Die Platiniodide PtI2 und Pt3I8

Platinum Iodides PtI₂ and Pt₃I₈ Powder samples of tetragonal Pt₃I₈ (a = 1166.4(1); c = 1068.2(2) pm) and the cubic α-form of PtI₂ (a = 1109 pm) were obtained by thermal decomposition of PtI₄ in closed quarz ampoules at a I₂ pressure of 2–3 bar and 8 bar, respectively, and at 320°C and 430°C and 430°C, respectively. Single crystals of the monoclinic α-Form of PtI₂ (a = 658.77(6); b = 871.50(34), c = 688.94(11) pm; β = 102.76°; Z = 4) were formed by hydrothermal synthesis from PtI₄, KI, and I₂ at 420°C. In the crystal structure of β-PtI₂ two square planar PtI₄-units are connected by a common edge to planar Pt₂I₆ groups which are linked by common corners to puckered layers. Crystals of Pt₃I₈ synthesized by hydrothermal synthesis from PtI₄, KI, and I₂ at 350°C were twinned and showed defects. As the result of X-ray studies the compound can be formulated as a mixed-valence platinum(II,IV) iodide PtI₄ · 2 PtI₂. Octahedral PtI₆ and square planar PtI₄ units are linked together to a three dimensional skeleton.     

Configuration-Odor Relationships in 5β-Ambrox

The four possible A/B cis-fused diastereoisomers of Ambrox® have been synthesized and their configurations and conformations established by X-ray and NMR analysis. Only 5β-ambrox (= 1,2,3a,4,5,5β,6,7,8,9,9a,9bα-dodecahydro-3aβ,6,6,9aβ-tetramethylnaphtho[2,1-b]furan; 5 ) has an odor quality comparable to Ambrox®. The 1,3-synperiplanar/diaxial conformation of the substituents at C(8) ( = C(3a)) and C(10) (= C(9a)) has thus been confirmed to be a compulsory structure element for the particular odor.     

Targeting apoptosis via chemical design: inhibition of bid-induced cell death by small organic molecules

Bid is a key member of the Bcl-2 family proteins involved in the control of the apoptotic cascade in cells, leading to cell death. Uncontrolled cell death is associated with several human pathologies, such as neurodegenerative diseases and ischemic injuries. Therefore, Bid represents a potential yet unexplored and challenging target for strategies aimed at the development of therapeutic agents. Here we show that a multidisciplinary NMR-based approach that we named SAR by ILOEs (structure activity relationships by interligand nuclear Overhauser effect) allowed us to rationally design a series of 4-phenylsulfanyl-phenylamine derivatives that are capable of occupying a deep hydrophobic crevice on the surface of Bid. These compounds represent the first antiapoptotic small molecules targeting a Bcl-2 protein as shown by their ability to inhibit tBid-induced SMAC release, caspase-3 activation, and cell death.     

A general mass spectrometry-based assay for the quantitation of protein-ligand binding interactions in solution

A new method that utilizes matrix-assisted laser desorption/ionization (MALDI) mass spectrometry and exploits the hydrogen/deuterium (H/D) exchange properties of proteins was developed for measuring the thermodynamic properties of protein-ligand complexes in solution. Dissociation constants (Kd values) determined by the method for five model protein-ligand complexes that included those with small molecules, nucleic acids, peptides, and other proteins were generally in good agreement with Kd values measured by conventional methods. Important experimental advantages of the described method over existing methods include: the ability to make measurements in a high-throughput and automated fashion, the ability to make measurements using only picomole quantitities of protein, and the ability to analyze either purified or unpurified protein-ligand complexes.     

Vibrational dephasing time of a molecular subgroup investigated by ultrashort coherent probing techniques

Normal vibrational modes which are broadened by a distribution of frequencies are coherently excited via transient stimulated Raman scattering. The dephasing time of a subgroup of molecules is observed using a new selective k-vector technique. In this way, one studies the homogeneous linewidth of an inhomogeneously broadened vibrational band. Results are reported on CH-stretching modes of methanol and ethylene glycol.     

