Regioselectivity of metalation of alkylmercaptoolefins

The monosulfoxide of cis-dialkylmercaptoethylene $\text{6}$ and the β-alkylmercapto acrylnitrile $\text{15}$ deliver on deprotonation with tert.-butyllithium almost exclusively α-deprotonated species. According to reactions with electrophiles these functionally substituted vinyllithium derivatives are configurationally labile.     

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Synthesis and structure of K+ [iPrN=C=P]-, a 1-aza-3lambda3-phospha-3-allenide

2-Isopropyl(trimethylsilyl)amino-1lambda3-phosphaalkyne 1 reacts with potassium tert-butoxide to form potassium 1-isopropyl-1-aza-3lambda3-phospha-3-allenide (2). This compound was structurally characterized as the corresponding 18-crown-6 ether complex 3. The molecular structure of 1 was also determined in order to compare the bonding situation in the anion and the neutral lambda3-phosphaalkyne. Compound 3 contains a nitrogen-carbon-phosphorus group for which the parameters were shown by X-ray structural analysis and quantum chemical calculations to lie between the extrema N-C[triple bond]P and N=C=P, suggesting reactivity typical of an ambident anion. This is indeed the case, as subsequent reaction of 2 with chlorotrimethylsilane at nitrogen regenerates the lambda3-phosphaalkyne 1; with chlorotriphenylsilane the new derivative 4 is formed. In contrast, chlorotrimethylstannane reacts at phosphorus, giving the 1-aza-3lambda3-phosphaallene isopropyliminomethylidene(trimethylstannyl)phosphane 5.     

Crystallization behavior of supercooled smectic cholesteryl myristate nanoparticles containing phospholipids as stabilizers

Supercooled smectic nanoparticles based on physiological cholesterol esters are under investigation as a potential novel carrier system for lipophilic drugs. The present study investigates the very complex crystallization behavior of such nanoparticles stabilized with the aid of phospholipids. Phospholipid and phospholipid/bile salt stabilized cholesteryl myristate dispersions were prepared by high-pressure melt homogenization and characterized by particle size measurements, differential scanning calorimetry, X-ray diffraction and electron microscopy. To obtain fractions with very small smectic nanoparticles, selected dispersions were ultracentrifuged. A mixture of cholesteryl myristate and the phospholipid used for the stabilization of the dispersions was also investigated by light microscopy. The nanoparticles usually display a bimodal crystallization event which depends on the thermal treatment and cannot be attributed to crystalline polymorphism. The ratio of the particle fractions crystallizing in the two successive steps strongly depends on the particle size of the dispersions. The presence of larger particles leads to an increased fraction crystallizing at higher temperature and a higher recrystallization tendency upon storage. The observed peculiarities of the crystallization behavior seem to be mainly caused by the presence of particles with different shapes (cylindrical and spherical) as observed in electron microscopy. Alterations in the composition of the nanoparticles may also play a role.     

Measuring Lineup Difficulty By Matching Distance Metrics With Subject Choices in Crowd-Sourced Data

Graphics play a crucial role in statistical analysis and data mining. Being able to quantify structure in data that is visible in plots, and how people read the structure from plots is an ongoing challenge. The lineup protocol provides a formal framework for data plots, making inference possible. The data plot is treated like a test statistic, and lineup protocol acts like a comparison with the sampling distribution of the nulls. This article describes metrics for describing structure in data plots and evaluates them in relation to the choices that human readers made during several large Amazon Turk studies using lineups. The metrics that were more specific to the plot types tended to better match subject choices, than generic metrics. The process that we followed to evaluate metrics will be useful for general development of numerically measuring structure in plots, and also in future experiments on lineups for choosing blocks of pictures. Supplementary materials for this article are available online.     

Some contributions to the model order reduction of large scale non-linear electric circuits

Model order Reduction (MOR) has become an ubiquitous technique in the simulation of large-scale dynamical systems (i.e. 10⁴ and more equations). One technique for non-linear MOR is the trajectory piecewise-linear approach (TPWL) [1]. TPWL approximates a non-linear differential system by a weighted sum of linear systems which have a significantly reduced number of equations. One open question is which weight representations provide physical meaning of the weighted sum [2]. In this article we propose two representations. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)