Semiconductor gas sensors in bioreactor control

A simple semiconductor gas sensor (TGS 812) is used for the on-line measurement and control of indole during the production of l-tryptophan from indole and l-serine with immobilized E. coli cells. Indole is estimated in the reactor gas space. In combination with an automatic indole supply system, a feed-batch process became possible. The indole concentration was monitored and kept within the optimal range (300–600 mg l^?1). A simple gas-sensing electrode dipped in the reaction medium provides direct measurement of organic solvents and gases in the liquid. Such a system is suitable for on-line determination of ethanol (10–70 g l^?1) during continuous production of ethanol with immobilized yeast cells.     

Basische metalle : XXXVII. Zur reaktivität der ethylen(hydrido)rhodium-komplexe [C5H5RhH(C2H4)PR3]X gegenüber nucleophilen: insertion versus substitution

The complex [C₅H₅RhH(C₂H₄)PMe₃]BF₄ (I) reacts with NaF and NaCN by deprotonation to give C₅H₅Rh(PMe₃)C₂H₄ but with NaCl, NaBr and NaI the ethylrhodium compounds C₅H₅RhC₂H₅(PMe₃)X (II–IV) are obtained. The reactions of I with CO and PPrⁱ₃ yield the BF₄ salts of the cations [C₅H₅RhH(CO)PMe₃]⁺ and [C₅H₅RhH(PPrⁱ₃)PMe₃]⁺ (V, VI), respectively, from which the uncharged complexes C₅H₅Rh(CO)PMe₃ (VII) and C₅H₅Rh(PPRⁱ₃)PMe₃ (VIII) are prepared. The carbonyl compound VII is also accessible either from C₅H₅Rh(CO)₂ and PMe₃ or from C₅H₅Rh(PMe₃)₂ and CO. The reaction of I with ethylene leads to the BF₄ salt of the cation [C₅H₅RhC₂H₅(PMe₃)C₂H₄]⁺ (X) which on treatment with PMe₃ forms the complex [C₅H₅RhC₂H₅(PMe₃)C₂H₄PMe₃]BF₄ (XI). The compound [C₅H₅RhH(C₂H₄)PPrⁱ₃]BF₄ (XII) reacts with NaI by insertion to yield C₅H₅RhC₂H₅(PPrⁱ₃)I (XIII) whereas with PPrⁱ₃ the salt [C₅H₅RhH(PPrⁱ₃)₂]BF₄ (XIV) is produced. The bis(triisopropylphosphine) complex C₅H₅Rh(PPrⁱ₃)₂ (XVI) is obtained from XIV and NaH.     

Totalsynthese von (+)-D-Homoöstron-3-methyläther

Total Synthesis of (+)-D-Homoestrone 3-methyl ether A novel total synthesis of (+)-D-homoestrone 3-methyl ether ( 21 ) is described starting from (S)-8a-methyl-3,4,8,8a-tetrahydro-2H, 7H-naphthalene-1,6-dione ( 1 ) as a chiral synthon for the rings C and D. The key step involves alkylation of the derived 3 with m-methoxyphenacyl bromide ( 4 ) as an AB-building block to give the dioxo-secosteroid 5 . Hydrogenation of 5 affords the trans-decalone 11 . As by-products the epimeric cis-decalones 12 and 13 were characterized. Cyclization of 11 leads under kinetic control predominantly to the Δ⁹⁽¹¹⁾-tetraene 14 . Catalytic hydrogenation of 14 and subsequent modification in ring D give the title compound 21 . It was found that 14 and also the derived Δ⁸-isomer 15a add hydrogen from the α-face of the molecule to an extent of about 80%. The 8α-D-homoestrone derivatives 20a and 23 as well as the 9β-isomers 19a and 22 were characterized.     

Hydrazones and new Oximes of 4-Aminobicyclo[2.2.2]octanones and their Antiprotozoal Activities

Summary. 4-Aminobicyclo[2.2.2]octan-2-ones and -ols showed activity against the causative organisms of East African sleeping sickness and Malaria tropica. Several imino derivatives of the ketones were more active. Now hydrazono analogues and 3-hydroximino derivatives of the ketones and alcohols were synthesized. The structures of the obtained isomers were elucidated by NMR spectroscopy. A single phenylhydrazone exhibited quite good antitrypanosomal activity in the range of already known imino analogues.     

Hydrazones and new Oximes of 4-Aminobicyclo[2.2.2]octanones and their Antiprotozoal Activities

4-Aminobicyclo[2.2.2]octan-2-ones and -ols showed activity against the causative organisms of East African sleeping sickness and Malaria tropica. Several imino derivatives of the ketones were more active. Now hydrazono analogues and 3-hydroximino derivatives of the ketones and alcohols were synthesized. The structures of the obtained isomers were elucidated by NMR spectroscopy. A single phenylhydrazone exhibited quite good antitrypanosomal activity in the range of already known imino analogues.     