Neue Phellandren-Derivate aus dem Wurzelöl von Angelica archangelicaL

New Phellandrene Derivatives from the Root Oil of Angelica archangelica L . 2-Nitro-1,5-p-menthadiene ( 5 ), trans- and cis-6-nitro-1(7), 2-p-menthadiene ( 6 and 7 ), trans-1(7), 5-p-menthadien-2-yl acetate ( 9 ) and a formal phellandrene derivative, 7-isopropyl-5-methyl-5-bicyclo [2.2.2]octen-2-one ( 16 ), have been identified in the root oil of Angelica archangelica L . Starting from (?)-(R)-α-phellandrene ( 1 ) (R)- 5 , (4R, 6S)- 6 /(4R, 6R)- 7 , (2S, 4R)- 9 and (1R, 4R, 7R)- 16 as well as (2S, 4R)- 11 , (2R, 4R)- 12 and (2R, 4R)- 10 have been prepared.     

Über Osmiumbromide

On Osmiumbromides OsBr₄ was obtained by reaction of OsCl₄ with bromine in a closed system at 330°C and 120 bar Br₂ pressure. The compound crystallizes orthorhombic (a = 633.99(18) pm; b = 1 210.92(16) pm; c = 1 461.5(10) pm; Z = 8; space group Pbca) in a TcCl₄ type structure. OsBr₆ octahedra are connected by two common edges to \documentclass{article}\pagestyle{empty}\begin{document}${}_\infty ^1 \left[ {{\rm OsBr}_{{{\rm 2} \mathord{\left/ {\vphantom {{\rm 2} 1}} \right. \kern-\nulldelimiterspace} 1}} {\rm Br}_{{{\rm 4} \mathord{\left/ {\vphantom {{\rm 4} 2}} \right. \kern-\nulldelimiterspace} 2}} } \right]$\end{document} chains with a cis arrangement of the two non-bridging Br atoms. Mixed crystals OsBr_xCl_4?x(0 < x < 2.3) with CsCl₄ type structure are formed by reactions at lower Br₂ pressure up to 12 bar. They are built up from chains consisting of edge-sharing octahedra. The terminal atoms have a trans arrangement. Attempts to synthesize single crystals of OsBr₃ by decomposition of OsBr₄ resulted in formation of three different phases OsBr_x (3 < x < 4).     

ansa-Metallocene derivatives: VIII. Syntheses and crystal structures of ethylene-bridged titanocene and zirconocene derivatives with permethylated ring ligands

Ethylene-bridged titanocene and zirconocene derivatives with permethylated ring ligands, C₂H₄(C₅(CH₃)₄)₂TiCl₂ and C₂H₄(C₅(CH₃)₄)₂ZrCl₂, have been synthesized and their crystal structures determined.     

Effect of polymer and ion concentration on mechanical and drug release behavior of gellan hydrogels using factorial design

Developing optimized hydrogel products requires an in-depth understanding of the mechanisms that drive hydrogel tunability. Here, we performed a full 4 × 4 factorial design study investigating the impact of gellan, a naturally derived polysaccharide (1%, 2%, 3%, or 4% w/v) and CaCl₂ concentration (1, 3, 7, or 10 mM) on the viscoelastic, swelling, and drug release behavior of gellan hydrogels containing a model drug, vancomycin. These concentrations were chosen to specifically provide insight into gellan hydrogel behavior for formulations utilizing polymer and salt concentrations expanding beyond those commonly reported by previous studies exploring gellan. With increasing gellan and CaCl₂ concentration, the hydrogel storage moduli (0.1–100 kPa) followed a power-law relationship and on average these hydrogels had higher liquid absorption capability and greater total drug release over 6 days. We suggest that the effects of gellan and CaCl₂ concentration and their interactions on hydrogel properties can be explained by various phenomena that lead to increased swelling and increased resistance to network expansion.     

Multiobjective Optimal Control Methods for the Navier-Stokes Equations Using Reduced Order Modeling

In a wide range of applications it is desirable to optimally control a dynamical system with respect to concurrent, potentially competing goals. This gives rise to a multiobjective optimal control problem where, instead of computing a single optimal solution, the set of optimal compromises, the so-called Pareto set, has to be approximated. When the problem under consideration is described by a partial differential equation (PDE), as is the case for fluid flow, the computational cost rapidly increases and makes its direct treatment infeasible. Reduced order modeling is a very popular method to reduce the computational cost, in particular in a multi query context such as uncertainty quantification, parameter estimation or optimization. In this article, we show how to combine reduced order modeling and multiobjective optimal control techniques in order to efficiently solve multiobjective optimal control problems constrained by PDEs. We consider a global, derivative free optimization method as well as a local, gradient-based approach for which the optimality system is derived in two different ways. The methods are compared with regard to the solution quality as well as the computational effort and they are illustrated using the example of the flow around a cylinder and a backward-facing-step channel flow.