Conformational Control of Polysilanes: Use of CH2 Spacers in the Silicon Backbone
By the reaction of a number of oligosilyl potassium compounds with (trimethylsilyl)chloromethane, derivatives containing the (trimethylsilyl)methyl substituent were prepared. Using X-ray single-crystal structure analysis and UV spectroscopy the conformational properties of some of the compounds were studied. It was found that the (trimethylsilyl)methylated examples exhibit UV absorption properties which correspond to lower energy transitions in comparison to those of analogous trimethylsilylated molecules. The influence of this effect decreases, however, with increasing chain lengths.
Incorporating Methyl and Phenyl Substituted Stannylene Units into Oligosilanes. The Influence on Optical Absorption Properties
Molecules containing catenated heavy group 14 atoms are known to exhibit the interesting property of σ-bond electron delocalization. While this is well studied for oligo- and polysilanes the current paper addresses the UV-absorption properties of small tin containing oligosilanes in order to evaluate the effects of Sn–Si and Sn–Sn bonds as well as the results of substituent exchange from methyl to phenyl groups. The new stannasilanes were compared to previously investigated oligosilanes of equal chain lengths and substituent pattern. Replacing the central SiMe2 group in a pentasilane by a SnMe2 unit caused a bathochromic shift of the low-energy band (λmax = 260 nm) of 14 nm in the UV spectrum. If, instead of a SnMe2, a SnPh2 unit is incorporated, the bathochromic shift of 33 nm is substantially larger. Keeping the SnMe2 unit and replacing the two central silicon with tin atoms causes shift of the respective band (λ = 286 nm) some 26 nm to the red. A similar approach for hexasilanes where the model oligosilane [(Me3Si)3Si]2(SiMe2)2 (λmax = 253 nm) was modified in a way that the central tetramethyldisilanylene unit was exchanged for a tetraphenyldistannanylene caused a 50 nm bathochromic shift to a low-energy band with λmax = 303 nm.
Pharmacokinetics of Mivacurium Isomers and Their Metabolites in Healthy Volunteers after Intravenous Bolus Administration
Background Previous studies report the pharmacokinetics of mivacurium isomers after an infusion using venous blood sampling. Although the extent of the mivacurium arterial‐venous gradient is not known, the sampling site is likely to influence mivacurium pharmacokinetic parameters because the drug is rapidly metabolized as it traverses the circulation. The objectives of this study were (1) to determine the pharmacokinetics of mivacurium isomers in healthy persons after intravenous bolus administration using intensive arterial blood sampling, and (2) to characterize the formation and elimination of mivacurium metabolites in human plasma. Methods Eight persons classified as American Society of Anesthesiologists physical status 1 or 2 who were scheduled to undergo elective surgery under balanced anesthesia received 0.15 mg/kg mivacurium chloride as an intravenous bolus. Arterial blood samples were collected every 10 s during the first 2 min and at frequent intervals for 4 h thereafter. Plasma concentrations of mivacurium isomers and their metabolites were determined by two stereoselective high‐performance liquid chromatographic methods coupled with fluorometric detection and noncompartmental pharmacokinetic parameters. Results Mean elimination half‐lives of the trans‐trans, cis‐trans, and cis‐cis isomers were 2.4, 2, and 28.5 min, respectively, with corresponding mean plasma clearances of 29.2, 45.7, and 6.7 ml [center dot] min‐1 [center dot] kg‐1. The volumes of distribution at steady state of the trans‐trans, cis‐trans, and cis‐cis isomers were 0.047, 0.054, and 0.189 l/kg, respectively. Plasma concentrations of monoester and alcohol metabolites peaked 25 s (median) after mivacurium injection, with half‐lives in the range of 90 min, except for the cis alcohol metabolite, which was only negligibly and transiently formed. Conclusions Substantial hydrolysis of mivacurium isomers by cholinesterases was confirmed by the rapid appearance of mivacurium metabolites in plasma. The intensive arterial sampling proved to be critical for the trans‐trans and cis‐trans isomers because the area under the curve between 0 and 2 min accounted for 75% and 86% of the total, respectively.