Raman spectroscopy. This multitechnique approach has been employed to elucidate the behavior of surface degree of substitution (DOS) with acid mix composition over a 40°C temperature range. The data obtained have prompted a reinterpretation of previously reported work. Surface “equilibrium DOS” is shown to be established within 1 s at all temperatures investigated. but, at lower temperatures (> 5°C) the surface DOS as monitored by ESCA is observed to “dip” after immersion times of t < 5 s. This change in DOS is correlated with major structural changes in the fiber as observed by SEM. At low temperatures, e.g., ?15°C, nitration is shown to be complete throughout the cellulose fiber after 10 h nitration. Solution state ¹³C-NMR is used to compare the nitrate ester substitution distribution in cellulose nitrates prepared from acid mixes of the same composition at different temperatures.     

The role of the automation development group in analytical research and development at Dupont Merck

Laboratory robotics has been firmly established in many non-QC laboratories as a valuable tool for automating pharmaceutical dosage form analysis. Often a single project or product line is used to justify an initial robot purchase thus introducing robotics to the laboratory for the first time. However, to gain widespread acceptance within the laboratory and to justify further investment in robotics, existing robots must be used to develop analyses for existing manual methods as well as new projects beyond the scope off the original purchase justification. The Automation Development Group in Analytical Research and Development is a team of analysts primarily devoted to developing new methods and adapting existing methods for the robot. This team approach developed the expertise and synergy necessary to significantly expand the contribution of robotics to automation in the authors'' laboratory.     

Heat exchanger network synthesis with detailed exchanger designs: Part 1. A discretized differential algebraic equation model for shell and tube heat exchanger design

A new method for the detailed design of shell and tube heat exchangers is presented through the formulation of coupled differential heat equations, along with algebraic equations for design variables. Heat exchanger design components (tube passes, baffles, and shells) are used to discretize the differential equations and are solved simultaneously with the algebraic design equations. The coupled differential algebraic equation (DAE) system is suitable for numerical optimization as it replaces the nonsmooth log mean temperature difference (LMTD) term. Discrete decisions regarding the number of shells, fluid allocation, tube sizes, and number of baffles are determined by solving an LMTD-based method iteratively. The resulting heat exchanger topology is then used to discretize the detailed DAE model, which is solved as a nonlinear programming model to obtain the detailed exchanger design by minimizing an economic objective function through varying the tube length. The DAE model also provides the stream temperature profiles inside the exchanger simultaneously with the detailed design. It is observed that the DAE model results are almost equal to the LMTD-based design model for one-shell heat exchangers with constant stream properties but shows significant differences when streams properties are allowed to vary with temperature or the number of shells are increased. The accuracy of the solutions and the required computational costs show that the model is well suited for solving heat exchanger network synthesis problems combined with detailed exchanger designs, which is demonstrated in Part 2 of the paper.     

Factors affecting the corrosion rate of steel in carbonated mortars

The corrosion of steel in carbonated mortar has been investigated by monitoring polarization resistance, corrosion potential and mortar resistivity. The results suggest that factors such as relative humidity and chloride contamination affect the corrosion rate via their influence on mortar resistivity. To account for the observed electrochemical relationships, most notably the linear correlation between corrosion rate and conductivity, and the exponential increase in corrosion rate with fall in corrosion potential, it is proposed that the corrosion kinetics of steel in carbonated mortar are subject to anodic control with the anodic reaction rate being limited by the resistance of the mortar. In this model, termed anodic resistance control, resistivity is viewed as a factor which may limit a half reaction rate in a similar way to diffusion and activation polarization. It is also shown that, when such a model is operating, the use of polarization resistance to monitor corrosion rate changes may still be justified provided the cathodic reaction rate is an exponential function of potential.