Studien über Arylsulfochloride,II

Ohne Zusammenfassung     

Comparison of the Wetting Properties of Three Commonly Used Simulated Intestinal Fluids Used as Dissolution Media in the Characterization of Drugs

Simulated intestinal fluids (SIFs) are described in the United States Pharmacopoeia (USP) and the International Pharmacopoeia (IntPh) as recommended dissolution media for the characterization of solid drugs. This study was carried out to compare their wettability properties. Six different model substrates were used as surrogates for solid drugs. These surrogate solid substrates were characterized by the Lifshitz-van der Waals, electron donor and electron acceptor terms, which are the three components of the total surface energy obtained by the van Oss model, which is based upon Young’s equation. Contact angles of the SIFs on the surrogate solid-substrates were determined dynamically by image analysis up to five minutes after applying a drop of the fluid on the solid surface. Observed time-dependent spreading behavior was accounted for by a linear extrapolation of the experimental data to zero contact time to obtain the apparent equilibrium contact angle at zero time. Additionally, the pH, osmolality and buffer capacity of the SIFs were experimentally determined. Although some differences in osmolality and buffer capacity were observed, no statistically significant differences in the wetting properties of the three SIFs were detected. This confirms recent findings that there are no observed differences in dissolution behavior among these simulated intestinal fluids. Harmonization of these SIFs is thus recommended.     

Refined enumerations of alternating sign matrices: monotone (<Emphasis Type="Italic">d</Emphasis>,<Emphasis Type="Italic">m</Emphasis>)-trapezoids with prescribed top and bottom row

Monotone triangles are plane integer arrays of triangular shape with certain monotonicity conditions along rows and diagonals. Their significance is mainly due to the fact that they correspond to n×n alternating sign matrices when prescribing (1,2,…,n) as bottom row of the array. We define monotone (d,m)-trapezoids as monotone triangles with m rows where the d−1 top rows are removed. (These objects are also equivalent to certain partial alternating sign matrices.) It is known that the number of monotone triangles with bottom row (k ₁,…,k _n ) is given by a polynomial α(n;k ₁,…,k _n ) in the k _i ’s. The main purpose of this paper is to show that the number of monotone (d,m)-trapezoids with prescribed top and bottom row appears as a coefficient in the expansion of a specialisation of α(n;k ₁,…,k _n ) with respect to a certain polynomial basis. This settles a generalisation of a recent conjecture of Romik et al. (Adv. Math. 222:2004–2035, 2009). Among other things, the result is used to express the number of monotone triangles with bottom row (1,2,…,i−1,i+1,…,j−1,j+1,…,n) (which is, by the standard bijection, also the number of n×n alternating sign matrices with given top two rows) in terms of the number of n×n alternating sign matrices with prescribed top and bottom row, and, by a formula of Stroganov for the latter numbers, to provide an explicit formula for the first numbers. (A formula of this type was first derived by Karklinsky and Romik using the relation of alternating sign matrices to the six-vertex model.)     

Recent advances in ultrafast time‐resolved chirality measurements: perspective and outlook

Observing chirality changes as they occur is an important topic of research. It provides information that deepens the understanding of biomolecular configuration and conformation under environmental changes. Also, knowing the specific steps in chiral synthesis would simplify the production of specific chiral enantiomers that have a specific function. To gain better insight to the initial steps of conformational and configurational changes, the time‐resolution of chiral spectroscopy is continually pushed toward a shorter time‐scale. Recent advances have produced measurements of chirality changes with a femtosecond time‐resolution. These measurements are hindered by the inherently weak chirality signal, which can be overshadowed by different optical artefacts. This minireview will look at the so far successful techniques which measure chirality changes with femtosecond time‐resolution and discuss the advantages and disadvantages of these techniques. A short outlook will also look at new techniques that could improve the ability to measure chirality changes on an ultrafast time‐scale.     

Photoelastic Tomography with Linear and Non-linear Algorithms

Tomography is a powerful method for the investigation of the internal structure of 3D objects from human bodies to atomic reactors. Classical tomography has been elaborated for the determination of scalar fields, i.e. fields, each point of which is characterized by a scalar. Due to that, algorithms of classical tomography can not be directly applied by investigating stress fields since stress is a tensor. In this paper it is shown that photoelastic tomography can be based on the equations of integrated photoelasticity. In the linear approximation the problem of stress field tomography is decomposed into a number of problems of scalar field tomography for single components of the stress tensor. In the non-linear case the axisymmetric stress field can be determined using a genetic algorithm. The paper is illustrated by several examples.     

A resting state network in the motor control circuit of the basal ganglia

Background  

In the absence of overt stimuli, the brain shows correlated fluctuations in functionally related brain regions. Approximately ten largely independent resting state networks (RSNs) showing this behaviour have been documented to date. Recent studies have reported the existence of an RSN in the basal ganglia - albeit inconsistently and without the means to interpret its function. Using two large study groups with different resting state conditions and MR protocols, the reproducibility of the network across subjects, behavioural conditions and acquisition parameters is assessed. Independent Component Analysis (ICA), combined with novel analyses of temporal features, is applied to establish the basis of signal fluctuations in the network and its relation to other RSNs. Reference to prior probabilistic diffusion tractography work is used to identify the basal ganglia circuit to which these fluctuations correspond.     