Investigation of the pharmacokinetics of celecoxib by liquid chromatography-mass spectrometry

A new method for the quantification of celecoxib in human plasma based on reversed-phase high-performance liquid chromatography (HPLC) coupled to atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) after liquid-liquid extraction is presented. The method is rapid, sensitive and highly selective. The retention time of celecoxib was 2.3 min. The limit of quantification was 5 microg/L. Rofecoxib was used as internal standard. After validation, the method was used to study the pharmacokinetic profile of celecoxib following administration of a single oral dose (200 mg) in 12 healthy volunteers. Since celecoxib should be metabolized primarily by cytochrome 2C9 (CYP2C9), a poor metabolizer (PM) for this cytochrome P450 enzyme was included in the study. Pharmacokinetic characteristics (mean +/- SD) of extensive metabolizers (EM) were t(max) 2.9+/-1.2h, c(max) 842+/-280 microg/L, AUC(infinity) 6246+/-2147 microg h/L and t(1/2) 7.8+/-2.7h. The area under the curve (AUC(infinity)) for the PM was 12561 microg h/L. However, we found no noticeable increase in half life in the PM (11.5 h) after a single dose of celecoxib.     

An Improved Method of Determining the zeta-Potential and Surface Conductance

In the classical "slope-intercept" method of determining the zeta potential and the surface conductance, the relationship between DeltaP and E(s) is measured experimentally at a number of different channel sizes (e.g., the height of a slit channel, h). The parameter (epsilon(r)epsilon(0)DeltaP/μE(s)lambda(b)) is then plotted as a function of 1/h and linear regression is performed. The y-intercept of the regressed line is then related to the zeta-potential and its slope to the surface conductance. However, in this classical method, the electrical double layer effect or the electrokinetic effects on the liquid flow are not considered. Consequently, this technique is valid or accurate only when the following conditions are met: (1) relatively large channels are used; (2) the electrical double layer is sufficiently thin; and (3) the streaming potential is sufficiently small that the electroosmotic body force on the mobile ions in the double layer region can be ignored. In this paper a more general or improved slope-intercept method is developed to account for cases where the above three conditions are not met. Additionally a general least-squares analysis is described which accounts for uncertainty in the measured channel height as well as unequal variance in the streaming potential measurements. In this paper, both the classical and the improved slope-intercept techniques have been applied to streaming potential data measured with slit glass channels, ranging in height from 3 μm to 66 μm, for several aqueous electrolyte solutions. The comparison shows that the classical method will always overestimate both the zeta-potential and the surface conductance. Significant errors will occur when the classical method is applied to systems with small channel heights and low ionic concentrations. Furthermore, it is demonstrated that traditional regression techniques where the uncertainty is confined only to the dependent variable and each measurement is given equal weight may produce physically inconsistent results. Copyright 2000 Academic Press.     

Amperometric carbohydrate detection in flow systems by means of a bismuth modified platinum electrode

Bismuth modified platinum electrodes are used for constant-potential amperometric determination of carbohydrates in flow systems. The monitored response is stable and reproducible over more than two days. An attempt is made to gain more detailed information about the characteristics of the modified layer by electrochemical methods and X-ray photoelectron spectroscopy. The response proved to be linear over the investigated concentration range (1.1–1200 mol/L) and detection limits for glucose and fructose were found to be 1.1 mol/L.     

Characterization of thermo-oxidative stability of polymer optical fibers using chemiluminescence technique

The thermo-oxidative stability of commercially available polymer optical fibers (POFs) and their components (cores and claddings) was investigated. All the bare POFs (core and cladding only) studied here were based on poly(methyl methacrylate) (PMMA) core. The fibers were exposed to 100 °C/low humidity for about 4200 h. Chemiluminescence (CL) technique was applied to investigate the thermo-oxidative stability and for measuring the transmission loss during exposure a prototype device called multiplexer was used. POFs exhibited variation in thermo-oxidative stability although they possessed identical core material PMMA. This was due to difference in the chemical compositions of claddings. Claddings were more susceptible to the thermo-oxidative degradation compared to cores. The thermo-oxidative degradation of both the cladding and the core was found in POFs as a result of climatic exposure. POFs showed an early drop-off followed by a slow decline of transmission. The early drop-off of transmission was attributed to physical changes like thermal expansion and the slow decline of transmission to chemical changes like oxidative degradation of POFs. A good linear relationship between optical transmission stability and thermo-oxidative stability of POFs was established from these studies.     

Isolierung,Konstitution und Synthese der (R)-(−)-Eucominsäure

From the bulbs of Eucomis punctata L'Hérit. (Liliaceae) and of a hitherto undefined species of Eucomis a new optically active phenolic carboxylic acid, eucomic acid, was isolated. Structure 1 was assigned on the basis of chemical and spectral evidence. The absolute configuration of eucomic acid was determined by its correlation with piscidic acid ((2 R, 3 S)-2-(4′-hydroxybenzyl)-tartaric acid) ( 8 ). Consequently, eucomic acid is (R)-(?)-2-(4′-hydroxybenzyl)-malic acid ( 1 ). For the stereospecific synthesis, methyl cis-p-methoxybenzylidene-succinic acid ( 22 ) was transformed into the γ-lactone 24 which, by catalytic hydrogenolysis, yielded (±)-2-(4′-hydroxybenzyl)-malic acid 1-methyl ester ( 27 ). Resolution with (?)-quinine led to the enantiomeric acids 29 and 30 . The methyl ester of the levorotatory enantiomer 30 was identical with the dimethyl ester 3 of 4′-O-methyl-eucomic acid.