Synthesis of substituted alkoxy benzene minilibraries, for the discovery of new insect olfaction or gustation inhibitors

We describe methods for the rapid generation of minilibraries of substituted alkoxy benzenes (consisting of 4-5 compounds), for screening as insect olfaction or gustation inhibitors. Synthetic or commercially available monoalkoxy benzene compounds were mixed and reacted with various alkyl halides to afford a first set of minilibraries. A second and third set were generated from allyloxy minilibraries via the Claisen rearrangement and subsequent alkylation of the ortho-allyl phenols. We have chosen to prepare a collection of small libraries (as opposed to one large library) to test the response insects exhibit toward blends of compounds. We demonstrate how our minilibraries can be screened, both against insect antennae and against expressed pheromone-binding proteins from the gypsy moth, Lymantria dispar.     

A reactivity change of a strontium monohydroxide by umpolung to an acid

Controlled hydrolysis of strontium amide LSrN(SiMe 3) 2(thf) (L = CH(CMe2,6- i-Pr 2C 6H 3N) 2) ( 1) gave an unprecedented example of a hydrocarbon-soluble strontium hydroxide, [LSr(thf)(mu-OH) 2Sr(thf) 2L] ( 2). In compound 2, the tetrahydrofuran (THF) molecules can easily replaced by benzophenone and triphenylphosphine oxide to yield [LSr(mu-OH)(OCPh 2)] 2 ( 3) and [LSr(mu-OH)(OPPh 3)] 2 ( 4) compounds. Among the two strontium atoms of 2, one is coordinated to a single THF molecule, while the other is coordinated to two THF molecules. Interestingly, strontium hydroxide complex 2 behaves as an acid in its reaction with Zr(NMe 2) 4 and results in a heterobimetallic oxide, [LSr(mu-O)Zr(NMe 2) 3] 2 ( 5). Compound 5 is dimeric in the solid state and contains a Sr 2Zr 2O 2 core.     

Observation of a mixed-metal transition in heterobimetallic Au/Ag dicyanide systems

Crystals of the mixed-metal heterobimetallic Au/Ag dicyanide complex, K[AuxAg1-x(CN)2] (x = 0-->1), were obtained by slow evaporation. The mixed-metal complex K[Au0.44Ag0.56(CN)2] crystallizes in a rhombohedral crystal system, space group R. The crystal structure consists of layers of linear chains of Au(CN)2- and Ag(CN)2- ions and K+ ions that connect the layers through the N atoms. The excitation and emission spectra of single crystals of K[AuxAg1-x(CN)2] were recorded at 4.2-180 K using excitation wavelengths between 230 and 260 nm. Two emission bands due to Ag-Au interactions were observed at 343 and 372 nm. Lifetime measurements indicate the shorter-wavelength emission corresponds to fluorescence and the longer-wavelength band is phosphorescence. These new emission bands are not seen in the pure K[Ag(CN)2] or pure K[Au(CN)2] crystals. Extended Hückel calculations show that the LUMO of the mixed-metal system is bonding while the HOMO is antibonding or very weakly bonding. Moreover, excited-state extended Hückel calculations indicate the formation of exciplexes with shorter metal-metal distances and higher metal-metal overlap populations than the corresponding ground-state oligomers. The luminescence is assigned to a mixed-metal transition from a molecular orbital with Au character to a molecular orbital with Ag character.     

The combination of ionic surfactants with polyelectrolytes-a new material for membranes?

The combination of two oppositely charged polyelectrolytes results in polyelectrolyte complexes. The simultaneous interfacial reaction between the different polyions leads to formation of polyelectrolyte complex membranes. Some of these have a very good performance in the membrane process pervaporation, especially for dehydration of organic liquids. The combination of a polyelectrolyte with an ionic surfactant of opposite charge results like-wise membranes but with other separation properties. The differences between the two types of membranes, formed from cellulosesulfate in combination with cationic polyelectrolytes or cationic surfactants, will be discussed.     

Simple and precise detection of lipid compounds present within liposomal formulations using a charged aerosol detector

In recent decades the use of liposomal preparations as drug delivery systems has become very attractive in pharmaceutical development. Therefore, thorough characterization and quantification of the lipids which form liposomes is wished from both investigators and regulatory authorities when the application in humans is being considered. In this study a new HPLC method for the detection of lipids in liposomal formulations was established using corona charged aerosol detection (CAD) which has the advantage to be independent of the chemical properties of the analytes. The superiority of this method over UV detection was demonstrated. Compared to UV detection no absorption effects of the organic solvent in the mobile phase interfering with the lipid signals were observed with CAD. CAD showed good linearity (R² > 0.990) for all liposomal compounds. The acceptance criteria for precision including repeatability were met. The average recovery for each of the excipients of the liposomal formulation was in the range of 90.0–110%.     

Unusual In2N4 cores in complexes containing triazole-based chalcogen-phosphoranyl ligands

The 4,5-bis(diphenylphosphoranyl)-1,2,3-triazole [4,5-(P(E)Ph2)2tz] derivatives of indium {kappa3-N,N',E-[4,5-(P(E)Ph2)2(mu-tz)]InMe2}2 (E = O2, S3, Se4) were prepared in good yield. In addition, compound 5 (E = O, E' = Se) was obtained from 4 through the replacement of a selenium atom in the P-Se(In) moiety by an oxygen atom, giving the mixed-chalcogen complex. The crystal structures of 2 and 5 exhibit a central C4In2N6O2P4core with an almost planar arrangement (mean deviation = 0.019 and 0.042 A for 2 and 0.100 A for 5), while the C4In2N6S2P4 core in 3 is nonplanar (mean deviation = 0.223 A).     

Structure elucidation of cyclic pyoverdins and examination of rearrangement reactions in MS/MS experiments by determination of exact product ion masses

Structure elucidation of naturally occurring linear and cyclic peptidic compounds can be complicated by rearrangement reactions induced upon collision activation (CA) when parts of the molecule migrate, suggesting incorrect substitution patterns. Such complex rearrangements are examined and discussed for two iron complexing compounds produced by the bacterial genus Pseudomonas (so-called pyoverdins). Various MS2- and MS3-product ion experiments were performed using a quadrupole-ion trap (QIT) at low resolution and a FT-ICR at high resolution allowing accurate mass determinations. The results of the multidimensional study confirm the proposed processes. On the basis of the series of tandem-MS experiments the structure of a new pyoverdin from a P. fluorescens strain [PVD(D47)] is deduced.     

Visualization of Real‐Time Degradation of pH‐Responsive Polyglycerol Nanogels via Atomic Force Microscopy

Polyglycerol nanogels (nPG) have a huge impact in biomedical applications as drug deliverer due to their high biocompability. For such nPG nanogels, particle degradation is widely used as drug delivery method. The knowledge of this degradation process is limited up to date. In this communication, a real time visualization of such a degradation process is presented for pH‐responsive nPG nanogels via atomic force microscopy (AFM) under ambient and in liquid conditions. The particle height plays a major role in the degradation process and decays exponentially in the beginning of this process. The particle width increases during the process indicating a “decross‐linking” step of the particles into their starting monomers. Measurements under ambient conditions confirm this assumption and provide further insight in the “decross‐linking” step of the nanogels into individual dendritic particles. The present work gives a detailed insight in the particle degradation process, which is essential for further progress for the development of new drug delivery systems.