Determination of allergy-causing metals from coins

Abstract  The majority of everyday items contain metals and their alloys, although many of them may be harmful to human health. Nickel, originating from different sources such as coins, jewelry, or buttons, represents the most common cause of contact allergy dermatitis. Therefore, the aim of this research work was to estimate the possible risk of allergy resulting from skin exposure to coins. In order to obtain information on the amounts of metals released by their daily use, extraction experiments of coins were performed applying an artificial acidic sweat solution during varying extraction periods. After extraction, the mass of the metals released (copper, iron, nickel, and zinc) were determined by inductively coupled plasma-optical emission spectrometry (ICP-OES). The mass rate of Ni extracted per area considerably exceeded the permissible values according to the European norm: 50 times for 50-lipa coins, 80 times for 20-lipa coins, and 110 times for 1-kuna coins. This indicates that nickel-containing coins may represent a serious health hazard, especially to sensitive people. Graphical abstract        

A Symmetry Theorem on a Modified Jeu De Taquin

For their bijective proof of the hook-length formula for the number of standard tableaux of a fixed shape Novelli et al. define a modified jeu de taquin which transforms an arbitrary filling of the Ferrers diagram with 1, 2, , n(tabloid) into a standard tableau. Their definition relies on a total order of the cells in the Ferrers diagram induced by a special standard tableau, however, this definition also makes sense for the total order induced by any other standard tableau. Given two standard tableaux P, Q of the same shape we show that the number of tabloids which result in P if we perform the modified jeu de taquin with respect to the total order induced by Q is equal to the number of tabloids which result in Q if we perform the modified jeu de taquin with respect to P. This symmetry theorem extends to skew shapes and shifted skew shapes.     

Mono- and bisadducts from the addition of thianthrene cation radical salts to cycloalkenes and alkenes

Thianthrene cation radical salts, Th(*)(+) X(-)(X(-) = a, ClO(4)(-); b, PF(6)(-); c, SbF(6)(-)), add to cycloalkenes (C(5)-C(8)) in acetonitrile (MeCN) to form 1,2-bis(5-thianthreniumyl)cycloalkane salts and 1,2-(5,10-thianthreniumdiyl)cycloalkane salts, most of which have now been isolated and characterized. These are called bis- (3, 6, 9, 12) and monoadducts (4, 7, 10, 13). The proportional amount of the monoadduct obtained in the initial stage of the reaction varied with the cycloalkene in the order C(6) < C(5) < C(7) < C(8). Thus, the ratio bis:mono for C(5) and C(7) was, respectively, about 80/20 and 50/50. In contrast, only about 5% of the C(6) monoadduct (7a) and none of 7b,c was obtained, while for C(8) none of the bisadducts 12a-c was found. Bisadducts 3 and 9 lost thianthrene (Th) slowly in MeCN solution and changed into monoadducts 4 and 10. A comparable change from 6a into 7a was not observed. The monoadducts, themselves, lost a proton slowly in dry MeCN and opened into 1-(5-thianthreniumyl)cycloalkenes (5, 8, 11, 14). With 3 and 9, particularly, it was possible to follow with NMR spectroscopy the succession of changes, for example, 3 to 4 to 5. The opening of a monoadduct was made faster by adding a small amount of water to the solution. The bisadducts of 4-methylcyclohexene (15a) and 1,5-cyclooctadiene (17a) were isolated and characterized. Although a small amount of monodduct (16a) of 4-methylcyclohexene was found with NMR spectroscopy, it could not be isolated. Bis- and monoadducts were obtained also in additions of Th(*)(+) ClO(4)(-) to acyclic alkenes, in relative amounts that, again, varied with the alkene. From cis-2-butene the dominant product was the bisadduct (18), while the monoaduct (19) was characterized with NMR spectroscopy but could not be isolated. In contrast, trans-3-hexene gave mainly the monoadduct (21), while the bis adduct (20) could not be isolated. With 4-methyl-cis-2-pentene, both bis- (22) and monoadduct (23) were isolated, the former being dominant. The conversion of 18 into 19 was characterized with NMR spectroscopy. In all cycloalkene bisadducts, the configurational relationship of the two thianthrenium groups was trans, while in the monoadducts, the bonds to the single thianthrene dication were (necessarily) cis. In both bis- and monoadducts of acyclic alkenes, the configuration of the alkene was retained. The mechanisms of addition with retention of configuration, of conversion of a bis- into a monoadduct, and of opening of a monoadduct are discussed. Products were identified with a combination of NMR spectroscopy, X-ray crystallography, elemental analysis, and (for cycloalkene adducts) reaction with thiophenoxide ion.